Nickel-Catalyzed Enantioselective Pyridone C-H

Functionalizations Enabled by a Bulky

N-Heterocyclic Carbene Ligand

Johannes Diesel, Anastasiia M. Finogenova and Nicolai Cramer*

Laboratory of Asymmetric Catalysis and Synthesis, Institute of Chemical Sciences and

Engineering, Ecole Polytechnique Fédérale de Lausanne (EPFL), Lausanne, Switzerland.

*e-mail: nicolai.cramer@epfl.ch

Supplementary Information

Supplementary Information

Table of Content:

Ligand Synthesis S3
Substrate Synthesis S19
Nickel-Catalyzed Enantioselective Pyridone C-H Functionalization S30
Preparation of Transition Metal NHC complexes S55
References S59
NMR-Spectra S60

S1
General Methods
All reactions were carried out under an atmosphere of nitrogen in oven-dried glassware with
magnetic stirring, unless otherwise indicated. Toluene, dichloromethane, tetrahydrofuran,
acetonitrile and diethyl ether were purified by an Innovative Technology Solvent Delivery System.
Chemicals were used as obtained from the suppliers. Flash chromatography was performed with
Silicycle silica gel 60 (0.040-0.063 μm grade) or acidic alumina (C. Roth, Aluminium oxide 90 acidic).
Analytical thin-layer chromatography was performed with commercial glass plates coated with 0.25
mm silica gel (E. Merck, Kieselgel 60 F254). Compounds were either visualised under UV-light at
254 nm or by dipping the plates in an aqueous potassium permanganate solution followed by
heating. Proton nuclear magnetic resonance (1H-NMR) data were acquired on a Bruker AV400 (400
MHz) and a Bruker DRX600 (600 MHz). Chemical shifts (δ) are reported in parts per million (ppm)
relative to incompletely deuterated CDCl3 (s, 7.26 ppm), C6D6 (s, 7.16 ppm), CD3OD (p, 3.31 ppm).
Splitting patterns are designated as s, singlet; d, doublet; t, triplet; q, quartet; p, pentet; dd, doublet
of doublets; qd, quadruplet of dublets; m, multiplet; br, broad. Proton decoupled Carbon-13 nuclear
magnetic resonance (13C-NMR) data were acquired on a Bruker AV400 (100 MHz) and a Bruker
DRX600 (150 MHz) spectrometer. Chemical shifts are reported in ppm relative to CDCl3
(77.16 ppm), C6D6 (128.06 ppm), CD3OD (49.00 ppm). Proton decoupled Fluorine-19 nuclear
magnetic resonance (19F-NMR) were acquired at 376 MHz on a Bruker AV400 spectrometer.
Infrared (IR) data were recorded on an Alpha-P Bruker FT-IR Spectrometer. Absorbance frequencies
are reported in reciprocal centimeters (cm-1). HRMS measurements were performed by an Agilent
LC-MS TOF. High resolution mass are given in m/z. Enantiomeric excesses were measured on an
Agilent or Waters HPLC, or on a Thar SFC Investigator system using chiral stationary phase
columns. Optical rotations were measured on a Polartronic M polarimeter using a 0.5 cm cell with a
Na 589 nm filter. X-ray analysis was performed by Dr. R. Scopelliti and Dr. F. Fadaei Tirani at the
EPF Lausanne.

S2
Experimental procedures and characterization data

Ligand Synthesis

General overview of the ligand synthesis

S3
2-(1-(3,5-Dimethylphenyl)vinyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (S1):
Prepared according to a slight modification of the procedure reported by Hoveyda.[1]
In a round bottom flask NiCl2(dppp) (0.25 g, 0.46 mmol, 3 mol%) was dissolved in
THF (45 mL) and a 1.2 M solution of DIBAL (15.4 mL, 18.4 mmol, 1.2 eq) in toluene
was added dropwise at ambient temperature. The resulting dark brown solution was cooled to 0 °C
and a solution of 1-ethynyl-3,5-dimethylbenzene (2.00 g, 15.36 mmol, 1 eq) in THF (11 mL) was
added to the mixture dropwise over five minutes. The resulting solution was allowed to warm to
ambient temperature and was stirred for 2 hours. Subsequently, the mixture was cooled to 0°C and
2-methoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (7.87 mL, 46.1 mmol, 3.0 eq) was added
dropwise. The flask was equipped with a reflux condenser and the mixture was stirred at 80°C for
24h before the reaction was quenched by dropwise addition of water (40 mL) at 0 °C. Subsequently
a solution of EDTA-Na2 (40mL) was added and the aqueous layer was extracted with EtOAc (2X80
ml). The combined organic layers were dried over MgSO4, filtered and concentrated under reduced
pressure. The residue was purified by silica gel column (EtOAc:pentane, 1:40) affording 3.56 g (91%
yield) of the desired product as yellow oil.
H NMR (400 MHz, CDCl3) δ 7.07 (s, 2H), 6.90 (s, 1H), 6.03 (d, J=3.0 Hz, 1H), 6.01 (d, J=3.0 Hz,
1

1H), 2.31 (s, 6H), 1.33 (s, 12H) ppm; 13C NMR (150 MHz, CDCl3) δ 141.6, 137.6, 130.6, 128.9, 125.2,
83.9, 24.9, 21.6 ppm; IR (ATR): 2978, 2922, 2866, 1685, 1602, 1470, 1438, 1402, 1371, 1350,
1313, 1272, 1181, 1165, 1116, 968, 941, 865, 852, 837, 748, 724, 683, 676, 578, 521, 446, 402 cm-
1
; HRMS (ESI) calculated for [C16H23BO2+H]+: 259.1864, found: 259.1851; Rf: 0.40 (pentane:EtOAc
39:1)

2-(1-(3,5-Di-tert-butylphenyl)vinyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (S2):
Prepared according to a slight modification of the procedure reported by
Hoveyda.[1] In a round bottom flask NiCl2(dppp) (0.152 g, 0.280 mmol, 3 mol%) was
dissolved in THF (37 mL) and a 1.2 M solution of DIBAL (9.33 mL, 11.20 mmol, 1.2
eq) in toluene was added dropwise at ambient temperature. The resulting dark brown solution was
cooled to 0°C and a solution of 1,3-di-tert-butyl-5-ethynylbenzene (2 g, 9.33 mmol,1 eq) in THF (11
mL) was added to the mixture dropwise over five minutes. The resulting solution was allowed to
warm to ambient temperature and was stirred for 2 hours. Subsequently the mixture was cooled to
0°C and 2-methoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4.58 mL, 28.0 mmol, 3.0 eq) was
added dropwise. The flask was equipped with a reflux condenser and the mixture was stirred at 80°C
for 24h before the reaction was quenched by dropwise addition of water (35 mL) at 0 °C.
Subsequently a solution of EDTA-Na2 (35 mL) was added and the aqueous layer was extracted with
EtOAc (2X70 mL). The combined organic layers were dried over MgSO4, filtered and concentrated
under reduced pressure. The residue was purified by silica gel column (EtOAc:pentane, 1:60)
affording 2.66 g (82% yield) of the desired product as yellow oil.

S4
H NMR (600 MHz, CDCl3) δ 7.34 (m, 2H), 7.33 (m, 1H), 6.08 (d, J = 2.9 Hz, 1H), 6.01 (d, J = 2.9
1

Hz, 1H), 1.34 (s, 12H) 1.25 (s, 18H) ppm. 13C NMR (151 MHz, CDCl3) δ 150.2, 140.3, 129.7, 121.6,
121.3, 83.7, 82.8, 34.9, 31.5, 25.3, 24.9 ppm; IR (ATR): 3070, 2963, 2904, 2867, 1687, 1594,
1477, 1461, 1448, 1405, 1390, 1371, 1310, 1272, 1248, 1203, 1145, 1114, 968, 940, 899, 877, 866,
841, 746, 703, 677, 579, 478 cm-1; HRMS (ESI) calculated for [C22H35BO2+H]+ 343.2803, found
343.2802; Rf: 0.50 (pentane:EtOAc 66:1).

2,6-Bis(1-(3,5-dimethylphenyl)vinyl)-4-methylaniline (S3):
In a Schlenk tube 2,6-dibromo-4-methylaniline (0.77 g, 2.91 mmol, 1 eq),
PEPPSITM-IPr (99.0 mg, 0.145 mmol, 5 mol%) and ground KOH pellets
(0.36 g, 6.39 mmol, 2.2 eq) were dissolved in THF (48 mL). To this mixture,
a solution of boronate S1 (1.65 g, 6.39 mmol, 2.2 eq) in THF (10 mL) was added. Subsequently,the
mixture was degassed by means of freeze-pump-thaw. The suspension was stirred for 12h at 70°C.
After that another portion of KOH (0.18 g, 3.20 mmol, 1.1 eq) was added and the mixture was heated
for 8h. The reaction mixture was passed through a pad of silica washing with EtOAc and was
concentrated under reduced pressure. The residue was purified by silica gel column
(EtOAc:pentane, 1:100) affording 0.78 g (73% yield) of the desired product as white solid.

H NMR (600 MHz, CDCl3) δ 7.00 (s, 4H), 6.97 (s, 2H), 6.93 (s, 2H), 5.74 (d, J=1.4 Hz, 2H), 5.34 (d,
1

J=1.4 Hz, 2H), 2.32 (s, 3H), 2.28 (s, 12H) ppm; 13
C NMR (151 MHz, CDCl3) δ 147.7, 139.9, 138.8,
138.1, 130.9, 129.9, 128.3, 127.1, 124.5, 116.2, 21.5, 20.6 ppm; IR (ATR): 3472, 3882, 3086,
3018, 2945, 2915, 2861, 2732, 1803, 1777, 1671, 1616, 1597, 1456, 1378, 1316, 1300, 1277, 1249,
1198, 1131, 1086, 1038, 1001, 898, 871, 851, 799, 778, 733, 711, 669, 633, 591, 530, 473, 411 cm1;
HRMS (ESI) calculated for [C27H29N+H]+: 368.2372, found: 368.2378; Rf: 0.60 (pentane:EtOAc
99:1).

2,6-Bis(1-(3,5-di-tert-butylphenyl)vinyl)-4-methylaniline (S4):
In a Schlenk tube 2,6-dibromo-4-methylaniline (0.38 g, 1.43 mmol, 1
eq), PEPPSITM-IPr (50 mg, 0.07 mmol, 5 mol%) and ground KOH
pellets (0.18 g, 3.14 mmol, 2.2 eq) were dissolved in THF (20 mL). To
this mixture a solution of boronate S2 (1.08 g, 3.14 mmol), 2.2 eq) in THF (8.5 mL) was added.
Subsequently the mixture was degassed by freeze-pump-thaw. The suspension was stirred for 12h
at 70°C. After that another portion of KOH (90.0 mg, 1.57 mmol, 1.1 eq) was added and the mixture
was heated for 8h. The reaction mixture was passed through a pad of silica washing with EtOAc,
and was concentrated under reduced pressure. The residue was purified by silica gel column
(EtOAc:pentane, 1:100) affording 0.73 g (96% yield) of the desired product as white solid.

H NMR (600 MHz, CDCl3) δ 7.40 (m, 2H), 7.31 (m, 4H), 6.98 (s, 2H), 5.84 (d, J=1.3 Hz, 2H), 5.42(d,
1

J=1.3 Hz, 2H), 2.32 (s, 3H), 1.35 (s, 36H) ppm; 13
C NMR (151 MHz, CDCl3) δ 150.9, 148.2, 139.5,

S5
132.3, 130.8, 128.3, 122.7, 122.3, 121.2, 115.9, 108.9, 83.0, 35.0, 31.6, 25.4, 25.0, 20.6 ppm; IR
(ATR): 3477, 3385, 2960, 2904, 2867, 1686, 1616, 1590, 1478, 1458, 1392, 1362, 1313, 1248,
1212, 1145, 1087, 1061, 1002, 971, 897, 879, 851, 799, 777, 733, 704, 624, 542, 495 cm-1; HRMS
(ESI) calculated for [C39H53N+H]+: 536.4251, found: 536.4248; Rf: 0.65 (pentane:EtOAc 99:1).

General procedure for the asymmetric reduction of alkenyl anilines (GP1)[2b]

In a microwave tube, [Rh(nbd)2]BF4 (5 mol%) and (1R,1'R,2S,2'S)-DuanPhos (7 mol%) were

dissolved in DCM (1 ml) under a nitrogen atmosphere and stirred for 20 min. Subsequently a solution
of alkenyl aniline (1 eq) in a minimal amount of DCM was added. Subsequently MeOH (ratio
MeOH/DCM: >7/1, 0.2M) was added. The microwave tube was transferred into the autoclave and
the reactor was purged three times with H2. The reactor was pressurized to 50 bar H2 and the mixture
was stirred at ambient temperature for 48h. The reaction mixture was concentrated and purified by
silica gel column (EtOAc:pentane, 1:80).

(2,6-Bis((R)-1-(3,5-dimethylphenyl)ethyl)-4-methylaniline (S5):
Following GP1 using [Rh(nbd)2]BF4 (65.1 mg, 0.17 mmol, 5 mol%),
(1R,1'R,2S,2'S)-DuanPhos (93 mg, 0.24 mmol, 7 mol%) and alkenyl
aniline S3 (1.28 g, 3.48 mmol) gave 1.27 g (98%) of the title compound as
white foam, as a single diastereoisomer.

H NMR (600 MHz, CDCl3) δ 7.06 (s, 2H), 6.80 (s, 2H), 6.76 (s, 4H), 3.95 (q, J = 7.1 Hz, 2H), 2.39
1

(s, 3H), 2.23 (s, 12H), 1.57 (d, J = 7.1 Hz, 6H) ppm; 13
C NMR (151 MHz, CDCl3) δ 145.3, 138.3,
128.4, 126.7, 125.4, 40.4, 22.5, 21.5, 21.4 ppm; IR (ATR): 3474, 3439, 3377, 3010, 2966, 2916,
2870, 2731, 2555, 2290, 1962, 1891, 1759, 1738, 1600, 1519, 1468, 1453, 1375, 1326, 1293, 1257,
1239, 1201, 1157, 1061, 1037, 998, 944, 910, 865, 849, 774, 733, 707, 646, 612, 554, 530, 473 cm-
1
; HRMS (ESI) calculated for [C27H33N+H]+: 372.2685, found: 372.2690; Rf: 0.5 (pentane:EtOAc
99:1); [α]D20: -25° (c = 0.1, CHCl3).

2,6-Bis((R)-1-(3,5-di-tert-butylphenyl)ethyl)-4-methylaniline (S6):
Following GP1 using [Rh(nbd)2]BF4 (33.0 mg, 0.09 mmol, 5 mol%),
(1R,1'R,2S,2'S)-DuanPhos (47.0 mg, 0.12 mmol, 7 mol%) and alkenyl
aniline S4 (950 mg, 1.77 mmol, 1 eq) gave 595 mg (62%) of the title
compound as yellow oil, as a single diastereoisomer.

H NMR (400 MHz, CDCl3) δ 7.22 (t, J = 1.8 Hz, 2H), 7.02 (d, J = 1.7 Hz, 4H), 6.97 (s, 2H), 4.03 (q,
1

J = 6.7 Hz, 0H), 2.33 (s, 0H), 1.58 (d, J = 7.1 Hz, 1H), 1.24 (s, 5H) ppm 13C NMR (151 MHz, CDCl3)
δ 150.89, 126.48, 121.95, 121.87, 120.39, 120.28, 82.95, 41.00, 34.96, 31.63, 24.98, 22.22, 21.38
ppm; IR (ATR): 3475, 3435, 3371, 2962, 2904, 2868, 2292, 1762, 1686, 1624, 1597, 1519, 1470,
S6
1454, 1392, 1362, 1313, 1248, 1202, 1145, 1071, 1061, 971, 947, 910, 898, 874, 848, 804, 773,
734, 716, 647, 553, 542, 470 cm-1; HRMS (ESI) calculated for [C39H57N+H]+: 540.4564, found:
540.4559; Rf: 0.3 (pentane:DCM 4:1); [α]D20: 16.8° (c = 0.1, CHCl3).

4-(tert-Butyl)-2,6-bis((R)-1-phenylethyl)aniline (S7):
Following GP1 using [Rh(nbd)2]BF4 (27.8 mg, 0.07 mmol, 4 mol%) and
(1R,1'R,2S,2'S)-DuanPhos (42.6 mg, 0.11 mmol, 6 mol%) and 4-(tert-butyl)-
2,6-bis(1-phenylvinyl)aniline (656 mg, 1.86 mmol, 1.0 eq) gave 335 mg (51%)
of the title compound as colourless oil, as a single diastereoisomer.

H NMR (400 MHz, CDCl3) δ 7.29 (s, 2H), 7.24 (s, 2H), 7.22 (s, 2H), 7.19-7.12 (m, 6H), 4.03 (q,
1

J=7.2 Hz, 2H), 2.17 (s, 2H), 1.61 (d, J=7.1 Hz, 6H), 1.37 (s, 9H) ppm; 13C NMR (151 MHz, CDCl3) δ
145.56, 128.77, 127.65, 126.45, 122.84, 40.55, 34.60, 31.75, 22.56 ppm; IR (ATR): 3474, 3382,
3060, 3025, 2963, 2933, 2904, 2871, 2560, 2290, 1944, 1875, 1804, 1681, 1621, 1601, 1520, 1491,
1478, 1450, 1392, 1362, 1294, 1269, 1254, 1202, 1184, 1078, 1061, 1029, 991, 910, 882, 761, 731,
700, 608, 577, 522, 420 cm-1; HRMS (ESI) calculated for [C26H31N+H]+: 358.2529, found: 358.2523;
Rf: 0.3 (pentane:DCM 5:1); [α]D20: 7.8° (c = 0.1, CH2Cl2).

S7
Synthesis of bisketimines S8-S13

(1E,2E)-N1,N2-Bis(2,6-bis((R)-1-(3,5-dimethylphenyl)ethyl)-4-methylphenyl)ethane-1,2-diimine
(S8):
Aniline S5 (400 mg, 1.10 mmol, 1.0 eq) was suspended in EtOH (1 ml) and
a 40% solution of glyoxal (68.6 µl, 0.54 mmol, 0.5 eq) in water, and one
drop of formic acid (4.13 µl, 0.108 mmol) were added. The mixture was
sonicated for 5h. The crude mixture was concentrated and subsequently
recrystallized from EtOH to obtain the desired bisimine as brown solid (291 mg, 0.38 mmol, 35%
yield).

H NMR (600 MHz, CDCl3) δ 7.80 (s, 2H), 6.95 (s, 4H), 6.84-6.77 (m, 12H), 4.02 (q, J=7.1 Hz, 4H),
1

2.31 (s, 6H), 2.25 (s, 24H), 1.50 (d, J=7.1 Hz, 12H) ppm; 13
C NMR (151 MHz, CDCl3) δ 164.10,
146.33, 146.11, 137.95, 137.81, 134.37, 133.97, 127.89, 126.28, 125.57, 125.53, 39.65, 38.96,
22.42, 21.56, 21.48 ppm; IR (ATR): 3013, 2966, 2918, 2871, 2730, 2288, 2245, 1713, 1601, 1451,
1373, 1324, 1291, 1259, 1236, 1200, 1167, 1132, 1091, 1079, 1037, 999, 943, 910, 863, 847, 732,
706, 647, 519, 387 cm-1; HRMS (ESI) calculated for [C56H64N2+H]+: 765.5143, found: 372.2690
(aniline S5, bisimine not stable under ESI ); [α]D20: 159.6° (c = 0.1, CHCl3).

General procedure 2 (GP2)

In a two-necked flask, diketone (1.0 eq) and ZnCl2 (2.7 eq) were suspended in acetic acid (0.25 M)
and heated at 60 °C for 5 minutes. After that the chiral aniline (2.1 eq) was added and the mixture
was refluxed for 2 h. Subsequently the mixture was concentrated and taken up in DCM and treated
with a aqueous solution of sodium oxalate (1.25 eq) in a separating funnel. Upon washing a white
precipitate was formed in the aqueous layer. The DCM layer was separated and washed with brine,
dried over MgSO4, filtered and evaporated to provide the crude bisimine as brown solid. The crude
product was purified by silica gel column (EtOAc:pentane, 1:25, 0.1% NEt3) affording the title
compound.

(2E,3E)-N2,N3-Bis(4-methyl-2,6-bis((R)-1-phenylethyl)phenyl)butane-2,3-diimine (S9):
Following GP2 using diacetyl (0.07 µl, 0.76 mmol, 1.0 eq), ZnCl2 (279 mg,
2.05 mmol, 2.7 eq) and 4-methyl-2,6-bis((S)-1-phenylethyl)aniline2a (503 mg,
1.60 mmol, 2.1 eq) affording 225 mg (43%) of the title compound as brown
oil.
H NMR (600 MHz, CDCl3) δ 7.20 (m, 9H), 7.16-7.09 (m, 11H), 7.05 (s, 2H), 6.94 (s, 2H), 3.86 (q,
1

J=7.0 Hz, 2H), 3.81 (q, J=7.0 Hz, 2H), 2.33 (s, 6H), 1.59 (d, J=7.0 Hz, 6H), 1.49 (s, 6H), 1.47 (d,
J=7.0 Hz, 6H) ppm; 13C NMR (151 MHz, CDCl3) δ 168.73, 146.27, 144.85, 133.13, 132.44, 131.83,
128.49, 128.29, 127.92, 127.41, 126.10, 125.94, 125.86, 40.23, 39.25, 22.04, 21.42, 16.34 ppm; IR
S8
(ATR): 3082, 3059, 3024, 2966, 2931, 2872, 2288, 2265, 2247, 1945, 1872, 1803, 1751, 1702,
1644, 1601, 1493, 1447, 1423, 1371, 1360, 1321, 1246, 1207, 1138, 1120, 1079, 1030, 1010, 909,
864, 812, 760, 733, 698, 650, 576, 553, 528 cm-1; HRMS (ESI) calculated for [C50H52N2+H]+ :
681.4203, found: 681.4211; Rf: 0.45 (EtOAc:pentane, 1:25, 0.1% NEt3); [α]D20: 12.0° (c = 0.1,
CHCl3).

((1E,2E)-N1,N2-Bis(4-methyl-2,6-bis((R)-1-phenylethyl)phenyl)acenaphthylene-1,2-diimine (S10):
Following GP2 using acenaphthoquinone (138 mg, 0.76 mmol, 1.0 eq), ZnCl2
(278 mg, 2.04 mmol, 2.7 eq) and 4-methyl-2,6-bis((S)-1-phenylethyl)aniline1
(500 mg, 1.59 mmol, 2.1 eq) affording 412 mg (70%) of the title compound
as orange solid.

H NMR (400 MHz, CDCl3) δ 7.61 (d, J=8.1 Hz, 2H), 7.41 (d, J=7.6 Hz, 4H), 7.32-7.03 (m, 10H),
1

6.96 (s, 2H), 6.90 (d, J=7.5 Hz, 4H), 6.50 (t, J=7.5 Hz, 4H), 6.34 (t, J=7.5 Hz, 2H), 6.26 (d, J=7.6 Hz,
2H), 4.42 (q, J=7.2 Hz, 2H), 4.30 (q, J=7.2 Hz, 2H), 2.41 (s, 6H), 1.54 (d, J=7.2 Hz, 6H), 1.38 (d,
J=7.2 Hz, 6H) ppm; 13C NMR (151 MHz, CDCl3) δ 163.17, 146.16, 145.98, 145.86, 140.10, 133.43,
133.31, 133.28, 128.99, 128.26, 127.87, 127.82, 127.64, 127.47, 126.97, 126.90, 125.89, 125.03,
123.58, 40.95, 38.20, 22.62, 21.72, 21.23 ppm; IR (ATR): 3082, 3059, 3025, 2965, 2929, 2872,
2246, 2211, 1943, 1881, 1804, 1733, 1661, 1638, 1598, 1493, 1446, 1373, 1276, 1230, 1207, 1155,
1094, 1043, 1030, 1012, 907, 864, 830, 780, 758, 729, 698, 645, 575, 525 cm-1;HRMS
(ESI) calculated for [C58H52N2+H]+ : 777.4203, found: 777.4195; Rf: 0.25 (EtOAc:pentane, 1:25, 0.1%
NEt3); [α]D20: 25.2° (c = 0.1, CHCl3).

(1E,2E)-N1,N2-Bis(2,6-bis((R)-1-(3,5-dimethylphenyl)ethyl)-4-methylphenyl)acenaphthylene-1,2-
diimine (S11):
Following GP2 using acenaphthoquinone (297 mg, 1.63 mmol, 1.0 eq), ZnCl2
(610 mg, 4.48 mmol, 2.7 eq) and aniline S5 (1.24 g, 3.34 mmol, 2.05 eq)
affording 785 mg (54%) of the title compound as orange solid and 330 mg
(38%) of the coresponding monoimine which was reisolated and resubmitted
to these reaction conditions.

H NMR (400 MHz, CDCl3) δ 7.62 (d, J=8.2 Hz, 2H), 7.25 (s, 2H), 7.10 (s, 6H), 7.03 (m, 2H), 6.78
1

(m, 2H), 6.45 (s, 4H), 6.32 (d, J=7.2 Hz, 2H), 5.92 (s, 2H), 4.40 (q, J=7.2 Hz, 2H), 4.16 (q, J=7.2 Hz,
2H), 2.47 (s, 6H), 2.25 (s, 12H), 1.53 (s, 12H), 1.51 (d, J=7.2 Hz, 6H), 1.46 (d, J=7.2 Hz, 6H) ppm;
13
C NMR (151 MHz, CDCl3) δ 162.30, 146.31, 145.79, 145.50, 140.18, 137.64, 137.14, 133.15,
133.03, 132.95, 129.99, 129.47, 128.00, 127.75, 126.91, 126.68, 126.29, 125.80, 125.70, 125.39,
123.05, 40.69, 38.19, 22.92, 22.14, 21.87, 21.56, 20.76 ppm; IR (ATR): 3013, 2965, 2917, 2870,
2730, 2291, 2245, 2215, 1732, 1665, 1599, 1445, 1374, 1359, 1322, 1273, 1230, 1206, 1155, 1092,
1039, 999, 908, 862, 846, 829, 800, 779, 730, 702, 647, 605, 556, 522, 447 cm -1; HRMS (ESI)

S9
calculated for [C66H68N2+H]+: 889.5456, found: 889.5465; Rf: 0.5 (pentane:EtOAc 49:1); [α]D20:
116.0° (c = 0.1, CHCl3).

(1E,2E)-N1,N2-Bis(4-(tert-butyl)-2,6-bis((R)-1-phenylethyl)phenyl)acenaphthylene-1,2-diimine
(S12):
Following GP2 using acenaphthoquinone (81 mg, 0.44 mmol, 1.0 eq) and
ZnCl2 (163 mg, 1.20 mmol, 2.7 eq) and aniline S7 (325 mg, 0.91 mmol,
2.05 eq) affording 229 mg (60%) of the title compound as brown oil.

(Spectra contaminated with 0.25 eq. of aniline S7, separation after next
step) 1H NMR (600 MHz, CDCl3) δ 7.58 (d, J=8.2 Hz, 2H), 7.44 (d, J=1.6 Hz, 2H), 7.39 (d, J=7.6 Hz,
4H), 7.17-7.13 (m, 6H), 7.11 (t, J=7.3 Hz, 2H), 7.02 (t, J=7.5 Hz, 2H), 6.89 (d, J=7.5 Hz, 4H), 6.49
(t, J=7.5 Hz, 4H), 6.33 (t, J=7.3 Hz, 2H), 6.12 (d, J=7.2 Hz, 2H), 4.44 (q, J=7.2 Hz, 2H), 4.29 (q,
13
J=7.2 Hz, 2H), 1.56 (d, J=7.2 Hz, 6H), 1.42 (d, J=7.2 Hz, 6H), 1.38 (s, 18H) ppm; C NMR (151
MHz, CDCl3) δ 163.06, 146.70, 146.39, 146.12, 145.93, 145.82, 140.10, 132.55, 132.51, 128.83,
128.21, 127.85, 127.77, 127.61, 127.54, 126.91, 126.45, 125.81, 124.95, 123.41, 123.04, 122.57,
121.93, 41.25, 38.49, 34.81, 34.56, 31.83, 22.72, 22.52, 21.46 ppm; IR (ATR): 3060, 3026, 2963,
2932, 2905, 2872, 2286, 1959, 1941, 1873, 1736, 1664, 1633, 1600, 1492, 1477, 1449, 1373, 1362,
1189, 1029, 907, 881, 830, 780, 758, 731, 699, 577, 526, 431, 397 cm-1; HRMS (ESI) calculated for
[C64H64N2+H]+ : 861.5142, found: 861.5146; Rf: 0.3 (EtOAc:pentane, 1:25, 0.1% NEt3); [α]D20: 92.2°
(c = 0.1, CHCl3).

(1E,2E)-N1,N2-Bis(2,6-bis((R)-1-(3,5-di-tert-butylphenyl)ethyl)-4-methylphenyl)acenaphthylene-
1,2-diimine (S13)
In a thick-walled reaction vessel acenaphthoqoluinone (89.0 mg,
0.49 mmol), p-TsOH (18.7 mg, 0.10 mmol, 20 mol%) and aniline S6
(525 mg, 0.972 mmol) were dissolved in toluene (6.5 ml) and the
mixture was heated to 130°C for 72h. The reaction progress was
monitored by LC-MS. The reaction mixture was concentrated and
used as crude directly in the next step.

S10
Synthesis of imidazolium salts S14-S20

1,3-Bis(4-methyl-2,6-bis((R)-1-phenylethyl)phenyl)-1H-imidazol-3-ium chloride (S14):

Imidazolium salt S14 was synthesized according to literature.[2]

1,3-Bis(2,6-bis((R)-1-(3,5-dimethylphenyl)ethyl)-4-methylphenyl)-1H-imidazol-3-ium chloride (S15):

In a 100mL two-necked, roundbottom flask bisimine S8 (291 mg, 0.38 mmol,
1.0 eq) was dissolved in THF (12.7 ml) and the solution was heated to 70°C.
To this solution ZnCl2 (54.4 mg, 0.40 mmol, 1.05), a 4M solution of HCl in 1,4-
dioxane (0.12 ml, 0.48 mmol, 1.25 eq) and paraformaldehyde (12.6 mg, 0.42
mmol, 1.1 eq) were added successively and rapidly. The mixture was stirred at 70°C overnight. The
mixture was concentrated and the resulting residue was dissolved in DCM (50mL) and washed with
2M HCl (2x50mL) and brine of pH=8 (1x50ml). The organic solution was dried over MgSO4 and
concentrated. The reaction mixture was concentrated and purified by silica gel column (DCM to
DCM:Methanol, 9:1) to yield 83 mg (27%) of the title compound.

H NMR (600 MHz, CDCl3) δ 11.89 ( s, 1H), 7.16 (s, 2H), 6.98 (s, 4H), 6.92 (s, 2H), 6.85 (s, 2H),
1

6.74 (s, 2H), 6.67 (s, 2H), 6.33 (s, 4H), 3.65 (q, J=7.1 Hz, 4H), 2.36 (s, 6H), 2.31 (s, 12H), 2.16 (s,
12H), 1.57 (d, J=7.1 Hz, 6H), 1.44 (d, J=7.1 Hz, 6H) ppm; 13
C NMR (151 MHz, CDCl3) δ 145.46,
143.78, 142.87, 142.00, 141.72, 138.59, 138.04, 128.97, 128.67, 128.38, 128.27, 127.68, 125.57,
124.97, 124.51, 40.01, 38.64, 22.79, 22.22, 21.99, 21.57, 21.48 ppm; IR (ATR): 3010, 2969, 2917,
2872, 2768, 2734, 2171, 1735, 1602, 1531, 1461, 1378, 1318, 1284, 1272, 1258, 1218, 1154, 1078,
1064, 1037, 999, 958, 925, 910, 849, 772, 726, 687, 638, 531 cm-1; HRMS (ESI) calculated for
[C57H65N2]+: 777.5142, found: 777.5143; Rf: 0.30 (DCM:MeOH 9:1); [α]D20: 118.1° (c = 0.1, CHCl3).
m.p.: 257-261 °C.

4,5-Dimethyl-1,3-bis(4-methyl-2,6-bis((R)-1-phenylethyl)phenyl)-1H-imidazol-3-ium iodide (S16):

In a 250mL three-necked, roundbottom flask bisimine S9 (391 mg,
0.57 mmol, 1.0 eq) was dissolved in THF (19.1 mL) and the solution was
heated to 70 °C. To this solution ZnCl2 (82.0 mg, 0.60 mmol, 1.05 eq) was
added and the mixture was stirred for 5 minutes. A 4 M solution of HCl (0.18
mL, 0.72 mmol, 1.25 eq) and paraformaldehyde (18.96 mg, 0.632 mmol, 1.1 eq) were added
succesively and rapidly and stirred over night at 70 °C. The mixture was cooled to ambient
temperature and concentrated and the resultant residue was then dissolved in DCM (50mL) and
washed with 2M HCl (3x50mL) and brine (1x50mL) and brine of pH=8 (1x50ml), with 2 times back-

S11
extracting with DCM each time. The organic solution was dried over MgSO4 and concentrated. The
black crude oil was suspended in 10ml water and a solution of sodium iodide (500 mg, 3.34 mmol,
5.8 eq) in 12 ml acetone was added. The mixture was stirred for 4h at rt (sonicator to achieve
homogenous suspension). The black mixture was extracted with DCM and dried over MgSO 4. To
the DCM solution Hexane was added and the mixture was concentrated to give a thick black oil,
which was washed with diethylether over a frit to yield 106 mg (23%) of the title compound as a grey
powder.

H NMR (400 MHz, CDCl3) δ 10.36 (s, 1H), 7.46-7.39 (m, 4H), 7.37-7.28 (m, 7H), 7.17-7.05 (m, 9H),
1

6.64 (d, J=6.7 Hz, 4H), 3.67 (q, J=7.0 Hz, 2H), 3.31 (q, J=6.3 Hz, 2H), 2.45 (s, 6H), 1.72 (d, J=7.0
Hz, 6H), 1.26 (d, J=6.3 Hz, 6H), 1.16 (s, 6H) ppm; C NMR (101 MHz, CDCl3) δ 144.89, 143.18,
13

142.74, 142.58, 141.70, 129.59, 129.29, 128.57, 128.23, 128.17, 127.62, 127.56, 127.47, 127.05,
126.73, 40.42, 37.99, 23.28, 22.16, 21.05, 7.98 ppm; IR (ATR): 2984, 2912, 2843, 2725, 2191,
1785, 1632, 1532, 1441, 1365, 1274, 1265, 1259, 1222, 1164, 1092, 1064, 1034, 987, 918, 911,
865, 786, 734, 612, 609 cm-1; HRMS (ESI) calculated for [C51H53N2]+ 693.4203, found: 693.4212;
[α]D20: 78.3° (c = 0.1 CHCl3); m.p.: 232-233 °C.

General procedure for the acenaphthoquinone imidazolium salt formation (GP3)

In a flame dried Schlenk tube an excess of (chloromethoxy)ethane (30 eq) (neutralized over K2CO3)
was added to to the bisketimine (1eq) and the mixture was heated to 80 °C and stirred over night.
The crude reaction mixture was concentrated and purified by column chromatography (DCM,
DCM/MeOH 10%MeOH). The obtained crude oil was washed with ether over a frit to yied the desired
the desired acenaphthoquinone imidazolium salt.

7,9-Bis(4-methyl-2,6-bis((R)-1-phenylethyl)phenyl)-7H-acenaphtho[1,2-d]imidazol-9-ium chloride
(S17):
Following GP3 using (chloromethoxy)ethane (3.88 ml, 41.8 mmol, 30 eq)
and bisketimine S10 (1.08 g, 1.39 mmol, 1 eq) to give 649 mg (57%) of the
title compound as yellow solid.
1
H NMR (600 MHz, CDCl3) δ 11.80 (s, 1H), 7.77 (d, J=8.2 Hz, 2H), 7.44 (d,
J=7.6 Hz, 4H), 7.39 (t, J=7.4 Hz, 4H), 7.34 (s, 2H), 7.28 (t, J=7.5 Hz, 2H),
7.19 (t, J=7.2 Hz, 2H), 7.03 (s, 2H), 6.74 (d, J=7.0 Hz, 2H), 6.58 (d, J=4.2 Hz, 8H), 6.52-6.48 (m,
2H), 4.08 (q, J=6.9 Hz, 2H), 3.82 (q, J=6.8 Hz, 2H), 2.44 (s, 6H), 1.52 (d, J=7.0 Hz, 6H), 1.40 (d,
J=6.9 Hz, 6H) ppm; 13C NMR (151 MHz, CDCl3) δ 144.77, 143.44, 142.76, 142.41, 142.27, 137.68,
130.05, 129.57, 129.26, 129.09, 128.33, 128.04, 127.87, 127.73, 127.36, 127.14, 126.89, 125.97,
123.10, 122.69, 40.69, 38.59, 22.85, 22.12, 21.31 ppm; IR (ATR): 3058, 3026, 2971, 2932, 2904,
2875, 2796, 2731, 2684, 2465, 2456, 1712, 1602, 1515, 1494, 1446, 1418, 1377, 1329, 1221, 1186,
1156, 1139, 1064, 1030, 1013, 911, 891, 865, 823, 751, 700, 657, 572, 554, 530, 450, 409 cm -1;
S12
HRMS (ESI) calculated for [C59H53N2]+: 789.4203, found: 789.4208 Rf: 0.40 (DCM:MeOH 9:1); [α]D20:
-38.5° (c = 0.1 CHCl3); m.p.: 211-212 °C.

7,9-Bis(2,6-bis((R)-1-(3,5-dimethylphenyl)ethyl)-4-methylphenyl)-7H-acenaphtho[1,2-d]imidazol-9-
ium chloride (S18):
Following GP3 using (chloromethoxy)ethane (2.50 ml, 26.9 mmol, 31 eq)
and bisketimine S11 (780 mg, 0.88 mmol, 1 eq) to give 800 mg (97%) of
the title compound as brown solid. The crude product was obtained in high
purity and was converted in one pot to the free carbene without further
purification.
H NMR (600 MHz, CDCl3) δ 10.85 (s, 1H), 7.82 (d, J=8.2 Hz, 2H), 7.42 (s, 2H), 7.27 (d, J=7.3 Hz,
1

2H), 7.14 (s, 2H), 6.98 (s, 4H), 6.83 (s, 2H), 6.62 (d, J=7.0 Hz, 2H), 6.14 (s, 4H), 5.99 (s, 2H), 4.09
(q, J=7.0 Hz, 2H), 3.61 (q, J=7.0 Hz, 2H), 2.52 (s, 6H), 2.30 (s, 12H), 1.57 (d, J=7.1 Hz, 6H), 1.54
(s, 12H), 1.43 (d, J=7.0 Hz, 6H) ppm; 13C NMR (151 MHz, CDCl3) δ 144.44, 143.38, 142.75, 142.55,
142.27, 138.72, 137.95, 137.53, 130.09, 129.59, 128.81, 128.37, 128.14, 127.75, 127.32, 126.96,
125.38, 125.02, 122.59, 122.41, 41.07, 38.60, 22.50, 22.25, 22.15, 21.64, 20.67 ppm; IR (ATR):
3010, 2971, 2916, 2873, 2794, 2731, 2675, 2176, 2167, 1830, 1730, 1680, 1602, 1517, 1452, 1419,
1377, 1330, 1226, 1185, 1139, 1037, 998, 925, 910, 863, 847, 822, 769, 729, 707, 678, 638, 555,
535 cm-1; HRMS (ESI) calculated for [C67H69N2]+: 901.5455, found: 901.5452; Rf: 0.50 (DCM:MeOH
9:1); [α]D20: -39.1° (c = 0.1, CHCl3). m.p.: 178-180 °C.

7,9-Bis(2,6-bis((R)-1-(3,5-di-tert-butylphenyl)ethyl)-4-methylphenyl)-7H-acenaphtho[1,2-d]imidazol-
9-ium chloride (S19):
Following GP3 using (chloromethoxy)ethane (1.0 ml, 10.78 mmol,
68 eq) and bisketimine S13 (278 mg, 0.16 mmol, 1 eq) to give
101 mg (45%) of the title compound as brown solid.
H NMR (600 MHz, CDCl3) δ 8.78 (s, 1H), 7.92 (d, J=8.3 Hz, 2H),
1

7.42 (s, 2H), 7.31 (t, J=8.4 Hz, 2H), 7.28 (s, 2H), 7.23 (s, 2H), 6.87
(s, 4H), 6.85 (s, 2H), 6.69 (d, J=7.0 Hz, 2H), 6.42 (d, J=1.3 Hz, 4H),
4.03 (q, J=7.0 Hz, 2H), 3.20 (q, J=7.0 Hz, 2H), 2.51 (s, 6H), 1.61
13
(d, J=7.0 Hz, 6H), 1.17 (s, 36H), 1.12 (d, J=7.0 Hz, 6H), 0.86 (s, 36H) ppm; C NMR (151 MHz,
CDCl3) δ 151.29, 150.99, 143.05, 142.82, 142.54, 142.50, 142.26, 138.24, 138.02, 130.73, 130.13,
129.96, 128.67, 128.21, 127.74, 127.51, 123.08, 121.83, 121.15, 120.74, 41.27, 38.90, 34.98, 34.43,
31.56, 31.14, 23.26, 22.34, 22.14 ppm; IR (ATR): 3058, 2962, 2904, 2867, 2673, 2242, 2184,
2176, 1732, 1596, 1519, 1476, 1451, 1393, 1362, 1334, 1247, 1202, 1141, 1037, 922, 909, 872,
821, 768, 728, 639, 556, 543, 515, 418, 405 cm-1; HRMS (ESI) calculated for [C97H117N2]+:
1237.9211, found: 1237.9221; Rf: 0.70 (DCM:MeOH 9:1); [α]D20: -16.3° (c = 0.1, CHCl3); m.p.: 168-
170 °C.

S13
7,9-Bis(4-(tert-butyl)-2,6-bis((R)-1-phenylethyl)phenyl)-7H-acenaphtho[1,2-d]imidazol-9-ium
chloride (S20):
Following GP3 using (chloromethoxy)ethane (0.71 ml, 7.66 mmol, 30 eq)
and bisketimine S12 (220 mg, 0.26 mmol, 1 eq) to give 65 mg (28%) of
the title compound as brown solid.
1
H NMR (600 MHz, CDCl3) δ 11.20 (s, 1H), 7.63 (d, J=8.2 Hz, 2H), 7.46
(s, 2H), 7.30-7.20 (m, 6H), 7.08-7.03 (m, 6H), 7.01 (t, J=7.3 Hz, 2H),
6.49 (d, J=7.0 Hz, 2H), 6.44-6.37 (m, 8H), 6.35 (m, 2H), 4.01 (q, J=6.9 Hz, 2H), 3.64 (q, J=6.8 Hz,
2H) 1.41 (d, J=7.0 Hz, 6H), 1.28 (d, J=7.0 Hz, 6H), 1.23 (s, 18H) ppm; 13C NMR (151 MHz, CDCl3)
δ 155.16, 144.84, 142.94, 142.84, 141.74, 137.73, 129.95, 129.54, 129.27, 128.60, 128.06, 127.79,
127.37, 127.03, 126.91, 125.98, 124.61, 123.97, 122.98, 122.60, 40.92, 38.90, 35.49, 31.40, 23.05,
21.55 ppm; IR (ATR): 3060, 3027, 2967, 2933, 2905, 2874, 2688, 2468, 1601, 1516, 1494, 1477,
1447, 1418, 1377, 1365, 1339, 1278, 1234, 1204, 1076, 1061, 1029, 1005, 996, 908, 884, 822, 751,
700, 658, 573, 531, 512, 417 cm-1; HRMS (ESI) calculated for [C65H65N2]+: 873.5142, found:
873.5147; Rf: 0.40 (DCM:MeOH 9:1); [α]D20: 156.0° (c = 0.1, CHCl3); m.p.: 283-284 °C.

S14
General procedure for the preparation of the N-heterocyclic carbenes L9-L16 (GP4)
Inside a glove box KH (3 eq), KOtBu (10 mol%) and the imidazolium salt (1 eq) were combined in a
Schlenk tube. The mixture was dissolved in THF and Toluene (1/1, 0.05 M). The Schlenk tube was
sealed and taken out of the glove box and the suspension was sonicated for the indicated amount
of time. Subsequently the mixture was concentrated using a Schlenk line and the crude mixture was
taken up in toluene (3-4 ml) inside the glove box and was filtered through celite, washing with toluene
(2x0.5 mL). The mixture was concentrated and dried under high vaccum giving the pure
imidazol-2-ylidenes, which were characterized by 1H- and 13C-NMR.

1,3-Bis(4-methyl-2,6-bis((R)-1-phenylethyl)phenyl)-1H-imidazol-3-ium-2-ide (L9):
Following GP4 using KH (34.3 mg, 0.86 mmol, 3 eq), KOtBu (3.2 mg, 0.029
mmol, 10 mol%) and imidazolium salt S14 (200 mg, 0.29 mmol, 1 eq). The
reaction mixture was sonicated for 2h. The title compound was obtained as
a pale yellow solid, 189 mg (99%). This carbene was crystallised by slow
evaporation from toluene and its absolute configuration was assigned by X-ray crystallography as
(R;R;R;R).

H NMR (400 MHz, C6D6) δ 7.84 (d, J=7.8 Hz, 4H), 7.34-7.27 (m, 9H), 7.21-7.07 (m, 11H), 6.55 (s,
1

2H), 4.66 (q, J=7.2 Hz, 2H), 4.55 (q, J=7.1 Hz, 2H), 2.10 (s, 6H), 1.70 (d, J=7.2 Hz, 6H), 1.57 (d,
J=7.2 Hz, 6H) ppm; 13
C NMR (101 MHz, C6D6) δ 220.40, 147.21, 145.83, 143.38, 138.63, 136.99,
128.64, 128.44, 128.36, 127.94, 127.46, 126.63, 126.39, 126.07, 122.47, 39.96, 38.01, 22.87, 21.43,
21.37 ppm.

S15
4,5-Dichloro-1,3-bis(4-methyl-2,6-bis((R)-1-phenylethyl)phenyl)-1H-imidazol-3-ium-2-ide (L10):
Inside a glove box carbene L9 (50.0 mg, 0.08 mmol, 1.0 eq) was dissolved
in THF (1.0 ml) in a Schlenk tube. To this mixture a solution of CCl4 (15 µL,
0.16, 2.05 eq) in THF (0.2 mL) was added and the reaction mixture was
stirred for 30min at ambient temperature. Subsequently all volatiles were
removed under reduced pressure and the title compound was obtained as pink solid, 55.0 mg (99%).
H NMR (400 MHz, C6D6) δ 7.64 (d, J=8Hz, 4H), 7.18-7.06 (m, 12H), 7.04-6.96 (m, 6H), 6.94 (m,
1

13
2H), 4.49-4.38 (m, 4H), 1.89 (s, 6H), 1.67 (d, J=7.2 Hz, 6H), 1.42 (d, J=6.9 Hz, 6H) ppm; C NMR
(101 MHz, C6D6) δ 221.42, 146.19, 145.43, 144.59, 139.96, 133.65, 128.68, 128.62, 128.50, 128.17,
127.94, 127.67, 127.47, 127.17, 126.44, 118.17, 67.83, 40.14, 38.05, 25.83, 22.80, 21.37,20.46
ppm;

4,5-Dimethyl-1,3-bis(4-methyl-2,6-bis((R)-1-phenylethyl)phenyl)-1H-imidazol-3-ium-2-ide (L11):
Following GP4 using KH (26.0 mg, 0.86 mmol, 5 eq), KOtBu (1.5 mg, 0.01
mmol, 10 mol%) and imidazolium salt S16 (106 mg, 0.13 mmol, 1.0 eq). The
reaction mixture was sonicated for 2h. The title compound was obtained as
dark green solid, 89 mg (99%).
H NMR (400 MHz, C6D6) δ 7.83 (d, J = 7.7 Hz, 4H), 7.13 (d, J = 7.2 Hz, 6H), 7.02 (h, J = 8.3, 7.4
1

Hz, 14H), 4.56 – 4.44 (m, 4H), 2.02 (s, 6H), 1.65 (d, J = 7.2 Hz, 6H), 1.40 (d, J = 7.2 Hz, 6H), 1.33
(s, 6H) ppm; 13C NMR (101 MHz, C6D6) δ 217.29, 146.35, 145.71, 145.51, 143.60, 138.10, 135.51,
128.98, 128.21, 126.97, 126.36, 125.93, 125.70, 125.35, 125.21, 39.68, 37.04, 23.06, 21.16,
20.03, 8.77 ppm.

1,3-Bis(2,6-bis((R)-1-(3,5-dimethylphenyl)ethyl)-4-methylphenyl)-1H-imidazol-3-ium-2-ide (L12):
Following GP4 using KH (9.17 mg, 0.33 mmol, 3 eq), KOtBu (0.90 mg, 0.01
mmol, 10 mol%) and imidazolium salt S15 (62.0mg, 0.08 mmol, 1.0 eq). The
reaction mixture was sonicated for 2h. The title compound was obtained as
yellow solid, 58 mg (98%)
H NMR (400 MHz, C6D6) δ 7.42 (s, 4H), 7.15-7.00 (m, 6H), 6.80 (s, 2H), 6.72-6.68 (m, 4H), 6.65 (s,
1

2H), 4.69 (q, J=7.1 Hz, 2H), 4.50 (q, J=7.1 Hz, 2H), 2.14 (s, 12H), 2.05 (s, 12H), 2.00 (s, 6H), 1.63
(d, J=7.2 Hz, 6H), 1.60 (d, J=7.2 Hz, 6H) ppm; 13C NMR (151 MHz, C6D6) δ 221.07, 147.08, 146.20,
145.74, 143.73, 138.53, 137.84, 137.60, 137.09, 129.33, 128.57, 126.34, 126.01, 125.70, 122.55,
39.94, 38.02, 23.18, 21.98, 21.51, 21.49, 21.45 ppm.

S16
7,9-Bis(4-methyl-2,6-bis((R)-1-phenylethyl)phenyl)-7H-acenaphtho[1,2-d]imidazol-9-ium-8-ide
(L13):
Following GP4 using KH (60.7 mg, 1.51 mmol, 5 eq), KOtBu (3.2 mg, 0.03
mmol, 10 mol%) and imidazolium salt S17 (250 mg, 0.30 mmol, 1.0 eq). The
reaction mixture was sonicated for 12 h. The title compound was obtained
as black solid, 248 mg (98 %).
1
H NMR (400 MHz, C6D6) δ 7.73 (d, J=7.7 Hz, 4H), 7.28 (d, J=8.2 Hz, 2H),
7.20-7.10 (m, 8H), 7.09-6.96 (m, 6H), 6.91 (t, J=7.2 Hz, 2H), 6.78-6.71 (m, 6H), 6.69-6.63 (m, 2H),
4.87 (q, J=7.0 Hz, 2H), 4.78 (q, J=7.0 Hz, 2H), 2.01 (s, 6H), 1.55 (dd, J=6.6 Hz, 12H) ppm; 13C NMR
(101 MHz, C6D6) δ 231.48, 145.93, 145.81, 145.74, 144.42, 141.03, 139.14, 137.89, 135.51, 131.41,
129.83, 129.33, 128.57, 128.18, 127.19, 126.90, 126.37, 125.89, 125.70, 120.66, 40.43, 38.24,
22.80, 21.52, 21.45, 21.02 ppm.

7,9-Bis(4-(tert-butyl)-2,6-bis((R)-1-phenylethyl)phenyl)-7H-acenaphtho[1,2-d]imidazol-9-ium-8-ide
(L14):
Following GP4 using KH (11.0 mg, .28 mmol, 5 eq), KOtBu (0.62 mg,
5.50 µmol, 10 mol%) and imidazolium salt S20 (50.0mg, 0.06 mmol, 1.0
eq). The reaction mixture was sonicated for 12h. The title compound was
obtained as black solid, 48 mg (99 %).

H NMR (400 MHz, C6D6) δ 7.75 (d, J=7.6 Hz, 4H), 7.52 (d, J=2.1 Hz, 2H), 7.43 (d, J=2.1 Hz, 2H),
1

7.24-7.11 (m, 4H), 7.08 (d, J=7.4 Hz, 5H), 7.06-6.99 (m, 3H), 6.84-6.72 (m, 8H), 6.69-6.63 (m, 2H),
4.97 (q, J=7.1 Hz, 2H), 4.83 (q, J=7.1 Hz, 2H), 1.63 (d, J=7.1 Hz, 6H), 1.59 (d, J=7.1 Hz, 6H), 1.21
(s, 18H) ppm. 13C NMR (101 MHz, C6D6) δ 231.41, 151.97, 146.01, 145.85, 145.44, 143.90, 141.04,
135.62, 131.37, 129.80, 129.33, 128.61, 128.20, 128.15, 127.94, 127.12, 126.74, 126.37, 125.90,
123.87, 123.26, 120.72, 40.80, 38.67, 35.08, 31.43, 22.91, 21.38 ppm.

7,9-Bis(2,6-bis((R)-1-(3,5-dimethylphenyl)ethyl)-4-methylphenyl)-7H-acenaphtho[1,2-d]imidazol-9-
ium-8-ide (L15):
Following GP4 using KH (128 mg, 3.20 mmol, 5 eq), KOtBu (7.18 mg, 0.06
mmol, 10 mol%) and imidazolium salt S18 (600.0mg, 0.64 mmol, 1.0 eq).
The reaction mixture was sonicated for 12h. The title compound was
obtained as dark green solid, 560 mg (97 %).
H NMR (400 MHz, C6D6) δ 7.51 (s, 4H), 7.31 (d, J=1.2 Hz, 2H), 7.27 (d,
1

J=8.2 Hz, 2H), 7.22 (d, J=1.2 Hz, 2H), 7.12 (d, J=1.5 Hz, 2H), 7.01 (d, J=7.5 Hz, 2H), 6.92-6.87 (m,
2H), 6.74-6.68 (m, 4H), 6.22 (s, 2H), 5.00 (q, J=7.1 Hz, 2H), 4.87 (q, J=7.1 Hz, 2H), 2.14 (s, 12H),
2.08 (s, 6H), 1.72 (d, J=7.2 Hz, 6H), 1.69 (s, 12H), 1.64 (d, J=7.2 Hz, 6H) ppm. 13C NMR (101 MHz,
C6D6) δ 231.68, 146.13, 145.95, 145.69, 144.68, 141.24, 139.01, 137.87, 137.25, 135.68, 131.46,

S17
129.62, 129.33, 128.57, 127.94, 127.63, 127.56, 126.94, 126.76, 126.39, 126.32, 126.17, 125.70,
120.29, 40.61, 38.28, 22.79, 21.80, 21.65, 21.52, 21.46, 21.01 ppm.

7,9-Bis(2,6-bis((R)-1-(3,5-di-tert-butylphenyl)ethyl)-4-methylphenyl)-7H-acenaphtho[1,2-d]imidazol-
9-ium-8-ide (L16):
Following GP4 using KH (10.3 mg, 0.25 mmol, 5 eq), KOtBu
(0.57 mg, 5.10 µmol, 10 mol%) and imidazolium salt S19 (72.0
mg, 0.05 mmol, 1.0 eq). The reaction mixture was sonicated for
12h. The title compound was obtained as dark green solid, 61
mg (97%).
1
H NMR (400 MHz, C6D6) δ 7.72 (d, J=1.2 Hz, 4H), 7.44 (s, 2H),
7.34-7.29 (m, 4H), 7.15-7.11 (m, 4H), 7.07-6.95 (m, 6H), 6.84 (d,
J=6.8 Hz, 2H), 5.04 (q, J=7.2 Hz, 2H), 4.64 (q, J=7.1 Hz, 2H), 1.99 (s, 6H), 1.74 (d, J=7.2 Hz, 6H),
1.69 (d, J=7.1 Hz, 6H), 1.37 (s, 36H), 1.06 (s, 36H) ppm; 13C NMR (101 MHz, C6D6) δ 233.01, 150.51,
150.43, 145.77, 145.15, 144.86, 141.19, 138.79, 135.47, 131.64, 130.21, 129.33, 128.57, 128.17,
127.94, 127.64, 127.58, 127.25, 126.75, 126.54, 125.70, 122.95, 122.51, 120.28, 120.12, 41.24,
38.78, 35.20, 34.69, 31.92, 31.53, 23.97, 21.88, 21.57 ppm.

S18
Substrate synthesis

Synthesis of N-alkylated 2-pyridones

General procedure 5 (GP5)

According to our procedure published previously.3 A solution of the corresponding mesylate (1 eq)
in MeCN (2 mL) was added dropwise over 1h to a mixture of 2-hydroxypyridine (1.7 equiv) and
K2CO3 (1.7 equiv) in MeCN (1M) at 70 °C. After stirring for 12 h at 70 °C the reaction mixture was
evaporated to dryness under reduced pressure and diluted with toluene (10 mL). Filtration through
a pad of celite followed by concentration of the filtrate under reduced pressure afforded the crude
product, which was purified by column chromatography on silica gel using the indicated eluent.

General procedure 6 (GP6)

Vinyl iodide was obtained applying procedure GP5. In a schlenk tube 1-(3-iodobut-3-en-1-yl)pyridin-
2(1H)-one (1 eq), corresponding aryl boronic acid (1.1 eq), Na2CO3 (1.5 eq) and Pd(PPh3)4 (5 mol%)
were combined and dissolved in a toluene/water mixture (5/1). The suspension was degassed by
three consecutive evacuation, nitrogen purge cycles. Subsequently the mixture was heated to 75 °C
and was stirred for 12 h. Then water was added and the mixture was extracted with DCM and washed
with sat. NH4Cl solution and dried over MgSO4. After concentrating under reduced pressure the
crude product was obtained, which was purified by column chromatography on silica gel using the
indicated eluent.

1-(3-Methylbut-3-en-1-yl)pyridin-2(1H)-one (1a)
Following GP5 using 3-methylbut-3-en-1-yl methanesulfonate (2.29 g, 14.0 mmol, 1.0
eq), giving 1.28 g (63 %) of the title compound as pale yellow solid.

H NMR (400 MHz, CDCl3) δ 7.29 (t, J = 7.9 Hz, 1H), 7.23–7.16 (m, 1H), 6.55 (d, J = 9.1 Hz, 1H),
1

6.13 (d, J = 6.7 Hz, 1H), 4.79 (s, 1H), 4.67 (s, 1H), 4.03 (t, J = 7.3 Hz, 2H), 2.43 (t, J = 7.3 Hz, 2H),
1.78 (s, 3H) ppm; C NMR (101 MHz, CDCl3) δ 162.6, 141.8, 139.4, 137.7, 121.1, 113.0, 105.8,
13

48.4, 37.1, 22.6 ppm; IR (ATR): 3076, 2941, 1655, 1583, 1538, 1465, 1443, 1396, 1377, 1351,
1315, 1242, 1162, 1143, 1051, 891, 843, 765, 733, 573, 527, 488, 437 cm-1; HRMS (ESI) calculated
for [C10H13NO+H]+: 164.1070, found: 164.1069; Rf: 0.2 (pentane:EtOAc 1:1); m.p. 64-66°C.
S19
1-(3-Phenylbut-3-en-1-yl)pyridin-2(1H)-one (1b)

Following GP5 using 3-phenylbut-3-en-1-yl methanesulfonate (432 mg, 1.91 mmol, 1.0
eq) giving 209 mg (54%) of the title compound as pale yellow oil.

H NMR (400 MHz, CDCl3) δ 7.49–7.44 (m, 2H), 7.40–7.27 (m, 4H), 6.99 (dd, J1 = 6.8 Hz, J2 = 1.9
1

Hz, 1H), 6.58 (d, J = 9.1 Hz, 1H), 6.06 (td, J1 = 6.7 Hz, J2 = 1.0 Hz, 1H), 5.36 (d, J = 1.1 Hz, 1H), 5.06
(d, J = 1.1 Hz, 1H), 4.01 (t, J = 7.0 Hz, 2H), 3.00 (td, J1 =7.0 Hz, J2 = 0.9 Hz, 2H) ppm; 13C NMR (151
MHz, CDCl3) δ 162.7, 144.5, 139.9, 139.6, 138.2, 128.8, 128.0, 126.2, 121.0, 115.5, 105.6, 49.7,
34.5 ppm; IR (ATR): 3081, 2949, 1657, 1627, 1587, 1538, 1495, 1464, 1444, 1396, 1350, 1241,
1190, 1163, 1143, 1028, 903, 883, 843, 765, 708, 569, 527, 488, 440 cm-1; HRMS (ESI) calculated
for [C15H15NO+H]+: 226.1226, found: 226.1232; Rf: 0.3 (pentane:EtOAc 1:1).

1-(3-(4-Methoxyphenyl)but-3-en-1-yl)pyridin-2(1H)-one (1c)

Following GP6 using 1-(3-iodobut-3-en-1-yl)pyridin-2(1H)-one (300 mg, 1.09

mmol, 1.0 eq) and 4-methoxyphenylboronic acid (174 mg, 1.15 mmol, 1.05 eq)
giving 150 mg (54%) of the title compound as pale yellow oil.

H NMR (600 MHz, CDCl3) δ 7.41 (m, 2H), 7.29 (m, 1H), 6.98 (dd, J1 = 6.9 Hz, J2 = 1.7 Hz, 1H), 6.89
1

(d, J = 8.8 Hz, 2H), 6.56 (d, J = 9.0 Hz, 1H), 6.05 (td, J1 = 6.6 Hz, J2 = 1.1 Hz, 1H), 5.27 (d, J = 1.7
13
Hz, 1H), 4.96 (s, 1H), 4.00 (t, J = 7.0 Hz, 2H), 3.82 (s, 3H), 2.96 (t, J = 7.0 Hz, 2H) ppm; C NMR
(151 MHz, CDCl3) δ 162.7, 159.5, 143.7, 139.6, 138.3, 132.2, 127.4, 121.0, 114.1, 113.8, 105.7,
55.4, 49.8, 34.6 ppm; IR (ATR): 2955, 2836, 1658, 1587, 1538, 1512, 1464, 1441, 1288, 1249,
1182, 1165, 1144, 1031, 896, 882, 838, 812, 766, 732, 542, 418 cm-1;HRMS (ESI) calculated for
[C16H17NO2+H]+: 256.1332, found: 256.1328; Rf: 0.25 (pentane:EtOAc 1:1).

1-(3-(4-(Trifluoromethyl)phenyl)but-3-en-1-yl)pyridin-2(1H)-one (1d)

Following GP6 using 1-(3-iodobut-3-en-1-yl)pyridin-2(1H)-one (721 mg, 2.62

mmol, 1.0 eq) and 4-trifluoromethylphenylboronic acid (597 mg, 3.15 mmol, 1.2
eq) giving 280 mg (36%) of the title compound as yellow oil.

H NMR (600 MHz, CDCl3) δ 7.61 (d, J = 8.4 Hz, 2H), 7.57 (d, J = 7.3 Hz, 2H), 7.30 (m, 1H), 7.01
1

(dd, J1 = 6.8 Hz, J2 = 2.0 Hz, 1H), 6.57 (d, J = 9.1 Hz, 1H), 6.08 (td, J1 = 6.7 Hz, J2 = 1.2 Hz, 1H),
5.45 (s, 1H), 5.19 (s, 1H), 4.00 (t, J = 7.1 Hz, 2H), 3.02 (t, J = 7.1 Hz, 2H) ppm; 13C NMR (151 MHz,
CDCl3) δ 162.7, 143.6, 143.5, 139.8, 137.9, 126.5, 125.7, 121.2, 117.4, 106.0, 49.9, 34.3 ppm; 19F
NMR (376 MHz, CDCl3) δ -62.58 ppm; IR (ATR): 3085, 2947, 1660, 1616, 1588, 1539, 1464,

S20
1435, 1408, 1325, 1242, 1165, 1119, 1067, 1015, 911, 883, 848, 764, 732, 652, 631, 596, 566, 527,
514, 484, 433 cm-1;HRMS (ESI) calculated for [C16H14F3NO+H]+: 294.1100, found: 294.1106; Rf:
0.35 (pentane:EtOAc 1:1).

1-(3-(o-Tolyl)but-3-en-1-yl)pyridin-2(1H)-one (1e)

Following GP6 using 1-(3-iodobut-3-en-1-yl)pyridin-2(1H)-one (200 mg, 0.73 mmol,

1.0 eq) and o-tolylboronic acid (109 mg, 0.80 mmol, 1.1 eq) giving 103 mg (59%) of
the title compound as yellow oil.

H NMR (400 MHz, CDCl3) δ 7.36–7.26 (m, 1H), 7.20–7.07 (m, 5H), 6.58 (d, J = 9.1 Hz, 1H), 6.11
1

(td, J1 = 6.7 Hz, J2 = 1.3 Hz, 1H), 5.26 (d, J = 1.4 Hz, 1H), 5.00 (d, J = 1.5 Hz, 1H), 3.96 (t, J = 7.6
Hz, 2H), 2.84 (t, J = 7.6 Hz, 2H), 2.31 (s, 3H) ppm; C NMR (151 MHz, CDCl3) δ 162.7, 145.9,
13

141.6, 139.5, 137.8, 135.1, 130.6, 128.5, 127.4, 125.8, 121.2, 117.1, 105.9, 49.1, 36.6, 20.2 ppm;
IR (ATR): 3078, 3019, 2978, 2951, 2927, 2866, 1658, 1588, 1538, 1487, 1464, 1444, 1396, 1349,
1312, 1274, 1240, 1192, 1164, 1143, 1108, 1088, 1035, 908, 883, 843, 765, 732, 583, 573, 528,
514, 458, 440 cm-1; HRMS (ESI) calculated for [C16H17NO+H]+: 240.1383, found: 240.1384; Rf: 0.3
(pentane:EtOAc 1:1).

1-(3-(Naphthalen-2-yl)but-3-en-1-yl)pyridin-2(1H)-one (1f)

Following GP6 using 1-(3-iodobut-3-en-1-yl)pyridin-2(1H)-one (250 mg, 0.91

mmol, 1.0 eq) and 2-naphthylboronic acid (172 mg, 1.00 mmol, 1.1 eq) giving
170 mg (68%) of the title compound as yellow oil.

H NMR (400 MHz, CDCl3) δ 7.91 (s, 1H), 7.86–7.74 (m, 3H), 7.60 (dd, J1 = 8.6 Hz, J2 = 1.8 Hz, 1H),
1

7.54–7.43 (m, 2H), 7.31–7.24 (m, 1H), 6.97 (dd, J1 = 6.8 Hz, J2 = 1.8 Hz, 1H), 6.57 (d, J = 9.0 Hz,
1H), 6.02 (td, J1 = 6.6 Hz, J2 = 1.2 Hz, 1H), 5.51 (d, J =0 .8 Hz, 1H), 5.17 (d, J = 0.8Hz, 1H), 4.06 (t,
J = 7.0Hz, 2H), 3.12 (d, J = 7.0 Hz, 2H) ppm; 13
C NMR (101 MHz, CDCl3) δ 162.7, 144.2, 139.6,
138.3, 137.0, 133.5, 133.1, 128.4, 127.6, 126.5, 126.3, 125.0, 124.4, 121.0, 116.0, 105.7, 49.9, 34.4
ppm; IR (ATR): 3078, 3055, 2993, 2947, 1657, 1622, 1587, 1537, 1505, 1464, 1433, 1396, 1349,
1312, 1274, 1241, 1163, 1143, 1081, 1032, 896, 861, 842, 821, 759, 732, 618, 568, 526, 477 cm-1;
HRMS (ESI) calculated for [C19H17NO+H]+: 276.1383, found: 276.1382; Rf: 0.2 (pentane:EtOAc 1:1).

1-(3-(Furan-2-yl)but-3-en-1-yl)pyridin-2(1H)-one (1g)
Prepared according to the procedure published previously.3

S21
H NMR (400 MHz, CDCl3) δ 7.37 (d, J = 1.5 Hz, 1H), 7.31 (m, 1H), 7.10 (dd, J1 = 6.7 Hz, J2 = 2.0
1

Hz, 1H), 6.58 (d, J = 9.1 Hz, 1H), 6.51 (d, J = 3.3 Hz, 1H), 6.39 (dd, J1 = 3.4 Hz, J2 = 1.8 Hz, 1H),
6.08 (td, J1 = 6.7 Hz, J2 = 1.4 Hz, 1H), 5.55 (s, 1H), 4.94 (s, 1H), 4.11 (t, J=7.1 Hz, 2H), 2.82 (t, J=7.1
Hz, 2H) ppm; 13C NMR (101 MHz, CDCl3) δ 162.7, 153.8, 142.4, 139.7, 138.2, 133.8, 121.0, 112.2,
111.5, 107.0, 105.9, 50.3, 33.0 ppm; IR (ATR): 3444, 3099, 2949, 1656, 1584, 1538, 1489, 1465,
1435, 1396, 1352, 1243, 1194, 1162, 1145, 1091, 1017, 884, 844, 764, 733, 667, 595, 529, 506,
470, 433 cm-1; HRMS (ESI) calculated for [C13H13NO2+H]+: 216.1019, found: 216.1013; Rf: 0.3
(pentane:EtOAc 1:2).

(S)-1-(3-(4-Methylcyclohex-3-en-1-yl)but-3-en-1-yl)pyridin-2(1H)-one (1h)
Following GP5 using (S)-3-(4-methylcyclohex-3-en-1-yl)but-3-en-1-yl
methanesulfonate (250 mg, 1.02 mmol, 1.0 eq) giving 198 mg (80%, 89:11 er) of
the title compound as pale yellow oil .
(S)-3-(4-methylcyclohex-3-en-1-yl)but-3-en-1-yl methanesulfonate was obtained from S-limonene
applying a procedure reported by Snider.4 Partial racemization of the starting material was observed
under these reaction conditions.
H NMR (400 MHz, CDCl3) δ 7.30 (m, 1H), 7.21 (dd, J1 = 6.7Hz, J2 = 1.8Hz, 1H), 6.56 (d, J = 9.1 Hz,
1

1H), 6.13 (td, J1 = 6.7 Hz, J2 = 1.3 Hz, 1H), 5.38 (s, 1H), 4.86 (s, 1H), 4.76 (d, J = 1.0 Hz, 1H), 4.03
(m, 2H), 2.47 (t, J = 7.6 Hz, 2H), 2.17–1.76 (m, 6H), 1.64 (s, 3H), 1.46 (m, 1H) ppm; 13C NMR (151
MHz, CDCl3) δ 162.6, 150.4, 139.5, 137.8, 133.9, 121.2, 120.5, 110.2, 105.8, 49.5, 39.9, 34.1, 31.2,
30.7, 28.2, 23.6 ppm; IR (ATR): 3080, 2959, 2916, 2855, 2834, 1656, 1587, 1537, 1465, 1438,
1396, 1377, 1350, 1310, 1279, 1242, 1161, 1143,1104, 1035, 1019, 894, 842, 798, 764, 732, 593,
566, 527, 480, 430 cm-1; HRMS (ESI) calculated for [C16H21NO+H]+: 244.1696, found: 244.1696; Rf:
0.25 (pentane:EtOAc 1:1).

(R)-1-(3-(4-Methylcyclohex-3-en-1-yl)but-3-en-1-yl)pyridin-2(1H)-one (1i)
Following GP5 using (R)-3-(4-methylcyclohex-3-en-1-yl)but-3-en-1-yl
methanesulfonate (250 mg, 1.02 mmol, 1.0 eq) giving 176 mg (71%, 97:3 er) of
the title compound as pale yellow oil.
(R)-3-(4-methylcyclohex-3-en-1-yl)but-3-en-1-yl methanesulfonate was obtained from R-limonene
applying a procedure reported by Snider.4 Partial racemization of the starting material was observed
under these reaction conditions.
H NMR (400 MHz, CDCl3) δ 7.39–7.28 (m, 1H), 7.24–7.19 (m, 1H), 6.57 (m, 1H), 6.19–6.10 (m,
1

1H), 5.38 (s, 1H), 4.86 (s, 1H), 4.76 (d, J = 0.6 Hz, 1H), 4.07–3.98 (m, 2H), 2.48 (t, J = 7.5 Hz, 2H),
2.17–1.77 (m, 6H), 1.64 (s, 3H), 1.46 (m, 1H) ppm; 13
C NMR (101 MHz, CDCl3) δ 162.6, 150.4,
139.5, 137.9, 133.9, 121.2, 120.5, 110.3, 106.0, 77.4, 49.6, 40.0, 34.1, 31.3, 30.7, 28.2, 23.6 ppm;
IR (ATR): 3080, 3010, 2960, 2917, 2855, 2834, 1657, 1588, 1537, 1465, 1438, 1396, 1377, 1350,

S22
1311, 1278, 1242, 1161, 1142, 1104, 1048, 1035, 1019, 914, 894, 842, 798, 764, 732, 593, 567,
526, 512, 479, 431 cm-1; HRMS (ESI) calculated for [C16H21NO+H]+: 244.1696, found: 244.1701; Rf:
0.25 (pentane:EtOAc 1:1).

2-(3-Phenylbut-3-en-1-yl)isoquinolin-1(2H)-one (1j)
Following GP5 using 3-phenylbut-3-en-1-yl methanesulfonate (329 mg, 1.45 mmol,
1.0 eq) giving 232 mg (58%) of the title compound as white solid.
1
H NMR (400 MHz, CDCl3) δ 8.44 (m, 1H), 7.65–7.60 (m, 1H), 7.53–7.45 (m, 4H),
7.40–7.33 (m, 2H), 7.32–7.27 (m, 1H), 6.85 (d, J = 7.4 Hz, 1H), 6.41 (d, J = 7.1 Hz, 1H), 5.36 (d, J =
1.2 Hz, 1H), 5.09 (d, J = 1.1 Hz, 1H), 4.10 (t, J = 7.1 Hz, 2H), 3.05 (m, 2H) ppm; 13C NMR (101 MHz,
CDCl3) δ 162.2, 144.8, 140.0, 137.2, 132.3, 132.2, 128.7, 127.9, 127.9, 126.8, 126.4, 126.2, 126.0,
115.3, 105.8, 49.3, 34.7 ppm; IR (ATR): 3059, 2948, 1649, 1625, 1599, 1556, 1491, 1457, 1421,
1372, 1326, 1294, 1258, 1180, 1151, 1134, 1107, 1027, 963, 902, 783, 747, 707, 693, 579, 494, 420
cm-1; HRMS (ESI) calculated for [C19H17NO+H]+: 276.1383, found: 276.1380; Rf: 0.4 (pentane:EtOAc
3:1).

1-(4-Phenylpent-4-en-1-yl)pyridin-2(1H)-one (1k)
Following GP5 using 1-(4-phenylpent-4-en-1-yl)pyridin-2(1H)-one (430 mg, 1.79 mmol,
1.0 eq) giving 295 mg (69%) of the title compound as yellow solid.

H NMR (400 MHz, CDCl3) δ 7.41–7.27 (m, 6H), 7.16 (ddd, J1 = 6.8 Hz, J2 = 2.0 Hz, J3 = 0.5 Hz, 1H),
1

6.57 (d, J = 9.1 Hz, 1H), 6.13 (td, J1 = 6.7 Hz, J2 = 1.3 Hz, 1H), 5.31 (m, 1H), 5.11 (q, J = 1.3 Hz, 1H),
3.94 (t, J = 7.5 Hz, 2H), 2.58 (t, J = 8.0 Hz, 2H), 1.94 (p, J = 7.6 Hz, 2H) ppm; 13C NMR (101 MHz,
CDCl3) δ 162.7, 147.3, 140.9, 139.4, 137.6, 128.5, 127.7, 126.2, 121.2, 113.2, 106.0, 49.4, 32.3,
27.7 ppm; IR (ATR): 3471, 3081, 3029, 2943, 1656, 1585, 1538, 1494, 1464, 1441, 1396, 1348,
1271, 1241, 1161, 1143, 1076, 1046, 1028, 899, 843, 766, 731, 706, 572, 528, 445 cm-1; HRMS
(ESI) calculated for [C16H17NO+H]+: 240.1383, found: 240.1384; Rf: 0.2 (pentane:EtOAc 1:2).

(Z)-1-(Pent-3-en-1-yl)pyridin-2(1H)-one ((Z)-1l)
Prepared according to the procedure published previously.3

H NMR (400 MHz, CDCl3) δ 7.30 (m, 1H), 7.21 (dd, J1 = 6.7 Hz, J2 = 2.0 Hz, 1H), 6.55 (d, J = 9.1
1

Hz, 1H), 6.11 (td, J1 = 6.7 Hz, J2 = 1.3 Hz, 1H), 5.58 (m, 1H), 5.39 (m, 1H), 3.94 (t, J = 6.9 Hz, 2H),
2.52 (q, J = 7.2 Hz, 2H), 1.51 (dd, J1 = 6.8 Hz, J2=0.9 Hz, 3H) ppm; 13
C NMR (101 MHz, CDCl3) δ
162.7, 139.5, 138.1, 127.9, 125.3, 121.0, 105.7, 49.8, 26.5, 12.7 ppm; IR (ATR): 3472, 3076,
3017, 2938, 1652, 1579, 1537, 1465, 1435, 1396, 1349, 1306, 1241, 1194, 1164, 1146, 1085, 1029,

S23
998, 970, 944, 877, 844, 765, 735, 704, 569, 529, 460, 433 cm-1; HRMS (ESI) calculated for
[C10H13NO+H]+: 164.1070, found: 164.1072; Rf: 0.3 (pentane:EtOAc 1:2).

(E)-1-(Pent-3-en-1-yl)pyridin-2(1H)-one ((E)-1l)
Following GP5 using (E)-pent-3-en-1-yl methanesulfonate (200 mg, 1.22 mmol, 1.0 eq)
giving 98.0 mg (49 %) of the title compound as yellow liquid.

H NMR (400 MHz, CDCl3) δ 7.30 (m, 1H), 7.20 (dd, J1 = 6.7 Hz, J2 = 2.0 Hz, 1H), 6.55 (d, J = 9.1
1

Hz, 1H), 6.12 (td, J1 = 6.7 Hz, J2 = 1.3 Hz, 1H), 5.46 (m, 1H), 5.40 (m, 1H), 3.93 (t, J = 7.1 Hz, 2H),
2.42 (q, J = 7.1 Hz, 2H), 1.63 (dd, J1 = 6.0 Hz, J2=1.0 Hz) ppm; 13C NMR (101 MHz, CDCl3) δ 162.7,
139.4, 137.9, 128.8, 126.5, 121.2, 105.6, 50.1, 32.3, 18.1 ppm; IR (ATR): 3489, 3079, 3024, 2936,
2918, 2855, 1655, 1585, 1538, 1465, 1436, 1396, 1377, 1351, 1328, 1277, 1241, 1194, 1165, 1147,
1089, 1069, 1040, 969, 946, 883, 844, 767, 733, 574, 527, 479, 437, 400 cm -1; HRMS (ESI)
calculated for [C10H13NO+H]+: 164.1070, found: 164.1076; Rf: 0.35 (pentane:EtOAc 1:2).

(E)-1-(4-Phenylbut-3-en-1-yl)pyridin-2(1H)-one ((E)-1m)
Following GP5 using (E)-(4-(methylsulfonyl)but-1-en-1-yl)benzene (741 mg, 3.29 mmol,
1.0 eq) giving 642 mg (57 %) of the title compound as yellow oil.

H NMR (400 MHz, CDCl3) δ 7.34–7.27 (m, 5H), 7.25–7.19 (m, 2H), 6.59 (d, J = 9.1 Hz, 1H), 6.42
1

(d, J = 5.8 Hz, 1H), 6.21–6.09 (m, 2H), 4.06 (t, J = 7.1 Hz, 2H), 2.70 (qd, J1 = 7.1 Hz, J2 = 1.2 Hz,
2H) ppm; 13
C NMR (151 MHz, CDCl3) δ 162.7, 139.6, 137.8, 137.2, 133.2, 128.7, 127.5, 126.2,
125.6, 121.2, 105.9, 50.0, 32.6 ppm; IR (ATR): 3451, 3026, 2946, 1656, 1586, 1537, 1495, 1464,
1445, 1396, 1351, 1241, 1163, 1144, 1066, 968, 884, 843, 765, 747, 694, 572, 526, 496, 443 cm -1;
HRMS (ESI) calculated for [C15H15NO+H]+: 226.1226, found: 226.1232; Rf: 0.2 (pentane:EtOAc 1:1).

1-(2-(Cyclopent-1-en-1-yl)ethyl)pyridin-2(1H)-one (1n)

Following GP5 using 1-(2-(methylsulfonyl)ethyl)cyclopent-1-ene (350 mg, 1.85 mmol,

1.0 eq) giving 199 mg (57 %) of the title compound as yellow oil.

H NMR (400 MHz, CDCl3) δ 7.30 (m, 1H), 7.19 (dd, J1 = 6.7 Hz, J2 = 1.9 Hz, 1H), 6.58 (d, J = 9.1
1

Hz, 1H), 6.13 (td, J1 = 6.7 Hz, J2 = 1.3 Hz, 1H), 5.38 (m, 1H), 4.04 (t, J = 7.3 Hz, 2H), 2.52 (t, J = 7.2
Hz, 2H), 2.28 (t, J = 7.2 Hz, 4H), 1.86 (p, J = 7.5 Hz, 2H) ppm; 13C NMR (151 MHz, CDCl3) δ 162.4,
140.1, 139.2, 137.5, 126.4, 120.9, 105.6, 48.4, 35.1, 32.5, 30.5, 23.3 ppm; IR (ATR): 3040, 2948,
2844, 1655, 1584, 1537, 1465, 1442, 1396, 1349, 1280, 1241, 1163, 1143, 1048, 950, 881, 842,
765, 732, 593, 563, 528, 477, 436 cm-1; HRMS (ESI) calculated for [C12H15NO+H]+: 190.1226, found:
190.2227; Rf: 0.35 (EtOAc).
S24
To a suspension of ethyltriphenylphosphonium bromide (4.71 g, 12.68 mmol) in THF (55 ml) a 2.5 M
solution of n-butyllithium (4.65 ml, 11.63 mmol) was added dropwise at -78°C. The mixture was
warmed to 0°C and stirred for 1h. Subsequently the mixture was recooled to -78°C and a solution of
1-(3-oxobutyl)pyridin-2(1H)-one (1.746g, 10.57 mmol) in THF (5 ml) was added dropwise and the
mixture was slowly warmed to RT and stirred overnight. The reaction was stopped by adding a
saturated solution of NH4Cl (10mL). The mixture was extracted with Et2O, washed with water and
brine and was dried over MgSO4. After concentrating under reduced pressure the crude product was
obtained, which was purified by column chromatography on silica gel (pentane:EtOAc 1:1 – EtOAc).
The product was obtained as a yellow oil, 1.46 g (78%) as 1:1 mixture of double bond isomers, which
were separated by preparative HPLC (Chiralpak IC, hexane:EtOH 80:20, 18.0 mL/min, 312 nm; tR (Z-
isomer) = 25.3 min, tR (E-isomer) = 29.0 min, 1:1 dr).

(E)-1-(3-methylpent-3-en-1-yl)pyridin-2(1H)-one (1o)
1
H NMR (400 MHz, CDCl3) δ 7.29 (ddd, J = 9.0, 6.6, 2.1 Hz, 1H), 7.14 (dd, J = 6.8,
2.0 Hz, 1H), 6.55 (dd, J = 9.2, 1.3 Hz, 1H), 6.11 (td, J = 6.7, 1.4 Hz, 1H), 5.17 (tdt, J
= 6.6, 5.3, 1.4 Hz, 1H), 3.98 (t, J = 7.2 Hz, 2H), 2.38 (t, J = 7.2 Hz, 2H), 1.66 (t, J =
1.3 Hz, 3H), 1.53 (dt, J = 6.8, 1.2 Hz, 3H); 13C NMR (151 MHz, CDCl3) δ 162.5, 139.3, 137.7, 131.5,
122.0, 120.9, 105.5, 48.6, 38.9, 15.8, 13.5; IR (ATR): 3451, 3067, 3027, 2917, 2859, 1655, 1583,
1538, 1439, 1381, 1351, 1241, 1191, 1162, 1143, 1049, 996, 884, 765, 731, 696, 582, 542, 498 cm-
1
; HRMS (ESI) calculated for [C11H15NO+H]+: 178.1226, found: 178.1228; Rf: 0.35 (EtOAc); >20:1
dr.

(Z)-1-(3-methylpent-3-en-1-yl)pyridin-2(1H)-one (1p)
1
H NMR (400 MHz, CDCl3) δ 7.29 (ddd, J = 8.9, 6.6, 2.0 Hz, 1H), 7.14 (dd, J =
6.8, 2.0 Hz, 1H), 6.53 (d, J = 9.1 Hz, 1H), 6.09 (td, J = 6.7, 1.3 Hz, 1H), 5.33 (q, J
= 6.9 Hz, 1H), 3.96 (t, J = 6.9 Hz, 2H), 2.46 (t, J = 6.9 Hz, 2H), 1.73 (t, J = 1.6 Hz,
3H), 1.38 (dd, J = 6.9, 1.7 Hz, 3H); 13C NMR (151 MHz, CDCl3) δ 162.7, 139.3, 137.9, 131.3, 123.1,
120.8, 105.5, 48.1, 30.8, 23.5, 13.1; IR (ATR): 3468, 3081, 3029, 2963, 2919, 2860, 1655, 1585,
1537, 1460, 1444, 1377, 1354, 1160,1142, 1117, 1073, 1018, 930, 883, 842, 765, 730, 573, 525cm-
1
; HRMS (ESI) calculated for [C11H15NO+H]+: 178.1226, found: 178.1218; Rf: 0.35 (EtOAc ); >96:4
dr.

S25
1-(4-methylpent-3-en-1-yl)pyridin-2(1H)-one (1q)
Following GP5 using 5-bromo-2-methylpent-2-ene (189 mg, 1.16 mmol, 1.1 eq)
giving 89.0 mg (48 %) of the title compound as yellow oil.

H-NMR (400 MHz, CDCl3): δ = 7.31 (ddd, J1 = 9.2 Hz, J2 = 6.6 Hz, J3 = 2.1 Hz, 1H), 7.19 (ddd, J1 =
1

6.8 Hz, J2 = 2.1 Hz, J3 = 0.7 Hz, 1H), 6.56 (ddd, J1 = 9.2 Hz, J1 = 1.4 Hz, J1 = 0.7 Hz, 1H), 6.11 (td,
J1 = 6.7 Hz, J1 = 1.4 Hz, 1H), 5.08-5.15 (m, 1H), 3.90 (t, J = 7.0 Hz, 2H), 2.40-2.48 (m, 2H), 1.68 (s,
3H), 1.50 (s, 3H); C{1H}-NMR (150 MHz, CDCl3): δ = 162.7, 139.3, 138.0, 135.8, 121.0, 119.5,
13

~
105.4, 50.1, 27.7, 25.8, 17.6; IR (ATR):  = 3026, 2968, 2928, 1655, 1586, 1538, 1464, 1438, 1395,
1377, 1346, 1305, 1243, 1159, 1142, 1097, 1043, 884, 841, 765, 732; HRMS (ESI) calculated for
[M+H]+ = [C11H15NOH]+: 178.1226, found: 178.1227; Rf: 0.37 (EtOAc).

3-Methyl-1-(3-phenylbut-3-en-1-yl)pyrimidine-2,4(1H,3H)-dione (3a)
A mixture of tert-butyl 3-methyl-2,4-dioxo-3,4-dihydropyrimidine-1(2H)-carboxylate5
(2.262 g, 10 mmol, 1 eq) and K2CO3 (0.691 g, 5 mmol, 0.5 eq) in MeOH (100 mL)
was stirred for 10 h at 23°C. Evaporation under reduced pressure afforded the K-salt
of the 3-methyluracil, which was directly alkylated with 3-phenylbut-3-en-1-yl methanesulfonate (2.31
g, 11.0 mmol, 1.1 eq) following GP5 yielding 730 mg (57%) of the title compound as white solid.
H NMR (400 MHz, CDCl3) δ 7.42–7.27 (m, 5H), 6.80 (d, J = 7.8 Hz, 1H), 5.59 (d, J = 7.9 Hz, 1H),
1

5.39 (d, J = 1.1 Hz, 1H), 5.11 (d, J = 1.0 Hz, 1H), 3.82 (t, J = 6.9 Hz, 2H), 3.32 (s, 3H), 2.95 (td, J1 =
6.7 Hz, J2 = 0.8 Hz, 2H) ppm; 13C NMR (101 MHz, CDCl3) δ 163.4, 151.6, 144.2, 142.7, 139.5, 128.9,
128.2, 126.2, 116.1, 101.0, 49.6, 34.5, 27.8 ppm; IR (ATR): 3084, 2953, 1705, 1656, 1574, 1531,
1495, 1460, 1411, 1381, 1355, 1290, 1224, 1193, 1158, 1117, 1028, 999, 951, 905, 803, 780, 763,
711, 521, 501, 450, 416 cm-1; HRMS (ESI) calculated for [C15H16N2O2+H]+: 257.1285, found:
257.1290; Rf: 0.35 (pentane:EtOAc 1:1).

3-Benzyl-1-(3-phenylbut-3-en-1-yl)pyrimidine-2,4(1H,3H)-dione (3b)
A mixture of 3-benzylpyrimidine-2,4(1H,3H)-dione5 (613 mg, 2.03 mmol, 1 eq) and
K2CO3 (280 mg, 2.03 mmol, 1 eq) in MeOH (34 mL) was stirred for 10 h at 23°C.
Evaporation under reduced pressure afforded the K-salt of the 3-methyluracil, which
was directly alkylated with 3-phenylbut-3-en-1-yl methanesulfonate (470 mg , 2.23 mmol, 1.1 eq)
following GP5 yielding 324 mg (48%) of the title compound as white solid.
H NMR (400 MHz, CDCl3) δ 7.48–7.42 (m, 2H), 7.38–7.23 (m, 8H), 6.75 (d, J = 7.9 Hz, 1H), 5.59
1

(d, J = 7.8 Hz, 1H), 5.35 (d, J = 0.9 Hz, 1H), 5.10 (s, 2H), 5.05 (d, J = 0.8 Hz, 1H), 3.80 (t, J = 6.7
Hz, 2H), 2.94 (t, J = 6.7 Hz, 2H) ppm; 13
C NMR (151 MHz, CDCl3) δ 162.9, 151.2, 144.0, 142.7,
139.3, 136.8, 128.8, 128.7, 128.3, 128.0, 127.5, 126.0, 116.0, 100.9, 49.4, 44.1, 34.1 ppm; IR (ATR):
3085.14, 3061.37, 3031.66, 2956.65, 1705.59, 1657.24, 1494.75, 1451.12, 1392.11, 1369.60,
1348.21, 1223.16, 1203.95, 1122.84, 1086.78, 1028.91, 971.38, 905.78, 803.58, 779.45, 764.24,
S26
702.90, 600.59, 534.38, 503.42, 471.86, 455.38, 422.55, 408.00 cm-1; HRMS (ESI) calculated for
[C21H20N2O2+H]+: 333.1598, found: 333.1600; Rf: 0.4 (pentane:EtOAc 1:1).

S27
Synthesis of N-alkylated 4-pyridones

General procedure 7 (GP7)

In a 25ml two-neck flask corresponding alkyl iodide (1 eq) was dissolved in acetonitrile (0.5M) and
heated to 80 °C. To this mixture 4-((trimethylsilyl)oxy)pyridine6 (1.1 eq, distilled liquid, in neat) was
added dropwise over 1h and the mixture was stirred at 80 °C for 12h. Subsequently the mixture was
cooled to ambient temperature and K2CO3 (1.5 eq) and methanol (3 mL) were added. The mixture
was stirred for 30 min and then evaporated to dryness and taken up in toluene (10 mL). Filtration
through a pad of celite followed by concentration under reduced pressure afforded the crude product,
which was purified by column chromatography on silica gel using the indicated eluent.

General procedure 8 (GP8)

Vinyl iodide was obtained applying GP7. In a schlenk tube 1-(3-iodobut-3-en-1-yl)pyridin-4(1H)-one

(1eq), aryl boronic acid (1.1 eq), Na2CO3 (1.5 eq) and Pd(PPh3)4 (5 mol%) were combined and
dissolved in a toluene/water mixture (5/1). The suspension was degassed by three consecutive
evacuation, nitrogen purge cycles. Subsequently the mixture was heated to 75 °C and was stirred
for 12h. Then water was added and the mixture was extracted with DCM, washed with sat. NH4Cl-
solution and dried over MgSO4. After concentrating under reduced pressure the crude product was
obtained, which was purified by column chromatography on silica gel using the indicated eluent.

1-(3-(Naphthalen-2-yl)but-3-en-1-yl)pyridin-4(1H)-one (3c)
Following GP8 using 1-(3-iodobut-3-en-1-yl)pyridin-4(1H)-one (250 mg, 0.91
mmol, 1.0 eq), giving 134 mg (54 %) of the title compound as colourless oil.
1
H NMR (400 MHz, CD3OD) δ 7.92–7.81 (m, 4H), 7.64–7.56 (m, 2H), 7.52–
7.44 (m, 2H), 7.15 (m, 1H), 6.35 (m, 2H), 5.52 (d, J = 0.9 Hz, 1H), 5.15 (d, J = 0.8 Hz, 1H), 4.12 (t, J
= 6.7 Hz, 2H), 3.18 (t, J = 6.7 Hz, 2H) ppm; 13
C NMR (101 MHz, CD3OD) δ 180.7, 145.2, 143.3,
137.7, 134.9, 134.5, 129.9, 129.3, 129.2, 128.6, 127.5, 127.3, 126.3, 126.1, 125.4, 118.1, 117.1,
57.1, 37.4 ppm IR (ATR): 3390, 3078, 3054, 2955, 1639, 1563, 1523, 1505, 1467, 1405, 1378,
1232, 1190, 1134, 1104, 1015, 898, 849, 824, 755, 724, 527, 478, 401 cm-1; HRMS (ESI) calculated
for [C19H17NO+H]+: 276.1383, found: 276.1386; Rf: 0.35 (DCM:MeOH 9:1).
S28
1-(3-Phenylbut-3-en-1-yl)pyridin-4(1H)-one (3d)
Following GP7 using (4-iodobut-1-en-2-yl)benzene (415 mg, 1.61 mmol, 1.0 eq)
giving 322 mg (89 %) of the title compound as colourless oil.
H NMR (400 MHz, CD3OD) δ 7.61–7.56 (m, 2H), 7.42–7.37 (m, 2H), 7.37–7.25 (m, 3H), 6.34 (m,
1

2H), 5.32 (d, J = 1.1 Hz, 1H), 5.02 (d, J = 1.1 Hz, 1H), 4.04 (t, J = 6.7 Hz, 2H), 3.05 (t, J = 6.7 Hz,
2H) ppm; C NMR (151 MHz, CD3OD) δ 180.6, 145.5, 143.3, 140.6, 129.8, 129.1, 127.3, 118.1,
13

116.5, 57.0, 37.4 ppm; IR (ATR): 3420, 3078, 3053, 3030, 2992, 2953, 1636, 1544, 1495, 1443,
1400, 1379, 1360, 1326, 1299, 1233, 1189, 1119, 1076, 1021, 998, 907, 851, 780, 709, 532, 488
cm-1; HRMS (ESI) calculated for [C15H15NO+H]+: 226.1226, found: 226.1233; Rf: 0.25 (DCM:MeOH
9:1).

1-(3-(Naphthalen-1-yl)but-3-en-1-yl)pyridin-4(1H)-one (3e)
Following GP8 using 1-(3-iodobut-3-en-1-yl)pyridin-4(1H)-one (250 mg, 0.91
mmol, 1.0 eq), giving 160 mg (64 %) of the title compound as colourless oil.
H NMR (400 MHz, CD3OD) δ 7.97–7.78 (m, 3H), 7.64 (d, J = 7.4 Hz, 2H), 7.52–
1

7.41 (m, 2H), 7.31 (d, J = 6.9 Hz, 1H), 7.16 (m, 1H), 6.33 (d, J = 7.3 Hz, 2H), 5.52 (s, 1H), 5.22 (s,
1H), 4.02 (t, J = 7.0 Hz, 2H), 3.13 (t, J = 6.9 Hz, 2H) ppm; 13
C NMR (101 MHz, CD3OD) δ 180.7,
145.6, 143.2, 140.4, 135.5, 132.2, 129.9, 129.6, 129.2, 129.1, 127.2, 127.0, 126.5, 126.4, 126.3,
119.7, 118.2, 56.8, 39.9 ppm; IR (ATR): 3389, 3313, 3077, 3044, 3008, 2951, 1638, 1562, 1506,
1463, 1438, 1406, 1380, 1358, 1291, 1241, 1189, 1142, 1096, 1014, 915, 849, 806, 782, 741, 724,
670, 613, 576, 527, 503, 480, 444 cm-1; HRMS (ESI) calculated for [C19H17NO+H]+: 276.1383, found:
276.1383; Rf: 0.35 (DCM:MeOH 9:1).

1-(3-Methylbut-3-en-1-yl)pyridin-4(1H)-one (3f)
Following GP7 using 4-iodo-2-methylbut-1-ene (200 mg, 1.02 mmol, 1.0 eq) giving
164 mg (98 %) of the title compound as colourless oil.
H NMR (400 MHz, CDCl3) δ 7.26–7.22 (m, 2H), 6.41–6.34 (m, 2H), 4.86 (s, 1H), 4.68 (s, 1H), 3.87
1

(t, J = 7.1 Hz, 2H), 2.44 (t, J = 7.1 Hz, 2H), 1.75 (s, 3H) ppm; C NMR (101 MHz, CDCl3) δ 179.0,
13

140.1, 139.7, 118.9, 114.6, 55.4, 39.1, 22.4 ppm; IR (ATR): 3385, 3076, 3045, 2970, 2937, 2916,
2854, 1636, 1554, 1522, 1510, 1459, 1406, 1377, 1361, 1234, 1190, 1100, 1048, 1014, 984, 895,
850, 568, 550, 506, 475 cm-1; HRMS (ESI) calculated for [C10H13NO+H]+: 164.1070, found: 164.1072;
Rf: 0.5 (DCM:MeOH 9:1).

S29
Nickel-Catalyzed Enantioselective Pyridone C-H Functionalization

General procedure 9 (GP9)

Inside a glove box a tube containing a magnetic stirring bar was charged with MAD 7 (19.0 mg,
40 mol%) and the substrate (0.1 mmol). In a separate tube containing a stirring bar, Ni(cod)2 (2.8 mg,
10 mol%) and L15 (9.9 mg, 11 mol%) were combined, dissolved in toluene (0.4 mL) and stirred for
15 min at ambient temperature. Subsequently this catalyst solution was added to the first tube
resulting in a homogenous dark red solution. The tube was sealed, taken out of the glove box and
the reaction mixture was stirred for 24 h at 40°C. Subsequently the reaction mixture was cooled to
ambient temperature and was quenched with 200μL of a 5% EDTA disodium salt solution. The
mixture was filtered over a short plug of MgSO4 and silica gel eluting with EtOAc or MeOH and was
concentrated under reduced pressure to afford the crude product, which was purified by silica gel
column (EtOAc or DCM/MeOH).

S30
(R)-8-Methyl-6,7,8,9-tetrahydro-4H-quinolizin-4-one (2a)
Obtained as pale yellow oil in 83% (13.5 mg). 1H NMR (400 MHz, CDCl3) δ 7.23 (dd,
J1 = 9.0 z, J2 = 6.9 Hz, 1H), 6.43 (d, J = 9.0 Hz, 1H), 5.97 (d, J = 6.9 Hz, 1H), 4.23 (dt,
J = 14.8, 4.7 Hz, 1H), 3.77 (m, 1H), 2.84 (dd, J1 = 16.5 Hz, J2 = 3.8 Hz, 1H), 2.41 (dd,
J1 = 10.2 Hz, J2 = 16.5 Hz, 1H), 2.08 (m, 1H), 1.94 (m, 1H), 1.51 (m. 1H), 1.07 (d, J = 6.6 Hz, 3H)
ppm; C NMR (101 MHz, CDCl3) δ 163.7, 147.3, 138.9, 116.8, 105.5, 42.2, 37.4, 30.7, 25.6, 21.5
13

ppm; IR (ATR): 3452, 2954, 2928, 2870, 1651, 1571, 1547, 1477, 1456, 1378, 1342, 1294, 1258,
1218, 1151, 1137, 1040, 788, 731, 545, 473 cm-1; HRMS (ESI) calculated for [C10H13NO+H]+:
164.1070, found: 164.1068; Rf: 0.18 (EtOAc); [α]D20: 19.3 (c = 0.1, CHCl3).
Chiral HPLC: (Chiralpak ID, 4.6 x 250 mm; hexane:i-PrOH 80:20, 1.0 mL/min, 312 nm; tR (major) =
18.6 min, tR (minor) = 19.8 min), 95.9:4.1 er.

S31
(R)-8-Phenyl-6,7,8,9-tetrahydro-4H-quinolizin-4-one (2b)
Obtained as pale yellow oil in 80% (18.0 mg). 1H NMR (600 MHz, CDCl3) δ 7.35 (t, J
= 7.5 Hz, 2H), 7.31–7.27 (m, 2H), 7.23 (d, J = 7.1 Hz, 2H), 6.52 (d, J = 9.0 Hz, 1H),
6.04 (d, J = 6.8 Hz, 1H), 4.39 (ddd, J = 14.8, 5.5, 4.3 Hz, 1H), 3.90 (m, 1H), 3.08 (m,
2H), 2.94 (m, 1H), 2.37 (m, 1H), 2.07 (m, 1H) ppm; 13
C NMR (151 MHz, CDCl3) δ 163.6, 147.0,
144.0, 139.2, 129.0, 127.2, 126.7, 117.0, 106.0, 42.9, 36.9, 36.7, 30.2 ppm; IR (ATR): 3482, 3028,
2948, 1654, 1574, 1545, 1496, 1454, 1436, 1141, 784, 759, 730, 702, 555, 505, 492, 431 cm -1;
HRMS (ESI) calculated for [C15H15NO+H]+: 226.1226, found: 226.1226; Rf: 0.24 (EtOAc); [α]D20:
30.2.° (c = 0.1, CHCl3).
Chiral HPLC: (Chiralpak AYH, 4.6 x 250 mm; hexane:i-PrOH 80:20, 1.0 mL/min, 312 nm; tR (minor)
= 26.9 min, tR (major) = 34.5 min, 98.9:1.1 er.

S32
(R)-8-(4-Methoxyphenyl)-6,7,8,9-tetrahydro-4H-quinolizin-4-one (2c)
Obtained as white solid in 75% (20.0 mg). 1H NMR (600 MHz, CDCl3) δ 7.27
(dd, J1 = 9.1 Hz, J2 = 6.9 Hz, 1H), 7.14 (d, J = 8.6 Hz, 2H), 6.88 (d, J = 8.6 Hz,
2H), 6.47 (d, J = 9.0 Hz, 1H), 6.01 (d, J = 6.8 Hz, 1H), 4.37 (dd, J = 5.3 Hz, J =
14.8 Hz, 1H), 3.87 (m, 1H), 3.80 (s, 3H), 3.04 (m, 2H), 2.90 (m, 1H), 2.35 (m, 1H), 2.02 (m, 1H) ppm;
C NMR (151 MHz, CDCl3) δ 163.7, 158.6, 147.0, 139.0, 136.1, 127.7, 117.1, 114.3, 105.6, 55.4,
13

42.8, 37.2, 35.8, 30.4 ppm; IR (ATR): 2933, 2835, 1654, 1611, 1573, 1545, 1514, 1463, 1440,
1344, 1297, 1285, 1247, 1180, 1142, 1033, 833, 787, 729, 617, 558, 518, 448, 427, 381 cm-1; HRMS
(ESI) calculated for [C16H17NO+H]+: 256.1332, found: 265.1332; Rf: 0.22 (EtOAc); [α]D20: 47.2°
(c = 0.1, CHCl3).
Chiral HPLC: (Chiralpak AYH, 4.6 x 250 mm; hexane:i-PrOH 80:20, 1.0 mL/min, 312 nm; tR (minor)
= 34.0 min, tR (major) = 44.1 min, 99.2:0.8 er.

S33
(R)-8-(4-(Trifluoromethyl)phenyl)-6,7,8,9-tetrahydro-4H-quinolizin-4-one (2d)
Obtained as colourless oil in 61% (18.0 mg). 1H NMR (600 MHz, CDCl3) δ
7.61 (d, J = 8.1 Hz, 2H), 7.35 (d, J = 8.1 Hz, 2H), 7.29 (m, J = 7.0 Hz, 1H),
6.52 (d, J = 9.0 Hz, 1H), 6.04 (d, J = 6.8 Hz, 1H), 4.42 (dt, J = 14.8, 4.8 Hz,
1H), 3.89 (m, 1H), 3.16 (m, 1H), 3.11 (m, 1H), 2.95 (dd, J1 = 16.3 Hz, J2 = 10.6
Hz), 2.39 (m, 1H), 2.07 (m, 1H) ppm; 13C NMR (151 MHz, CDCl3) δ 163.6, 148.0, 146.2, 139.1, 129.5
(q, J=33.5 Hz), 127.2, 126.0, 125.1, 123.3, 121.5, 117.4, 105.9, 42.5, 36.6, 30.0 ppm; 19F NMR (376
MHz, CDCl3) δ -62.48 ppm; IR (ATR): 3059, 3027, 3001, 2940, 2895, 1650, 1621, 1597, 1558,
1490, 1469, 1454, 1432, 1415, 1379, 1340, 1303, 1257, 1242, 1166, 1094, 1080, 1061, 1028, 1014,
917, 888, 814, 757, 694, 608, 566, 527, 479, 430, 410 cm-1; HRMS (ESI) calculated for
[C16H14F3NO+H]+: 294.1100, found: 294.1109; Rf: 0.28 (EtOAc); [α]D20: 28.0° (c = 0.1, CHCl3).
Chiral HPLC: (Chiralpak AYH, 4.6 x 250 mm; hexane:i-PrOH 80:20, 1.0 mL/min, 312 nm; tR (minor)
= 13.3 min, tR (major) = 14.7 min, 99.2:0.8 er.

S34
(R)-8-(o-Tolyl)-6,7,8,9-tetrahydro-4H-quinolizin-4-one (2e)
Obtained as yellow oil in 71% (17.0 mg); 1H NMR (600 MHz, CDCl3) δ 7.29
(dd, J1 = 9.0 Hz, J2 = 6.9 Hz, 1H), 7.23–7.13 (m, 4H), 6.52 (d, J = 9.0 Hz, 1H), 6.04
(d, J = 6.8 Hz, 1H), 4.39 (dt, J1 = 14.8 Hz, J2 = 5.1 Hz, 1H), 3.94 (m, 1H), 3.28 (m,
J = 5.0 Hz, 1H), 3.04 (m, J = 4.7 Hz, 1H), 2.90 (dd, J1 = 16.5 Hz, J2 = 10.8 Hz, 1H),
2.37 (s, 3H), 2.32 (m, 1H), 2.06 (m, 1H) ppm; C NMR (151 MHz, CDCl3) δ 163.7, 147.3, 142.1,
13

139.1, 135.5, 130.8, 126.9, 126.8, 125.0, 117.1, 105.8, 42.9, 36.2, 32.4, 29.5, 19.6 ppm; IR (ATR):
3055, 3022, 2948, 2928, 1655, 1575, 1544, 1491, 1461, 1436, 1383, 1344, 1290, 1262, 1243,
1161, 1141, 1122, 1052, 1033, 886, 847, 786, 758, 727, 562, 544, 521, 475, 455, 431 cm-1 HRMS
(ESI) calculated for [C16H17NO+H]+: 240.1383, found: 240.1387; Rf: 0.28 (EtOAc); [α]D20: 17.8°
(c = 0.1, CHCl3).
Chiral HPLC: (Chiralpak AYH, 4.6 x 250 mm; hexane:i-PrOH 80:20, 1.0 mL/min, 312 nm; tR (minor)
= 20.4 min, tR (major) = 22.6 min, 96.1:3.9 er.

S35
(R)-8-(Naphthalen-2-yl)-6,7,8,9-tetrahydro-4H-quinolizin-4-one (2f)
Obtained as yellow oil in 79% (21.7 mg). 1H NMR (600 MHz, CDCl3) δ 7.86–
7.77 (m, 3H), 7.66 (s, 1H), 7.52–7.45 (m, 2H), 7.38–7.30 (m, 2H), 6.61 (d, J =
9.0 Hz, 1H), 6.11 (d, J = 6.7 Hz, 1H), 4.46 (dt, J1 = 14.8 Hz, J2 = 5.2 Hz, 1H),
3.97 (m, 1H), 3.26 (m, 1H), 3.19 (dd, J1 = 16.6 Hz, J2 = 3.8 Hz, 1H), 3.07 (dd,
J1 = 16.5 Hz, J2 = 10.8 Hz, 1H), 2.47 (m, 1H), 2.18 (m, 1H) ppm; 13C NMR (151 MHz, CDCl3) δ 163.6,
147.0, 141.3, 140.4, 139.4, 133.6, 132.6, 128.8, 127.8, 126.5, 126.0, 125.2, 125.1, 117.8, 117.0,
43.0, 36.9, 36.8, 30.1 ppm; IR (ATR): 3052, 2955, 2917, 2849, 1655, 1573, 1544, 1508, 1473,
1436, 1422, 1341, 1264, 1238, 1216, 1142, 1063, 1018, 962, 894, 858, 820, 788, 752, 663, 623,
479, 425 cm-1; HRMS (ESI) calculated for [C19H17NO+H]+: 276.1383, found: 276.1380; Rf: 0.35
(EtOAc); [α]D20: 20.0° (c = 0.1, CHCl3).
Chiral HPLC: (Chiralpak AYH, 4.6 x 250 mm; hexane:i-PrOH 80:20, 1.0 mL/min, 312 nm; tR (minor)
= 29.4 min, tR (major) = 38.9 min, 99.0:1.0 er.

S36
(R)-8-(Furan-2-yl)-6,7,8,9-tetrahydro-4H-quinolizin-4-one (2g)
Obtained as yellow oil in 80% (16.0 mg). 1H NMR (600 MHz, CDCl3) δ 7.35 (d, J =
1.4 Hz, 1H), 7.27 (dd, J1 = 9.0 Hz, J2 = 6.9 Hz, 1H), 6.48 (d, J = 9.0 Hz, 1H), 6.31
(dd, J1 = 3.1 Hz, J2 = 2.9 Hz, 1H), 6.06 (m, 2H), 4.20 (dt, J1 = 14.7 Hz, J2 = 5.6 Hz,
1H), 3.98 (m, 1H), 3.21 (m, J = 4.8 Hz, 1H), 3.15 (dd, J1 = 16.4 Hz, J2 = 5.2 Hz, 1H),
2.96 (dd, J1 = 16.4 Hz, J2 = 9.6 Hz, 1H), 2.38 (m, 1H), 2.08 (m, 1H); C NMR (151 MHz, CDCl3) δ
13

163.5, 156.6, 146.0, 141.9, 139.0, 117.2, 110.3, 105.8, 104.8, 41.5, 33.8, 30.2, 27.6 ppm; IR (ATR):
3466, 3113, 2951, 2926, 2854, 1655, 1575, 1546, 1507, 1476, 1438, 1341, 1292, 1177, 1144,
1070, 1010, 944, 919, 884, 849, 788, 734, 600 cm-1; HRMS (ESI) calculated for [C13H13NO2+H]+:
216.1019, found: 216.1023; Rf: 0.25 (EtOAc); [α]D20: 28.5° (c = 0.1, CHCl3).
Chiral HPLC: (Chiralpak IF, 4.6 x 250 mm; hexane:EtOH 80:20, 1.0 mL/min, 312 nm; tR (major) =
26.8 min, tR (minor) = 29.9 min, 96.2:3.8 er.

S37
(R)-8-((S)-4-Methylcyclohex-3-en-1-yl)-6,7,8,9-tetrahydro-4H-quinolizin-4-one (2h)
Obtained as a colourless oil in 90% (22.0 mg). Contains minor amounts of
second set of diastereoisomers, resembling the enantiomeric excess of the
starting material. 1H NMR (600 MHz, CDCl3) δ 7.22 (dd, J = 8.9 Hz, 1H), 6.40 (d,
J = 9.0 Hz, 1H), 5.98 (d, J = 6.8 Hz, 1H), 5.36 (s, 1H), 4.19 (dt, J1 = 14.6 Hz, J2
= 5.2 Hz, 1H), 3.81 (m, 1H), 2.89 (dd, J1 = 16.2 Hz, J2 = 4.7 Hz, 1H), 2.54 (dd, J1 = 16.3 Hz, J2 = 10.3
Hz, 1H), 2.16–2.04 (m, 2H), 2.04–1.91 (m, 2H), 1.86–1.71 (m, 2H), 1.64–1.61 (m, 1H), 1.63 (s, 3H),
1.61–1.53 (m, 1H), 1.46–1.37 (m, 1H), 1.31 (m, 1H) ppm; 13C NMR (151 MHz, CDCl3) δ 163.6, 147.7,
138.9, 134.2, 120.1, 116.7, 105.4, 42.1, 37.9, 35.3, 33.2, 30.3, 29.0, 26.4, 26.3, 23.5 ppm; IR (ATR):
2957, 2912, 2884, 2832, 1656, 1577, 1545, 1477, 1438, 1377, 1342, 1308, 1287, 1220, 1141,
1103, 1052, 1017, 916, 842, 783, 729, 546, 429 cm-1; HRMS (ESI) calculated for [C16H21NO+H]+:
244.1696, found: 244.1699; Rf: 0.35 (DCM:MeOH 20:1); [α]D20: -26.3° (c = 0.1, CHCl3).
Chiral HPLC: (Chiralpak IA, 4.6 x 250 mm; hexane:EtOH 80:20, 1.0 mL/min, 312 nm; tR (major) =
12.2 min, tR (minor) = 13.9 min, 97.5:2.5 dr.

S38
(R)-8-((R)-4-Methylcyclohex-3-en-1-yl)-6,7,8,9-tetrahydro-4H-quinolizin-4-one (2i)

Obtained as colourless oil in 86% (21.0 mg). 1H NMR (400 MHz, CDCl3) δ 7.24
(dd, J1 = 9.0 Hz, J2 = 7.0 Hz, 1H), 6.44 (d, J= 9.0 Hz, 1H), 6.00 (d, J = 6.9 Hz,
1H), 5.37 (s, 1H), 4.20 (m, 1H), 3.84 (m, 1H), 2.83 (dd, J1 = 16.9 Hz, J2 = 4.5 Hz,
1H), 2.56 (dd, J1 = 16.2 Hz, J2 = 9.8 Hz, 1H), 2.19–2.04 (m, 2H), 1.97 (m, 2H),
1.89–1.71 (m, 2H), 1.70–1.55 (s, 3H), 1.53–1.50 (m, 2H), 1.47–1.35 (m, 1H), 1.33–1.23 (m, 1H)
ppm; 13C NMR (101 MHz, CDCl3) δ 163.7, 147.8, 139.0, 134.5, 120.0, 116.7, 105.6, 42.1, 38.0, 35.4,
33.0, 30.4, 29.3, 26.6, 26.3, 23.5 ppm; IR (ATR): 2956, 2911, 2885, 2854, 2833, 1657, 1578,
1546, 1438, 1377, 1344, 1308, 1287, 1238, 1141, 1059, 1046, 915, 895, 798, 782, 728, 423, 418,
406 cm-1;HRMS (ESI) calculated for [C16H21NO+H]+: 244.1696, found: 244.1695; Rf: 0.35
(DCM/MeOH 20:1); [α]D20: 66.7° (c = 0.1, CHCl3).
Chiral HPLC: (Chiralpak IA, 4.6 x 250 mm; hexane:EtOH 80:20, 1.0 mL/min, 312 nm; tR (major) =
10.7 min, tR (minor) = 14.5 min, 98.4:1.6 dr.

S39
(R)-2-Phenyl-1,2,3,4-tetrahydro-6H-pyrido[1,2-b]isoquinolin-6-one (2j)
Obtained as crystalline solid in 87% (24.0 mg). 1H NMR (600 MHz, CDCl3) δ 8.41
(d, J = 8.0 Hz, 1H), 7.60 (t, J = 7.0 Hz, 1H), 7.45–7.39 (m, 2H), 7.35 (t, J = 7.5
Hz, 2H), 7.27 (m, 2H), 6.35 (s, 1H), 4.47 (dt, J1 = 14.3 Hz, J2 = 5.3 Hz, 1H), 4.04
(m, 1H), 3.17–3.09 (m, 2H), 3.01 (dd, J1 = 17.9 Hz, J2 = 12.7 Hz, 1H), 2.41 (m, 1H), 2.10 (m, 1H)
ppm; C NMR (151 MHz, CDCl3) δ 163.1, 144.7, 140.0, 136.9, 132.3, 129.0, 127.9, 127.0, 126.8,
13

125.9, 125.2, 124.6, 104.5, 42.1, 37.2, 37.1, 30.8 ppm; IR (ATR): 3059, 3027, 3001, 2940, 2895,
1650, 1621, 1597, 1558, 1490, 1469, 1454, 1432, 1415, 1379, 1340, 1303, 1257, 1242, 1166, 1094,
1080, 1061, 1028, 1014, 917, 888, 814, 757, 694, 608, 566, 527, 479, 430, 410 cm -1; HRMS (ESI)
calculated for [C19H17NO+H]+: 276.1383, found: 276.1381; Rf: 0.55 (pentane:EtOAc 1:1); [α]D20:
4.17° (c = 0.1, CHCl3); m.p.: 140.7-142.1 °C. This compound was crystallised by slow evaporation
from EtOAc and its absolute configuration assigned by X-ray crystallography as R:

S40
Chiral HPLC: (Chiralpak OZH, 4.6 x 250 mm; hexane:i-PrOH 80:20, 1.0 mL/min, 312 nm; tR (major)
= 15.5 min, tR (minor) = 17.8 min, 98.8:1.2 er.

S41
(R)-9-Phenyl-7,8,9,10-tetrahydropyrido[1,2-a]azepin-4(6H)-one (2k)
Obtained as yellow oil in 82% (19.6 mg). 1H NMR (600 MHz, CDCl3) δ 7.35 (d, J = 7.5
Hz, 1H), 7.33 (d, J = 7.7 Hz, 1H), 7.25 (m, 1H), 7.22–7.17 (m, 3H), 6.50 (d, J = 9.0 Hz,
1H), 6.00 (d, J = 6.6 Hz, 1H), 5.42 (dd, J1 = 14.2 Hz, J2 = 6.9 Hz, 1H), 3.51 (m, J1 =
14.2 Hz, J2 = 10.9 Hz, 1H), 3.22 (m, J1 = 14.3 Hz, J2 = 10.8 Hz, 1H), 2.89 (d, J = 14.4 Hz, 1H), 2.77
(m, J = 12.4 Hz, 1H), 2.19 (m, 1H), 2.11 (dd, J1 = 13.8 Hz, J2 = 3.3 Hz, 1H), 1.83 (qd, J = 3.9 Hz, 1H),
1.58 (m, 1H) ppm; 13
C NMR (151 MHz, CDCl3) δ 163.4, 150.7, 146.9, 139.1, 128.9, 126.8, 126.5,
118.1, 106.6, 45.0, 43.1, 42.1, 38.7, 27.9 ppm; IR (ATR): 3059, 3027, 3002, 2925, 2852, 1656,
1579, 1550, 1493, 1469, 1452, 1435, 1348, 1299, 1233, 1159, 1138, 1083, 1064, 1035, 965, 943,
875, 849, 786, 754, 733, 703, 607, 569, 554, 533, 461, 430 cm-1; HRMS (ESI) calculated for
[C16H17NO+H]+: 240.1383, found: 240.1384; Rf: 0.4 (EtOAc); [α]D20: -174.1° (c = 0.1, CHCl3).
Chiral HPLC: (Chiralpak AYH, 4.6 x 250 mm; hexane:i-PrOH 80:20, 1.0 mL/min, 312 nm; tR (minor)
= 13.0 min, tR (major) = 17.7 min, 95.1:4.9 er.

S42
(R)-9-Methyl-6,7,8,9-tetrahydro-4H-quinolizin-4-one ((+)-2l)
Obtained as yellow oil in 82% (13.1 mg). 1H NMR (400 MHz, CDCl3) δ 7.28 (dd, J1 = 9.0
Hz, J2 = 7.0 Hz, 1H), 6.45 (d, J = 9.0 Hz, 1H), 6.07 (d, J = 7.0 Hz, 1H), 4.51 (dt, J1 = 14.7
Hz, J2 = 5.3 Hz, 1H), 3.61 (m, 1H), 2.82 (m, 1H), 2.06–1.80 (m, 3H), 1.42 (m, 1H), 1.32
(d, J = 6.8 Hz, 3H) ppm; 13C NMR (101 MHz, CDCl3) δ 163.4, 152.8, 138.7, 116.6, 103.4, 40.8, 32.3,
27.3, 20.4, 19.7 ppm; IR (ATR): 3426, 3205, 2946, 2874, 1651, 1568, 1549, 1464, 1419, 1377,
1356, 1328, 1281, 1146, 1049, 798, 734, 552 cm-1; HRMS (ESI) calculated for [C10H13NO+H]+:
164.1070, found: 164.1067; Rf: 0.24 (EtOAc:MeOH 30:1); [α]D20: 9.65° (c = 0.1, CHCl3).
Chiral HPLC: (Chiralpak IB, 4.6 x 250 mm; hexane:EtOH 90:10, 1.0 mL/min, 312 nm; tR (major) =
12.2 min, tR (minor) = 13.4 min, 82.3:17.7 er.

S43
(S)-9-Methyl-6,7,8,9-tetrahydro-4H-quinolizin-4-one ((−)-2l)
Obtained as yellow oil in 66% (10.8 mg). 1H NMR (600 MHz, CDCl3) δ 7.28 (dd, J1 = 9.0
Hz, J2 = 7.0 Hz, 1H), 6.44 (d, J = 9.0 Hz, 1H), 6.07 (d, J = 7.0 Hz, 1H), 4.51 (dt, J1 = 14.3
Hz, J2 = 5.4 Hz, 1H), 3.61 (m, 1H), 2.84 (m, 1H), 2.05–1.92 (m, 2H), 1.88 (m, 1H), 1.45–
1.36 (m, 1H), 1.32 (d, J = 6.9 Hz, 3H) ppm; 13C NMR (151 MHz, CDCl3) δ 163.5, 152.8, 138.7, 116.7,
103.3, 40.8, 32.3, 27.3, 20.5, 19.7 ppm; IR (ATR): 3422, 3212, 2946, 2960, 2941, 2873, 1654,
1575, 1550, 1465, 1420, 1379, 1354, 1323, 1282, 1163, 1146, 1057, 1045, 939, 850, 794v, 564,
535, 421 cm-1; HRMS (ESI) calculated for [C10H13NO+H]+: 164.1070, found: 164.1069; Rf: 0.25
(EtOAc:MeOH 30:1); [α]D20: -18.7° (c = 0.1, CHCl3).
Chiral HPLC: (Chiralpak IB, 4.6 x 250 mm; hexane:EtOH 90:10, 1.0 mL/min, 312 nm; tR (minor) =
12.3 min, tR (major) = 13.3 min, 87.3:12.7 er.

S44
9-Phenyl-6,7,8,9-tetrahydro-4H-quinolizin-4-one (2m)
Obtained as white solid in 77% (17.3 mg). 1H NMR (400 MHz, CDCl3) δ 7.39–7.27 (m,
4H), 7.25–7.13 (m, 2H), 6.56 (d, J = 8.9 Hz, 1H), 5.73 (d, J = 7.0 Hz, 1H), 4.22 (m, 1H),
4.06 (m, 1H), 2.18 (m, 1H), 2.13–1.93 (m, 3H) ppm; 13C NMR (101 MHz, CDCl3) δ 163.6,
150.6, 142.6, 138.7, 128.9, 128.5, 127.4, 117.0, 107.3, 45.3, 42.4, 28.0, 20.7 ppm; IR (ATR):
3437, 3060, 3029, 2947, 1967, 1654, 1576, 1543, 1494, 1474, 1453, 1420, 1277, 1163, 1138, 1026,
798, 766, 733, 702, 551, 536, 460, 422, 410 cm-1; HRMS (ESI) calculated for [C15H15NO+H]+:
226.1226, found: 226.1224; Rf: 0.35 (EtOAc:MeOH 20:1);
Chiral HPLC: (Chiralpak IB, 4.6 x 250 mm; hexane:i-PrOH 80:20, 1.0 mL/min, 312 nm; tR (minor) =
13.0 min, tR (major) = 15.6 min, 49.8:50.2 er.

S45
2',3'-dihydro-5'H-spiro[cyclopentane-1,1'-indolizin]-5'-one (2n)
Obtained as colourless oil in 74% (14.0 mg). 1H NMR (600 MHz, CDCl3) δ 7.25 (dd, J1
= 9.0 Hz, J2 = 6.9 Hz, 1H), 6.46 (d, J = 9.0 Hz, 1H), 5.96 (d, J = 6.9 Hz, 1H), 4.24 (m,
1H), 3.95 (m, 1H), 2.39 (m, 1H), 2.27 (m, 1H), 2.14 (m, 1H), 2.00 (m, 1H), 1.88 (m, 2H),
1.72 (m, 1H), 1.59 (m, 2H), 1.33 (m, 1H) ppm; 13
C NMR (151 MHz, CDCl3) δ 163.7,
151.9, 138.7, 117.2, 102.8, 46.7, 43.1, 39.8, 31.0, 27.4, 27.2, 23.0 ppm; IR (ATR): 3449, 2947,
2870, 1653, 1578, 1550, 1471, 1455, 1416, 1342, 1286, 1267, 1180, 1159, 1138, 1058, 999, 982,
952, 897, 850, 802, 740, 570, 549, 502, 451 cm-1; HRMS (ESI) calculated for [C12H15NO+H]+:
190.1226, found: 190.1231; Rf: 0.2 (EtOAc).

S46
(1S,2S)-1,2-dimethyl-3,4-dihydro-1H-quinolizin-6(2H)-one (2o)
Obtained as yellow oil in 42% (7.5 mg), 11:1 dr (cis/trans). 1H NMR (400 MHz, CDCl3)
δ 7.31 – 7.26 (m, 1H), 6.44 (dt, J = 9.1, 1.0 Hz, 1H), 6.10 (dt, J = 7.0, 1.2 Hz, 1H), 4.21
(ddd, J = 14.6, 6.4, 5.2 Hz, 1H), 3.86 (ddd, J = 14.3, 8.4, 4.5 Hz, 1H), 2.45 (p, J = 7.1
Hz, 1H), 2.00 (ddq, J = 10.4, 5.3, 2.9, 1.9 Hz, 1H), 1.65 – 1.51 (m, 2H); 13C NMR (151 MHz, CDCl3)
δ 163.4, 152.1, 138.7, 116.3, 104.3, 39.9, 39.7, 32.3, 29.1, 20.6, 19.3;b IR (ATR): 3486, 2959,
2931, 2873, 1649, 1574, 1543, 1456, 1421, 1374, 1340, 1268, 1153, 1135, 1087, 1038, 999, 851,
795, 763, 732, 563, 543 cm-1; HRMS (ESI) calculated for [C11H15NO+H]+: 178.1226, found: 178.1230;
Rf: 0.2 (EtOAc); [α]D20: -28.2° (c = 0.1, CHCl3).
Chiral HPLC: Chiralpak IB, 4.6 x 250 mm; hexane:EtOH 90:10, 1.0 mL/min, 280 nm; tR (minor) =
10.5 min, tR (major) = 12.0 min, 89:11 er.
The corresponding racemate was obtained as a 2:1 (cis/trans) mixture of isomers.

S47
(R)-2-methyl-6-phenyl-5,6,7,8-tetrahydro-1H-pyrido[1,2-c]pyrimidine-1,3(2H)-dione (4a)
Obtained as colourless oil in 91% (21.0 mg). 1H NMR (400 MHz, CDCl3) δ 7.39–
7.33 (m, 2H), 7.31–7.27 (m, 1H), 7.24–7.20 (m, 2H), 5.59 (s, 1H), 4.20 (dt, J1 = 9.7
Hz, J2 = 4.2 Hz, 1H), 3.74 (m, 1H), 3.36 (s, 3H), 3.04 (m, 1H), 2.93 (m, 1H), 2.82
13
(ddd, J1 = 16.8 Hz, J2 = 10.9 Hz, J3 = 1.5 Hz, 1H), 2.32 (m, 1H), 2.04 (m, 1H) ppm; C NMR (101
MHz, CDCl3) δ 162.7, 152.5, 151.8, 143.1, 129.1, 127.4, 126.6, 99.6, 43.6, 36.6, 36.0, 30.1, 27.9
ppm; IR (ATR): 3026, 2950, 1688, 1655, 1612, 1486, 1449, 1422, 1370, 1337, 1305, 1258, 1240,
1210, 1177, 1160, 1100, 1082, 1065, 1030, 993, 939, 914, 890, 817, 758, 722, 702, 679, 654, 609,
586, 540, 438, 402 cm-1; HRMS (ESI) calculated for [C15H16N2O2+H]+: 257.1285, found: 257.1294;
Rf: 0.2 (pentane:EtOAc 1:1); [α]D20: 12.4° (c = 0.1, CHCl3).
Chiral HPLC: (Chiralpak IF, 4.6 x 250 mm; hexane:i-PrOH 70:30, 1.0 mL/min, 270 nm; tR (major) =
27.7 min, tR (minor) = 31.8 min, 94.5:5.5 er.

S48
(R)-2-benzyl-6-phenyl-5,6,7,8-tetrahydro-1H-pyrido[1,2-c]pyrimidine-1,3(2H)-dione (4b)
Obtained as colourless oil in 86% (28.5 mg). 1H NMR (600 MHz, CDCl3) δ 7.50
(d, J = 7.2 Hz, 2H), 7.38–7.24 (m, 6H), 7.21 (d, J = 7.3 Hz, 2H), 5.60 (s, 1H), 5.14
(d, J = 2.1 Hz, 2H), 4.18 (dt, J1 = 13.8 Hz, J2 = 4.3 Hz, 1H), 3.70 (m, 1H), 3.01 (m,
1H), 2.93 (m, 1H), 2.79 (m, 1H), 2.30 (m, 1H), 2.01 (m, 1H) ppm; 13
C NMR (151 MHz, CDCl3) δ
162.4, 152.3, 152.1, 143.0, 137.1, 129.2, 129.1, 128.5, 127.7, 127.4, 126.6, 99.9, 44.4, 43.6, 36.6,
36.1, 30.0 ppm; IR (ATR): 3085, 3061, 3030, 3005, 2952, 2927, 2856, 1699, 1485, 1448, 1424,
1399, 1341, 1213, 1196, 1072, 1030, 933, 917, 819, 759, 723, 700, 608, 580, 543, 505, 445, 416
cm-1; HRMS (ESI) calculated for [C21H20N2O2+H]+: 333.1598, found: 333.1590; Rf: 0.49
(pentane:EtOAc 1:1); [α]D20: 7.8° (c = 0.1, CHCl3).
Chiral HPLC: (Chiralpak IG, 4.6 x 250 mm; hexane:EtOH 80:20, 1.0 mL/min, 270 nm; tR (minor) =
34.8 min, tR (major) = 37.9 min, 98.0:2.0 er.

S49
(R)-8-(naphthalen-2-yl)-6,7,8,9-tetrahydro-2H-quinolizin-2-one (4c)
Obtained as colourless oil in 58 % (16.0 mg). 1H NMR (600 MHz, CD3OD)
δ 7.81 (d, J = 17.2 Hz, 1H) 7.74(d, J = 8.5 Hz, 2H), 7.71 (d, J = 7.4 Hz, 1H),
7.46–7.39 (m, 3H), 6.43 (dd, J1 = 7.4 Hz, J2 = 2.7 Hz, 1H), 6.36 (d, J = 2.4
Hz, 1H), 4.23 (m, 1H), 4.17 (m, 1H), 3.31 (m, 1H), 3.18 (dd, J1 = 16.6 Hz, J2 = 4.8 Hz, 1H), 3.10 (dd,
J1 = 17.9 Hz, J2 = 10.8 Hz, 1H), 2.36 (m, 1H), 2.25 (m, 1H) ppm; C NMR (151 MHz, CD3OD) δ
13

180.3, 152.8, 143.7, 142.6, 135.1, 134.0, 129.6, 128.8, 128.6, 127.3, 126.8, 126.3, 126.1, 117.5,
117.3, 71.5, 52.7, 37.7, 36.5, 30.9 ppm; IR (ATR): 3393, 3305, 3270, 3053, 3020, 2927, 1635,
1600, 1508, 1486, 1415, 1360, 1351, 1313, 1266, 1228, 1197, 1172, 1111, 1016, 859, 821, 752,
660, 620 cm-1; HRMS (ESI) calculated for [C19H17NO+H]+: 164.1070, found: 276.1383; Rf: 0.25
(DCM:MeOH 9:1); [α]D20: -64.1° (c = 0.1, CHCl3).
SFC: (ODH column, 30.0 ppm MeOH in supercritical CO2 as eluent, 4 mL/min., 270 nm; tR (minor) =
16.8 min, tR (major) = 23.8 min, 98.8:1.2 er.

S50
(R)-8-phenyl-6,7,8,9-tetrahydro-2H-quinolizin-2-one (4d)

Obtained as colourless oil in 55 % (12.5 mg). 1H NMR (400 MHz, CD3OD) δ 7.71
(d, J = 7.5 Hz, 1H), 7.34–7.18 (m, 5H), 6.38 (dd, J1 = 7.4 Hz, J2 = 2.8 Hz, 1H), 6.31
(d, J = 2.5 Hz, 1H), 4.25–4.09 (m, 2H), 3.21–3.06 (m, 2H), 3.01 (dd, J1 = 17.4 Hz, J2 = 11.0 Hz, 1H),
2.29 (m, 1H), 2.17 (m, 1H) ppm; C NMR (151 MHz, CD3OD) δ 180.5, 152.7, 145.3, 143.6, 129.9,
13

128.0, 127.8, 117.6, 117.3, 52.6, 37.7, 36.7, 31.1 ppm; IR (ATR): 3396, 3061, 3029, 2954, 2923,
2852, 1636, 1553, 1487, 1453, 1426, 1414, 1358, 1266, 1226, 1197, 1169, 1110, 1098, 1082, 1030,
888, 857, 830, 753, 702, 556, 545, 517, 480, 436, 396 cm-1; HRMS (ESI) calculated for
[C15H15NO+H]+: 226.1226, found: 226.1230; Rf: 0.2 (DCM:MeOH 9:1); [α]D20: -14.5° (c = 0.1,
CHCl3).
SFC: (ODH column, 30.0 ppm MeOH in supercritical CO2 as eluent, 4 mL/min., 260 nm; tR (minor) =
4.3 min, tR (major) = 5.8 min, 98.1:1.9 er.

S51
(R)-8-(naphthalen-1-yl)-6,7,8,9-tetrahydro-2H-quinolizin-2-one (4e)
Obtained as a colourless oil in 51 % (14.0 mg). 1H NMR (600 MHz, CD3OD)
δ 8.15 (d, J = 8.5 Hz, 1H), 7.88 (d, J = 8.0 Hz, 1H), 7.83 (d, J = 7.4 Hz, 1H),
7.77 (d, J = 8.0 Hz, 1H), 7.54 (t, J = 7.0 Hz, 1H), 7.49 (t, J = 7.3 Hz, 1H), 7.44
(t, J = 7.4 Hz, 1H),7.40 (d, J = 7.0 Hz, 1H), 6.51 (dd, J1 = 7.4 Hz, J2 = 2.7 Hz, 1H), 6.44 (d, J = 2.4
Hz, 1H), 4.35–4.23 (m, 2H), 4.05 (m, J = 5.0 Hz, 1H), 3.31 (m, 1H), 3.14 (dd, J1 = 17.0 Hz, J2 = 10.4
Hz, 1H), 2.45 (m, 1H), 2.31 (m, 1H) ppm; 13C NMR (151 MHz, CD3OD) δ 179.5, 153.5, 144.1, 140.8,
135.6, 132.5, 130.1, 128.6, 127.5, 126.8, 126.7, 123.9, 123.6, 117.3, 117.0, 52.9, 36.3, 32.5, 30.6
ppm; IR (ATR): 3389, 3049, 2954, 2925, 1636, 1597, 1510, 1487, 1399, 1359, 1300, 1264, 1248,
1226, 1198, 1173, 1113, 1099, 1082, 1018, 948, 857, 830, 803, 785, 749, 658, 565, 437, 427 cm-.
HRMS (ESI) calculated for [C19H17NO+H]+: 276.1383, found: 276.1385; Rf: 0.25 (DCM:MeOH 9:1);
[α]D20: -11.5° (c = 0.1, CHCl3).
SFC: (ODH column, 30.0 ppm MeOH in supercritical CO2 as eluent, 4 mL/min., 210 nm; tR (minor) =
11.3 min, tR (major) = 29.6 min, 95.9:4.1 er.

S52
(R)-8-methyl-6,7,8,9-tetrahydro-2H-quinolizin-2-one (4f)

Obtained as a colourless oil in 86 % (14.0 mg). 1H NMR (600 MHz, CD3OD) δ 7.66
(d, J = 7.4 Hz, 1H), 6.34 (dd, J1 = 7.4 Hz, J2 = 2.8 Hz, 1H), 6.26 (d, J = 2.5 Hz, 1H),
4.09 (m, 1H), 3.99 (m, 1H), 2.90 (dd, J1 = 16.8 Hz, J2 = 5.0 Hz, 1H), 2.44 (dd, J1 = 16.8 Hz, J2 = 10.2
Hz, 1H), 2.06 (m, 1H), 1.98 (m, 1H), 1.60 (m, 1H), 1.07 (d, J = 6.6 Hz, 3H) ppm; 13C NMR (151 MHz,
CD3OD) δ 180.4, 152.8, 143.5, 117.4, 117.2, 52.3, 37.1, 31.5, 26.8, 21.6 ppm; IR (ATR): 3383,
3078, 3032, 2937, 2978, 1634, 1478, 1418, 1439, 1376, 1223, 1197, 1110, 1098, 1082, 874, 828,
772, 703, 552, 526 cm-1; HRMS (ESI) calculated for [C10H10NO]+ 164.1070, found 164.1070; ; Rf: 0.3
(DCM:MeOH 9:1); [α]D20: -3.21° (c = 0.1, CHCl3).
For er determination compound 4f was converted into pyridine-4-thiol 5.

S53
(R)-8-methyl-6,7,8,9-tetrahydro-2H-quinolizine-2-thione (5)
In a round bottom flask 4-pyridone 4f (10.0 mg, 0.06, 1 eq) and Lawesson`s reagent
(14.0 mg, 0.03 mmol, 0.55 eq) were suspended in toluene (1.2 mL) and heated at
110°C for 1h. Subsequently the reaction mixture was concentrated and purified by silica gel column
(DCM:MeOH, 20:1). The product was obtained as yellow solid in 82% (9.0 mg). 1H NMR (600 MHz,
CD3OD) δ 7.52 (d, J = 6.8 Hz, 1H), 7.26 (s, 1H), 7.25 (dd, J1 = 6.8 Hz, J2 = 2.2 Hz, 1H), 4.17 (m, 1H),
4.08 (m, 1H), 2.93 (dd, J1 = 17.2 Hz, J2 = 5.2 Hz, 1H), 2.48 (dd, J1 = 17.1 Hz, J2 = 10.2 Hz, 1H), 2.09
(m, 1H), 2.03 (m, 1H), 1.65 (d, J = 6.5 Hz, 1H), 1.23 (s, H) ppm; C NMR (151 MHz, CD3OD) δ
13

186.2, 148.3, 138.5, 131.4, 130.2, 53.2, 36.6, 31.1, 26.7, 21.5 ppm; IR (ATR): 3099, 3033, 2940,
2927, 2868, 2728, 1617, 1532, 1461, 1447, 1379, 1293, 1268, 1240, 1217, 1193, 1174, 1125, 1089,
1061, 1023, 967, 958, 938, 891, 857, 827, 753, 683, 568, 555, 432 cm-1; HRMS (ESI) calculated for
[C10H13NS+H]+: 180.0841, found: 180.0842; Rf: 0.4 (DCM:MeOH 20:1); ); [α]D20: -54.7° (c = 0.1,
CHCl3). m.p.: 144-146 °C.
Chiral HPLC: (Chiralpak IG, 4.6 x 250 mm; hexane:EtOH 80:20, 1.0 mL/min, 348 nm; tR (major) =
38.4 min, tR (minor) = 40.8 min, 94.2:5.8 er.

S54
Preparation of Transition metal NHC complexes

[L9Ni(Cp)Cl]
According to the procedure reported by Nolan.[8] Inside a glove box
in a 10ml microwave vial nickellocene (15.0 mg, 0.08 mmol) and
imidazolim salt S14 (55.7 mg, 0.079 mmol) were suspended in THF
(1.6 mL). The vial was sealed and the mixture was heated to 75°C
outside the glove box for 16h. Subsequently the reaction mixture
was concentrated, and the crude residue was dissolved in CH2Cl2 (3 mL) and was filtered over a bed
of Celite over silica (2 cm of each). The dark solution was concentrated to yield 51.2 mg (78%) of
the title compound as a violet solid. Crystals suitable for X-ray crystallography were obtained by slow
evaporation from CH2Cl2.

H NMR (400 MHz, CDCl3) δ 7.90 (d, J = 7.4 Hz, 4H), 7.46 (t, J = 7.3 Hz, 4H), 7.33 (s, 4H), 7.10 (d,
1

J = 7.2 Hz, 8H), 6.84 (s, 4H), 5.83 (s, 2H), 4.85 (d, J = 6.8 Hz, 2H), 4.39 (s, 5H), 3.74 (d, J = 6.8 Hz,
2H), 2.45 (s, 6H), 1.56 – 1.36 (m, 12H) ppm; 13C NMR (151 MHz, CDCl3) δ 166.18, 147.43, 145.67,
144.79, 142.14, 139.74, 136.39, 129.59, 129.02, 128.76, 128.00, 127.36, 126.96, 126.70, 126.42,
93.30, 41.19, 39.55, 24.31, 23.59, 22.13 ppm; IR (ATR): 3139, 3058, 2967, 2872, 1601, 1582,
1493, 1448, 1398, 1373, 1316, 1262, 1157, 1081, 1029, 947, 910, 866, 779,759, 699, 577 cm-1;
HRMS (ESI) calculated for [C54H53N2Ni]+: 787.3562, found: 787.3568; [α]D20: -24.0° (c = 0.1, CHCl3).
m.p.: decomposition above 205 °C.

S55
L13Ni(Cp)Cl]
According to the procedure reported by Nolan.[8] Inside a glove box
in a 20ml microwave vial nickellocene (49.0 mg, 0.26 mmol) and
imidazolim salt S17 (214 mg, 0.26 mmol) were suspended in THF
(5.2 mL). The vial was sealed and the mixture was heated to 75°C
outside the glove box for 16h. Subsequently the reaction mixture
was concentrated, and the crude residue was dissolved in CH2Cl2 (6
mL) and was filtered over a bed of Celite over silica (4 cm of each). The dark solution was
concentrated to yield 215 mg (87%) of the title compound as a violet solid. Crystals suitable for X-
ray crystallography were obtained by slow evaporation from toluene.

H NMR (400 MHz, CDCl3) δ 7.84 (s, 4H), 7.66 – 7.31 (m, 10H), 6.72 (d, J = 53.1 Hz, 8H), 6.29 (s,
1

6H), 5.86 (s, 2H), 4.99 (s, 2H), 4.37 (s, 5H), 3.95 (s, 2H), 2.61 (s, 6H), 1.50 (s, 12H), 0.08 (s, 6H);
13
C NMR (151 MHz, CDCl3) δ 173.3, 144.8, 144.5, 144.3, 143.1, 141.8, 139.5, 137.9, 134.6, 129.1,
128.8, 128.4, 128.3, 127.4, 127.2, 126.8, 126.4, 126.1, 125.3, 120.6, 92.9, 41.1, 39.2, 24.7, 24.0,
22.2; IR (ATR): 3058, 3027, 2967, 2930, 2872, 1700, 1602, 1582, 1478, 1448, 1374, 1306, 1261,
1084, 1070, 1050, 1030, 1017, 910, 866, 802, 762, 731, 698 cm-1; HRMS (ESI) calculated for
[C64H57N2Ni]+: 911.3870, found: 911.3865; [α]D20: -42.9° (c = 0.1, CHCl3).

S56
[L9AuCl]
In a 10ml flask L9 (50 mg, 0.08 mmol, 1.0 eq) and
chloro(dimethylsulfide)gold(I) (22.4 mg, 0.08 mmol, 1.0 eq) were
dissolved in THF (1.85 mL) inside a glove box. The mixture was
stirred for 5h at ambient temperature outside the glove box.
Subsequently a spatula of charcoal was added and the mixture was stirred for 20 mins and then
filtered over silica and celite, washing with THF and CH2Cl2. The crude mixture was concentrated to
yield 67 mg (99 %) of the desired complex as a off white solid. Crystals suitable for X-ray
crystallography were obtained by slow diffusion of Hexane into a saturated solution of [L9AuCl] in
THF.

H NMR (400 MHz, CDCl3) δ 7.52 (d, J = 7.6 Hz, 4H), 7.34 (t, J = 7.7 Hz, 4H), 7.22 (t, J = 7.3 Hz,
1

2H), 7.17 – 7.03 (m, 8H), 6.89 – 6.77 (m, 6H), 6.43 (s, 2H), 3.92 (dd, J = 14.7, 7.2 Hz, 4H), 2.32 (s,
6H), 1.54 (d, J = 7.1 Hz, 6H), 1.48 (d, J = 7.1 Hz, 6H) ppm; C NMR (101 MHz, CDCl3) δ 175.40,
13

146.03, 144.29, 143.48, 142.02, 140.50, 132.74, 128.62, 128.35, 128.02, 127.23, 126.56, 126.15,
125.53, 123.27, 39.80, 38.34, 22.65, 22.06, 21.76 ppm; IR (ATR): 3082, 3058, 3024, 2967, 2930,
2872, 1602, 1583, 1555, 1494, 1472, 1417, 1375, 1347, 1314, 1293, 1157, 1079, 1062, 1030, 1013,
951, 910, 892, 864, 786, 757, 700, 588, 574, 553, 474 cm-1; HRMS (ESI) calculated for
[C49H48N2Au+CH3CN]+: 902.3749, found: 902.3758; [α]D20: 260.3° (c = 0.1, CHCl3). m.p.: 317-
319 °C.

S57
[L13AuCl]
In a 10ml flask L13 (40 mg, 0.05 mmol, 1.0 eq) and
chloro(dimethylsulfide)gold(I) (15.1 mg, 0.05 mmol, 1.0 eq) were
dissolved in THF (1.7 mL) inside a glove box. The mixture was
stirred for 6h at ambient temperature outside the glove box.
Subsequently a spatula of charcoal was added and the mixture was
stirred for 20 mins and then filtered over silica and celite, washing
with THF and CH2Cl2. The crude mixture was concentrated to yield 49.5 mg (96 %) of the desired
complex as a brown solid. Crystals suitable for X-ray crystallography were obtained by slow diffusion
of Hexane into a saturated solution of [L13AuCl] in THF at -30°C.

H NMR (400 MHz, CDCl3) δ 7.69 (d, J = 8.3 Hz, 2H), 7.50 (d, J = 7.6 Hz, 4H), 7.30 (t, J = 7.6 Hz,
1

4H), 7.24 (s, 2H), 7.21 (t, J = 7.2 Hz, 4H), 6.97 (d, J = 10.4 Hz, 3H), 6.79 (d, J = 6.7 Hz, 4H), 6.75 –
6.66 (m, 7H), 4.28 – 4.21 (m, 2H), 4.01 (q, J = 7.1 Hz, 2H), 2.39 (s, 6H), 1.50 (d, J = 7.1 Hz, 6H),
1.45 (d, J = 7.5 Hz, 6H) ppm;13C NMR (101 MHz, CDCl3) δ 179.94, 144.82, 143.86, 143.64, 143.14,
140.72, 138.38, 135.76, 131.59, 128.58, 128.06, 127.88, 127.42, 127.32, 127.05, 126.47, 125.76,
125.53, 124.87, 121.79, 39.99, 38.55, 22.58, 21.91, 21.74 ppm; IR (ATR): 3084, 3059, 3025,
2966, 2930, 2872, 2234, 2803, 1729, 1602, 1478, 1389, 1375, 1318, 1156, 1030, 909, 864, 819,
767, 730, 699, 647, 608, 576, 555, 524 cm-1; HRMS (ESI) calculated for [C59H52N2Au+CH3CN]+:
1026.4062, found: 1026.4046; [α]D20: -20.0° (c = 0.1, CHCl3).

S58
References

(1) Gao, F.; Hoveyda, A. H. J. Am. Chem. Soc. 2010, 132, 10961.
(2) (a) Albright, A.; Eddings, D.; Black, R.; Welch, C. J.; Gerasimchuk, N. N.; Gawley, R. E. J. Org.
Chem. 2011, 76, 7341.
(b) Spahn, E.; Albright, A.; Shevlin, M.; Pauli, L. Pfaltz, A.; Gawley, R. E. J. Org. Chem. 2013, 78,
2731.
(3) Donets, P. A.; Cramer. N. Angew. Chem. Int. Ed. 2015, 54, 633.
(4) Rodini, D. J.; Kirk, T. C.; Cordova, R.; Snider, B. B. J. Am. Chem. Soc. 1982, 104, 555.
(5) Pizzirani, D.; Pagliuca, C.; Realini, N.; Branduardi, D.; Bottegoni, G.; Mor, M.; Bertozzi, F.;
Scarpelli, R.; Piomelli, D.; Bandiera, T. J. Med. Chem. 2013, 56, 3518.
(6) Guerry, P.; Neier, R. Synthesis 1984, 6, 485.
(7) Methylaluminum bis(2,6-di-tert-butyl 4-methylphenoxide): Maruoka, K.; Itoh, T.; Yamamoto, H. J.
Am. Chem. Soc. 1985, 107, 4573.
(8) Martin, A. R.; Makida, Y.; Meiries, S.; Slawin, A. M. Z.; Nolan, S. P. Organometallics 2013, 32,
6265.

S59
NMR-Spectra

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(Z)-1l

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