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PAPER www.rsc.org/greenchem | Green Chemistry

Palladium-catalyzed addition of diaryl disulfides and diselenides to terminal

alkynes in room temperature ionic liquids{
Mingzhong Cai,* Yongguang Wang and Wenyan Hao
Received 27th April 2007, Accepted 31st July 2007
First published as an Advance Article on the web 16th August 2007
DOI: 10.1039/b706320b

Palladium-catalyzed addition reactions of diaryl disulfides and diselenides to terminal alkynes can
proceed smoothly in room temperature ionic liquid, 1-butyl-3-methylimidazolium
hexafluorophosphate ([bmim][PF6]), to afford the corresponding (Z)-1,2-bis(arylthio)-1-alkenes
Published on 16 August 2007 on http://pubs.rsc.org | doi:10.1039/B706320B

or (Z)-1,2-bis(arylseleno)-1-alkenes in excellent yields. Our system not only avoids the use of
highly toxic benzene or toluene as a solvent but also solves the basic problem of palladium
catalyst reuse.

Introduction Recently, Beletskaya et al. described the stereoselective S–S

bond addition to terminal alkynes catalyzed by a polymer-
The development of environmentally friendly synthetic proce- supported palladium catalyst, the reaction was conducted in a
dures has become a major concern throughout the chemical sealed tube at 140 uC using toluene as the solvent and the
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industry, due to continuing depletion of natural resources and methodology was not applicable for Se–Se bond addition to
growing environmental awareness.1 One of the major efforts in alkynes.17 In this paper, we describe the palladium-catalyzed
academic research and industry is the search for replacements addition of diaryl disulfides and diselenides to terminal alkynes
to the environmentally damaging organic solvents used on a in room temperature ionic liquids. The developed methodo-
large scale, especially those which are volatile and difficult to logy has important practical advantages deserving special note.
contain. Room temperature ionic liquids, especially those
based upon the 1,3-dialkylimidazolium cation, have attracted
Results and discussion
growing interest in the last few years.2 They offer an
alternative and ecologically sound medium compared to We found that the Pd(PPh3)4-catalyzed addition reaction of
conventional organic solvents because of their negligible vapor diphenyl disulfide to 1-hexyne in [bmim][PF6] occurred
pressure, ease of handling and potential for recycling. smoothly at 60 uC, and was complete within 2 h to afford
Furthermore, their high compatibility with transition metal stereoselectively (Z)-1,2-bis(phenylthio)-1-hexene (2a) in 95%
catalysts and limited miscibility with common solvents, enables yield. The scope of the reaction has been studied for different
easy product and catalyst separation with the retention of the alkynes and diaryl disulfides (Scheme 1). The experimental
stabilized catalyst in the ionic phase. These and related ionic results are summarized in Table 1. As shown in Table 1, the
liquids have been successfully applied to hydrogenations,3 addition reactions of diaryl disulfides to a variety of terminal
alkene dimerizations,4 Friedel–Crafts reactions,5 Diels–Alder alkynes proceeded very smoothly to give stereoselectively the
reactions,6 Heck reactions,7 Bechmann condensations8 and
Suzuki reactions.9
Catalytic diaryl disulfides and diselenides additions to
terminal alkynes has been discovered by A. Ogawa, N.
Sonoda et al.10,11 The products of the addition reaction are
of high practical interest in organic chemistry12,13 and Scheme 1
materials science.14,15 The mechanism of this catalytic reaction Table 1 Palladium-catalyzed addition of Ar2S2 to various acetylenesa
has been extensively studied and proceeds via: (1) oxidative
Entry R Ar Product Yield (%)b
addition of S–S or Se–Se bond to Pd(0); (2) the stereoselective
insertion of acetylenes into the Pd–S or Pd–Se bond; (3) C–S or 1 n-C4H9 Ph 2a 95
C–Se reductive elimination.10,11,16 The reaction is catalyzed by 2 n-C4H9 4-CH3C6H4 2b 94
Pd(PPh3)4 at 80 uC using benzene as the solvent, however, the 3 HOCH2 Ph 2c 98
4 HOCH2 4-CH3C6H4 2d 96
homogeneous palladium catalyst can not be recovered and 5 CH3OCH2 4-CH3C6H4 2e 95
reused and the benzene is easily volatile and highly toxic. These 6 Ph 4-CH3C6H4 2f 94
disadvantages have so far precluded its practical applications. 7 n-C6H13 4-CH3C6H4 2g 96
8 H2NCH2 Ph 2h 93
9 n-C6H13 Ph 2i 95
Department of Chemistry, Jiangxi Normal University, Nanchang, a
Reactions were conducted under the conditions of 1.2 mmol of
330022, P. R. China. E-mail: caimzhong@163.com; acetylene 1 and 1.0 mmol of Ar2S2 in the presence of Pd(PPh3)4
Fax: +86-(791)-8517500 (2 mol%) in [bmim][PF6] (1.5 mL) at 60 uC for 2 h. b Isolated yield
{ Electronic supplementary information (ESI) available: based on the Ar2S2 used.
Supplementary information. See DOI: 10.1039/b706320b

1180 | Green Chem., 2007, 9, 1180–1184 This journal is ß The Royal Society of Chemistry 2007
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petroleum ether 3 times. The 95–97% product purity was

achieved after removing light petroleum ether and unreacted
alkynes under reduced pressure. The purity of the products 2
and 3 were established with 1H NMR, 13C NMR and
Scheme 2 elemental analysis. Z-Configuration of the double bond of
products 2 and 3 was determined with 2D NOESY experiment.
corresponding (Z)-1,2-bis(arylthio)-1-alkenes 2a–i in excellent Therefore, none of the special purification procedures were
yields, with high stereoselectivity (Z/E . 99 : 1) after 2 h of required, in contrast to the traditional method, which requires
reaction time. Some functional groups, such as hydroxy chromatography to remove catalyst and ligand.10 To evaluate
(entries 3, 4), amino (entry 8), and methoxy (entry 5) groups, the possibility of recycling the ionic liquid and palladium
did not affect the addition of Ar2S2 to alkynes. The ionic catalyst used in the reaction, Ph2Se2, 1-hexyne and Pd(PPh3)4
liquid, [bmim][PF6], has the advantages of rate acceleration, were allowed to react in [bmim][PF6] at 60 uC for 2 h and then
increase of yield and requiring a lower reaction temperature the product was extracted with light petroleum ether 3 times,
Published on 16 August 2007 on http://pubs.rsc.org | doi:10.1039/B706320B

over benzene as the solvent. For example, the preparation of affording the cleaned, ionic liquid, catalytic solution. After the
(Z)-1,2-bis(phenylthio)-3-hydroxy-1-propene (2c) was success- recovered ionic liquid containing the palladium catalyst was
ful in [bmim][PF6] after only 2 h and gave a 98% yield (entry 3), concentrated in vacuo (5.0 torr, r.t. for 1 h), a second amount
but the same reaction run in benzene gave a 79% yield when of reactants were added and the process was repeated up to 4
stopped after 12 h.10 times. It seems that there is no effect on the rate and yield of
The developed methodology was also applicable for Ar2Se2 the reaction during each cycle (Table 3), the result is important
addition to terminal alkynes. The palladium-catalyzed from a practical point of view.
addition reactions of Ar2Se2 to a variety of terminal alkynes
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were investigated (Scheme 2), the experimental results are Experimental

summarized in Table 2. As shown in Table 2, the addition
reactions of diaryl diselenides to a variety of terminal alkynes Chemicals were obtained from Aldrich and Merck and were
could also proceed very smoothly to afford stereoselectively used as received. 1H NMR spectra were recorded on a Bruker
the corresponding (Z)-1,2-bis(arylseleno)-1-alkenes 3a–m in AC-P400 (400 MHz) spectrometer, with TMS as an internal
excellent yields with high stereoselectivity (Z/E . 99 : 1) after standard using CDCl3 as the solvent. 13C NMR (100 MHz)
2 h of reaction time. The reaction can tolerate a number of spectra were recorded on a Bruker AC-P400 (400 MHz)
functional groups, such as hydroxy, amino, and methoxy. The spectrometer using CDCl3 as the solvent. IR spectra were
addition reaction run in [bmim][PF6] also has the advantages determined on an FTS-185 instrument as neat films. Mass
of rate acceleration, increase of yield and lower reaction spectra (EI, 70 eV) were determined on a Finnigan 8230 mass
temperature in contrast to the reaction run in benzene. For spectrometer. Microanalyses were measured using a Yanaco
example, the addition reaction of Ph2Se2 to 1-hexyne in MT-3 CHN microelemental analyzer.
[bmim][PF6] at 60 uC gave (Z)-1,2-bis(phenylseleno)-1-hexene
(3a) in 96% yield after 2 h of reaction time (entry 1), but the Typical procedure for the Ar2S2 addition to terminal alkynes
same reaction run in benzene at 80 uC gave (Z)-1,2- Into a two-necked flask equipped with a reflux condenser and
bis(phenylseleno)-1-hexene (3a) in 81% yield after 12 h. a magnetic stirring bar were placed Pd(PPh3)4 (24 mg,
Isolation of the (Z)-1,2-bis(arylthio)-1-alkenes 2 or (Z)-1,2- 0.02 mmol), diphenyl disulfide (218 mg, 1.0 mmol), 1-octyne
bis(arylseleno)-1-alkenes 3 from the [bmim][PF6] reaction (132 mg, 1.2 mmol), and [bmim][PF6] (1.5 mL) under an argon
mixtures can be conveniently achieved by extraction with light atmosphere. The color of the solution rapidly turned from
yellow to dark brown. The mixture was stirred at 60 uC for 2 h,
Table 2 Palladium-catalyzed addition of Ar 2 Se 2 to various
then cooled to 30 uC and extracted with light petroleum ether
acetylenesa
(3 6 10 mL). The recovered ionic liquid containing the
Entry R Ar Product Yield (%)b palladium catalyst was concentrated in vacuo (5.0 torr, r.t. for
1 n-C4H9 Ph 3a 96 1 h) and reused in the next run. Combined organic solution
2 n-C4H9 4-ClC6H4 3b 98 was evaporated and dried under reduced pressure to give
3 HOCH2 Ph 3c 95 312 mg (95%) of (Z)-1,2-bis(phenylthio)-1-octene (2i) as a
4 HOCH2 4-CH3C6H4 3d 94
5 CH3OCH2 4-CH3C6H4 3e 96 yellow oil (purity: 96%).
6 Ph 4-CH3C6H4 3f 95
7 n-C6H13 4-CH3C6H4 3g 96 Table 3 Ionic liquid and catalyst recycling in Ph2Se2 addition to
8 H2NCH2 Ph 3h 94 1-hexynea
9 n-C6H13 Ph 3i 97
10 n-C6H13 4-ClC6H4 3j 96 Cycle Yield (%)b Cycle Yield (%)
11 Ph 4-ClC6H4 3k 94
12 CH3OCH2 Ph 3l 95 1 96 3 94
13 CH3OCH2 4-ClC6H4 3m 96 2 95 4 95
a a
Reactions were conducted under the conditions of 1.2 mmol of Reaction was conducted under the conditions of 1.2 mmol of
acetylene 1 and 1.0 mmol of Ar2Se2 in the presence of Pd(PPh3)4 1-hexyne and 1.0 mmol of Ph2Se2 in the presence of Pd(PPh3)4
(2 mol%) in [bmim][PF6] (1.5 mL) at 60 uC for 2 h. b Isolated yield (2 mol%) in [bmim][PF6] (1.5 mL) at 60 uC for 2 h. b Isolated yield
based on the Ar2Se2 used. based on the Ph2Se2 used.

This journal is ß The Royal Society of Chemistry 2007 Green Chem., 2007, 9, 1180–1184 | 1181
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(Z)-1,2-Bis(phenylthio)-1-hexene 2a. Oil. 1H NMR (Z)-1,2-Bis[(4-methylphenyl)thio]-1-octene 2g. Oil. 1H NMR

(400 MHz, CDCl3) d 7.41–7.20 (m, 10H), 6.54 (s, 1H), 2.23 (400 MHz, CDCl3) d 7.33–7.26 (m, 4H), 7.14–7.09 (m, 4H),
(t, 2H, J = 7.4 Hz), 1.50–1.42 (m, 2H), 1.26–1.20 (m, 2H), 6.44 (s, 1H), 2.33 (s, 3H), 2.32 (s, 3H), 2.19 (t, J = 7.4 Hz, 2H),
0.82 (t, 3H, J = 7.4 Hz). 13C NMR (100 MHz, CDCl3) d 1.50–1.43 (m, 2H), 1.26–1.15 (m, 6H), 0.84 (t, 3H, J = 7.2 Hz).
13
135.9, 134.3, 133.8, 130.5, 129.7, 129.1, 129.0, 128.9, 126.8, C NMR (100 MHz, CDCl3) d 136.9, 134.4, 132.5, 131.2,
126.7, 36.8, 30.7, 21.9, 13.8. IR (neat) n (cm21) 3059, 2957, 130.1, 129.9, 129.8, 129.7, 128.5, 36.9, 31.5, 28.5, 22.5, 21.1,
2928, 1582, 1478, 1439, 1024, 739, 690. MS (EI), m/z (%): 21.0, 14.1. IR (neat) n (cm21) 3020, 2956, 2926, 1563, 1492,
300 (M+, 97), 167 (73), 147 (100), 135 (71), 109 (53). Anal. 1455, 1400, 1091, 1017, 806. MS (EI), m/z (%): 356 (M+, 35),
Calcd for C18H20S2: C, 71.95; H, 6.71. Found: C, 71.67; H, 233 (23), 195 (100), 161 (39), 149 (50). Anal. Calcd for
6.63. C22H28S2: C, 74.10; H, 7.92. Found: C, 73.89; H, 7.78.

(Z)-1,2-Bis[(4-methylphenyl)thio]-1-hexene 2b. Oil. 1H NMR (Z)-1,2-Bis(phenylthio)-3-amino-1-propene 2h10a. Oil. 1H

(400 MHz, CDCl3) d 7.33–7.27 (m, 4H), 7.14–7.09 (m, 4H), NMR (400 MHz, CDCl3) d 7.46–7.22 (m, 10H), 6.87 (s, 1H),
Published on 16 August 2007 on http://pubs.rsc.org | doi:10.1039/B706320B

6.46 (s, 1H), 2.34 (s, 3H), 2.33 (s, 3H), 2.20 (t, 2H, J = 7.4 Hz), 3.38 (s, 2H), 1.40 (s, 2H). 13C NMR (100 MHz, CDCl3) d
1.51–1.41 (m, 2H), 1.25–1.19 (m, 2H), 0.83 (t, 3H, J = 7.2 Hz). 135.2, 133.7, 133.2, 132.1, 130.3, 130.0, 129.2, 129.1, 127.3,
13
C NMR (100 MHz, CDCl3) d 136.9, 134.2, 132.4, 131.1, 126.9, 47.7. IR (neat) n (cm21) 3374, 3055, 1654, 1582, 1478,
130.2, 130.1, 129.9, 129.7, 128.7, 36.6, 30.7, 22.0, 21.2, 21.1, 816, 745, 691. MS (EI), m/z (%): 273 (M+, 100), 167 (41), 147
13.9. IR (neat) n (cm21) 3020, 2956, 2928, 1564, 1491, 1453, (69), 134 (80). Anal. Calcd for C15H15NS2: C, 65.89; H, 5.53;
1401, 1091, 1018, 805. MS (EI), m/z (%): 328 (M+, 65), 195 N, 5.12. Found: C, 65.64; H, 5.61; N, 4.82.
(100), 161 (57), 149 (81), 91 (54). Anal. Calcd for C20H24S2: C,
73.12; H, 7.36. Found: C, 72.86; H, 7.15. (Z)-1,2-Bis(phenylthio)-1-octene 2i. Oil. 1H NMR (400 MHz,
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CDCl3) d 7.42–7.19 (m, 10H), 6.56 (s, 1H), 2.24 (t, 2H, J =
(Z)-1,2-Bis(phenylthio)-3-hydroxy-1-propene 2c10a. Oil. 1H 7.4 Hz), 1.51–1.45 (m, 2H), 1.26–1.21 (m, 6H), 0.85 (t, 3H, J =
NMR (400 MHz, CDCl3) d 7.44–7.21 (m, 10H), 7.03 (s, 1H), 7.2 Hz). 13C NMR (100 MHz, CDCl3) d 136.0, 134.5, 133.9,
4.14 (s, 2H), 2.01 (br, 1H). 13C NMR (100 MHz, CDCl3) d 130.5, 129.7, 129.1, 129.0, 128.9, 126.8, 126.7, 37.2, 31.5, 28.6,
134.8, 134.7, 133.2, 130.5, 129.9, 129.3, 129.2, 127.5, 127.0, 28.5, 22.6, 14.1. IR (neat) n (cm21) 3073, 2955, 2927, 1582,
65.5. IR (neat) n (cm21) 3382, 3057, 1716, 1581, 1478, 1439, 1478, 1439, 1092, 1024, 740, 690. MS (EI), m/z (%): 328 (M+,
1091, 1024, 740, 690. MS (EI), m/z (%): 274 (M+, 47), 167 (48), 95), 167 (71), 147 (100), 135 (37), 109 (68). Anal. Calcd for
163 (73), 147 (75), 135 (100). Anal. Calcd for C15H14OS2: C, C20H24S2: C, 73.12; H, 7.36. Found: C, 73.24; H, 7.29.
65.66; H, 5.14. Found: C, 65.39; H, 5.25.
Typical procedure for the Ar2Se2 addition to terminal alkynes
(Z)-1,2-Bis[(4-methylphenyl)thio]-3-hydroxy-1-propene 2d.
Oil. 1H NMR (400 MHz, CDCl3) d 7.34–7.28 (m, 4H), 7.14– Into a two-necked flask equipped with a reflux condenser and
7.09 (m, 4H), 6.89 (s, 1H), 4.09 (s, 2H), 2.33 (s, 3H), 2.30 (s, a magnetic stirring bar were placed Pd(PPh3)4 (24 mg,
3H), 1.98 (br, 1H). 13C NMR (100 MHz, CDCl3) d 137.6, 0.02 mmol), diphenyl diselenide (312 mg, 1.0 mmol), 1-hexyne
137.3, 134.3, 131.4, 130.8, 130.6, 130.1, 130.0, 129.4, 65.4, 21.1. (99 mg, 1.2 mmol), and [bmim][PF6] (1.5 mL) under an argon
IR (neat) n (cm21) 3391, 3020, 1714, 1564, 1491, 1091, 1017, atmosphere. The color of the solution rapidly turned from
805. MS (EI), m/z (%): 302 (M+, 98), 246 (64), 163 (72), 161 yellow to dark brown. The mixture was stirred at 60 uC for 2 h,
(84), 149 (93), 123 (92), 91 (100). Anal. Calcd for C17H18OS2: then cooled to 30 uC and extracted with light petroleum ether
C, 67.51; H, 6.00. Found: C, 67.33; H, 6.05. (3 6 10 mL). The recovered ionic liquid containing the
palladium catalyst was concentrated in vacuo (5.0 torr, r.t. for
(Z)-1,2-Bis[(4-methylphenyl)thio]-3-methoxy-1-propene 2e. 1 h) and reused in the next run. Combined organic solution
Oil. 1H NMR (400 MHz, CDCl3) d 7.36–7.30 (m, 4H), 7.16– was evaporated and dried under reduced pressure to give
7.10 (m, 4H), 6.86 (s, 1H), 3.90 (s, 2H), 3.27 (s, 3H), 2.34 (s, 378 mg (96%) of (Z)-1,2-bis(phenylseleno)-1-hexene (3a) as a
3H), 2.33 (s, 3H). 13C NMR (100 MHz, CDCl3) d 137.5, 137.1, yellow oil (purity: 97%).
134.1, 131.6, 130.8, 130.7, 129.9, 129.8, 129.6, 127.3, 74.4, 58.0,
21.1. IR (neat) n (cm21) 3021, 1714, 1564, 1491, 1119, 1091, (Z)-1,2-Bis(phenylseleno)-1-hexene 3a. Oil. 1H NMR
1017, 806. MS (EI), m/z (%): 316 (M+, 59), 177 (43), 161 (100), (400 MHz, CDCl3) d 7.56–7.51 (m, 4H), 7.32–7.23 (m, 6H),
91 (39). Anal. Calcd for C18H20OS2: C, 68.31; H, 6.37. Found: 6.93 (s, 1H), 2.28 (t, 2H, J = 7.4 Hz), 1.51–1.43 (m, 2H), 1.27–
C, 68.38; H, 6.29. 1.20 (m, 2H), 0.82 (t, 3H, J = 7.2 Hz). 13C NMR (100 MHz,
CDCl3) d 136.3, 132.9, 132.7, 131.3, 129.6, 129.3, 129.2, 127.9,
(Z)-1,2-Bis[(4-methylphenyl)thio]styrene 2f. Oil. 1H NMR 127.4, 127.3, 39.7, 31.1, 21.9, 13.9. IR (neat) n (cm21) 3057,
(400 MHz, CDCl3) d 7.54–6.97 (m, 14H), 2.35 (s, 3H), 2.23 (s, 2955, 2927, 1577, 1476, 1437, 1022, 735, 690. MS (EI), m/z (%):
3H). 13C NMR (100 MHz, CDCl3) d 138.9, 137.7, 136.8, 135.8, 396 (M+, 95), 394 (86), 183 (57), 157 (100), 77 (66). Anal. Calcd
131.8, 131.1, 131.0, 130.0, 129.6, 129.2, 128.6, 128.3, 127.4, for C18H20Se2: C, 54.83; H, 5.11. Found: C, 54.61; H, 5.20.
126.8, 21.1, 21.0. IR (neat) n (cm21) 3020, 1714, 1539, 1490,
1091, 1017, 803. MS (EI), m/z (%): 348 (M+, 47), 246 (93), 123 (Z)-1,2-Bis[(4-chlorophenyl)seleno]-1-hexene 3b. Oil. 1H
(100), 91 (84), 77 (72). Anal. Calcd for C22H20S2: C, 75.82; H, NMR (400 MHz, CDCl3) d 7.49–7.42 (m, 4H), 7.29–7.23 (m,
5.78. Found: C, 75.57; H, 5.63. 4H), 6.88 (s, 1H), 2.27 (t, 2H, J = 7.4 Hz), 1.50–1.42 (m, 2H),

1182 | Green Chem., 2007, 9, 1180–1184 This journal is ß The Royal Society of Chemistry 2007
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1.27–1.21 (m, 2H), 0.83 (t, 3H, J = 7.2 Hz). 13C NMR (100 MHz, CDCl3) d 133.1, 132.5, 130.8, 130.6, 129.4, 129.3,
(100 MHz, CDCl3) d 136.7, 134.1, 134.0, 133.8, 133.7, 129.5, 128.9, 127.7, 127.5, 50.3. IR (neat) n (cm21) 3370, 3053, 1578,
129.4, 129.2, 128.0, 127.6, 39.7, 31.1, 21.9, 13.8. IR (neat) n 1477, 841, 735. MS (EI), m/z (%): 369 (M+, 11), 183 (58), 157
(cm21) 2955, 2927, 1712, 1570, 1473, 1387, 1090, 1011, 813, (76), 77 (100). Anal. Calcd for C15H15NSe2: C, 49.06; H, 4.12;
730. MS (EI), m/z (%): 464 (M+, 35Cl, 5.2), 217 (100), 191 (33), N, 3.81. Found: C, 49.29; H, 4.28; N, 3.99.
156 (57), 57 (38). Anal. Calcd for C18H18Cl2Se2: C, 46.68; H,
3.92. Found: C, 46.42; H, 3.75. (Z)-1,2-Bis(phenylseleno)-1-octene 3i. Oil. 1H NMR
(400 MHz, CDCl3) d 7.57–7.51 (m, 4H), 7.32–7.24 (m, 6H),
(Z)-1,2-Bis(phenylseleno)-3-hydroxy-1-propene 3c. Oil. 1H 6.93 (s, 1H), 2.28 (t, 2H, J = 7.4 Hz), 1.50–1.45 (m, 2H), 1.27–
NMR (400 MHz, CDCl3) d 7.59–7.53 (m, 4H), 7.40 (s, 1H), 1.17 (m, 6H), 0.84 (t, 3H, J = 6.8 Hz). 13C NMR (100 MHz,
7.33–7.28 (m, 6H), 4.15 (s, 2H), 1.93 (br, 1H). 13C NMR CDCl3) d 136.5, 132.9, 132.6, 131.3, 129.5, 129.3, 129.2, 127.8,
(100 MHz, CDCl3) d 133.4, 133.2, 132.4, 132.2, 130.3, 129.4, 127.4, 127.3, 40.0, 31.5, 28.9, 28.4, 22.5, 14.1. IR (neat)
129.3, 128.6, 127.8, 127.6, 67.6. IR (neat) n (cm21) 3388, 3057, n (cm21) 3057, 2956, 2926, 1710, 1577, 1476, 1438, 1071, 1022,
Published on 16 August 2007 on http://pubs.rsc.org | doi:10.1039/B706320B

1668, 1575, 1475, 1437, 1070, 1021, 735, 690. MS (EI), m/z (%): 735, 690. MS (EI), m/z (%): 424 (M+, 35), 183 (88), 115 (100),
370 (M+, 29), 183 (53), 157 (77), 77 (100). Anal. Calcd for 77 (76). Anal. Calcd for C20H24Se2: C, 56.88; H, 5.73. Found:
C15H14OSe2: C, 48.93; H, 3.83. Found: C, 48.71; H, 3.95. C, 56.59; H, 5.75.

(Z)-1,2-Bis[(4-methylphenyl)seleno]-3-hydroxy-1-propene 3d. (Z)-1,2-Bis[(4-chlorophenyl)seleno]-1-octene 3j. Oil. 1H

Oil. 1H NMR (400 MHz, CDCl3) d 7.48–7.43 (m, 4H), 7.28 (s, NMR (400 MHz, CDCl3) d 7.48–7.42 (m, 4H), 7.28–7.24 (m,
1H), 7.13–7.08 (m, 4H), 4.09 (s, 2H), 2.34 (s, 3H), 2.32 (s, 3H), 4H), 6.87 (s, 1H), 2.26 (t, 2H, J = 7.4 Hz), 1.49–1.42 (m, 2H),
1.86 (br, 1H). 13C NMR (100 MHz, CDCl3) d 137.9, 137.8, 1.27–1.18 (m, 6H), 0.85 (t, 3H, J = 6.8 Hz). 13C NMR
133.5, 133.0, 132.9, 132.3, 130.2, 130.1, 126.7, 124.7, 67.5, 21.2. (100 MHz, CDCl3) d 136.9, 134.2, 134.0, 133.8, 133.7, 129.5,
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IR (neat) n (cm21) 3377, 3018, 1709, 1574, 1488, 1447, 1072, 129.4, 129.2, 127.8, 127.6, 40.0, 31.5, 28.9, 28.4, 22.5, 14.0. IR
1015, 801. MS (EI), m/z (%): 398 (M+, 46), 226 (48), 197 (63), (neat) n (cm21) 2957, 2928, 1637, 1574, 1473, 1387, 1089, 1011,
171 (75), 91 (100). Anal. Calcd for C17H18OSe2: C, 51.53; H, 812. MS (EI), m/z (%): 492 (M+, 35Cl, 45), 193 (58), 191 (100),
4.58. Found: C, 51.31; H, 4.36. 156 (72), 112 (68), 109 (94), 67 (81). Anal. Calcd for
C20H22Cl2Se2: C, 48.90; H, 4.51. Found: C, 48.63; H, 4.45.
(Z)-1,2-Bis[(4-methylphenyl)seleno]-3-methoxy-1-propene 3e.
Oil. 1H NMR (400 MHz, CDCl3) d 7.48–7.44 (m, 4H), 7.25 (s, (Z)-1,2-Bis[(4-chlorophenyl)seleno]styrene 3k. Oil. 1H NMR
1H), 7.13–7.08 (m, 4H), 3.91 (s, 2H), 3.25 (s, 3H), 2.34 (s, 3H), (400 MHz, CDCl3) d 7.56–7.12 (m, 14H). 13C NMR (100 MHz,
2.33 (s, 3H). 13C NMR (100 MHz, CDCl3) d 137.8, 137.6, 133.4, CDCl3) d 140.1, 135.4, 134.6, 134.4, 133.0, 132.4, 132.1, 129.6,
133.2, 132.9, 130.1, 130.0, 129.1, 126.9, 125.0, 76.6, 57.9, 21.2. IR 129.3, 129.0, 128.5, 128.4, 127.9, 127.3. IR (neat) n (cm21)
(neat) n (cm21) 3018, 1697, 1573, 1488, 1101, 1015, 802. MS (EI), 3056, 1709, 1544, 1472, 1387, 1089, 1011, 810. MS (EI), m/z
m/z (%): 412 (M+, 37), 171 (69), 91 (100). Anal. Calcd for (%): 484 (M+, 35), 293 (38), 258 (100), 191 (99), 156 (60), 112
C18H20OSe2: C, 52.69; H, 4.91. Found: C, 52.44; H, 5.05. (42). Anal. Calcd for C20H14Cl2Se2: C, 49.72; H, 2.92. Found:
C, 49.93; H, 3.05.
(Z)-1,2-Bis[(4-methylphenyl)seleno]styrene 3f10a. Oil. 1H
NMR (400 MHz, CDCl3) d 7.52–6.97 (m, 14H), 2.35 (s, 3H), (Z)-1,2-Bis(phenylseleno)-3-methoxy-1-propene 3l. Oil. 1H
2.24 (s, 3H). 13C NMR (100 MHz, CDCl3) d 140.7, 138.0, NMR (400 MHz, CDCl3) d 7.59–7.54 (m, 4H), 7.36 (s, 1H),
136.6, 136.3, 133.5, 132.3, 131.4, 131.2, 130.2, 129.9, 128.2, 7.35–7.24 (m, 6H), 3.95 (s, 2H), 3.27 (s, 3H). 13C NMR
127.4, 127.3, 126.5, 21.1, 21.0. IR (neat) n (cm21) 3014, 2965, (100 MHz, CDCl3) d 133.4, 133.1, 132.6, 130.5, 129.4, 129.3,
1592, 1487, 1441, 1015, 801. MS (EI), m/z (%): 444 (M+, 95), 129.1, 128.9, 127.7, 127.5, 76.7, 58.0. IR (neat) n (cm21) 3055,
171 (58), 91 (100). Anal. Calcd for C22H20Se2: C, 59.74; H, 1692, 1577, 1475, 1098, 1021, 800, 738, 690. MS (EI), m/z (%):
4.56. Found: C, 59.51; H, 4.35. 384 (M+, 65), 195 (100), 147 (97), 115 (98), 77 (96). Anal. Calcd
for C16H16OSe2: C, 50.28; H, 4.22. Found: C, 50.35; H, 4.29.
(Z)-1,2-Bis[(4-methylphenyl)seleno]-1-octene 3g. Oil. 1H
NMR (400 MHz, CDCl3) d 7.45–7.41 (m, 4H), 7.10–7.06 (m, (Z)-1,2-Bis[(4-chlorophenyl)seleno]-3-methoxy-1-propene 3m.
4H), 6.83 (s, 1H), 2.32 (s, 3H), 2.31 (s, 3H), 2.22 (t, 2H, J = Oil. 1H NMR (400 MHz, CDCl3) d 7.51–7.45 (m, 4H), 7.30–
7.2 Hz), 1.48–1.42 (m, 2H), 1.26–1.14 (m, 6H), 0.83 (t, 3H, J = 7.25 (m, 5H), 3.94 (s, 2H), 3.28 (s, 3H). 13C NMR (100 MHz,
7.2 Hz). 13C NMR (100 MHz, CDCl3) d 137.4, 136.5, 133.5, CDCl3) d 134.5, 134.2, 134.0, 133.8, 133.4, 133.3, 129.6, 129.5,
133.0, 130.1, 130.0, 128.5, 127.6, 127.3, 125.8, 39.7, 31.6, 28.9, 128.5, 127.0, 77.2, 58.1. IR (neat) n (cm21) 3076, 1696, 1572,
28.5, 22.6, 21.2, 14.2. IR (neat) n (cm21) 3017, 2955, 2925, 1473, 1089, 1011, 812. MS (EI), m/z (%): 452 (M+, 35Cl, 28),
1574, 1488, 1453, 1015, 802. MS (EI), m/z (%): 452 (M+, 18), 229 (80), 181 (100), 156 (52), 112 (22). Anal. Calcd for
262 (88), 183 (100), 91 (63). Anal. Calcd for C22H28Se2: C, C16H14OCl2Se2: C, 42.60; H, 3.13. Found: C, 42.41; H, 3.20.
58.67; H, 6.27. Found: C, 58.38; H, 6.20.
Conclusions
(Z)-1,2-Bis(phenylseleno)-3-amino-1-propene 3h10a. Oil. 1H
NMR (400 MHz, CDCl3) d 7.61–7.50 (m, 4H), 7.33–7.26 (m, The present article describes the palladium-catalyzed addition
6H), 7.22 (s, 1H), 3.38 (br, 2H), 1.43 (br, 2H). 13C NMR reactions of diaryl disulfides and diselenides to terminal

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