Chem. Rev.

1995, 95, 2457-2483 2457

Palladium-Catalyzed Cross-Coupling Reactions of Organoboron Compounds

Norio Miyaura* and Akira Suzuki*1

Division of Molecular Chemistry, Faculty of Engineering, Hokkaido University, Sapporo 060, Japan

Received January 31, 1995 (Revised Manuscript Received August 17, 1995)

Contents
I. Introduction 2457
II. Synthesis of Organoboron Reagents 2458
A. Synthesis from Organolithium or Magnesium 2458
Reagents
B. Hydroboration of Alkenes and Alkynes 2458
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C. Haloboration of Terminal Alkynes 2459

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D. Miscellaneous Methods 2459

III. Palladium-Catalyzed Reactions of Organoboron 2460
Compounds and Their Mechanism
A. Cross-Coupling Reaction 2460
B. Other Catalytic Process by Transition-Metal 2464
Complexes
IV. Cross-Coupling Reaction 2465
Norio Miyaura was bom in Hokkaido, Japan in 1946. He received his
A. Coupling of 1-Alkenylboron Derivatives: 2465 B.Sc. and his Dr. from Hokkaido University. He became a research
Synthesis of Conjugated Dienes associate and an associate professor of A. Suzuki's research group and
B. Coupling of Arylboron Derivatives: Synthesis 2469 was promoted to the professor of the same group in 1994. In 1981, he
of Biaryls joined J. K. Kochi research group at Indiana University and studied the
C. Coupling of Alkyiboron Derivatives 2471 catalytic and noncatalytic epoxidation of alkenes with oxo-metal reagents.
His currenl interests are mainly in the field of transition-metal-catalyzed
D. Coupling with Triflates 2473 reactions of organoboron compounds, with emphasis on applications to
E. Synthesis of Vinylic Sulfides 2473 organic synthesis. For examples, cross-coupling reaction, catalytic
F. Coupling with lodoalkanes: Alkyl-Alkyl 2475 hydroboration, catalytic thioboration, and catalytic diboration of alkenes
Coupling and alkynes.
G. Coupling with Other Organic Halides and 2475
Boron Reagents
V. Head-to-Tail Coupling 2476
VI. Carbonylative Coupling 2476
VII. Alkoxycarbonylation and Dimerization 2478
VIII. Conclusion 2478

1. Introduction
The cross-coupling reaction now accessible via a
variety of organometallic reagents may provide a
fundamentally common synthetic methodology (eq 1).
Pd-catalyst
R-M + R*-X - R-R' (1)
Akira Suzuki was bom in Hokkaido, Japan, in 1930. He received his
undergraduate and graduate training at Hokkaido University and joined
In 1972, Kumada and Tamao1 and Corriu2 reported the faculty in 1961 as an assistant professor. He spent two years as a
independently that the reaction of organomagnesium postdoctoral associate with Professor Herbert C. Brown al Purdue
reagents with alkenyl or aryl halides could be mark- University and was promoted to the rank of professor in 1971. After
retirement from Hokkaido University, Akira Suzuki moved to Okayama
edly catalyzed by Ni(ll) complex. Kochi3 found the
University of Science as a chemistry professor in 1994. His current
efficiency of Fe(III) catalyst for the cross-coupling of interests are mainly in the field of organoboron chemistry, with emphasis
Grignard reagents with 1-halo-1-alkenes and Li2- on applications to organic synthesis, organometallic chemistry, and the
CuCl4 catalyst for haloalkanes. The palladium- study of reactive intermediates.
catalyzed reaction of Grignard reagents was first
reported by Murahashi,4 the synthetic utility of which reagents. After those discoveries, many other orga-
was then amply demonstrated by Negishi5 on the nometallic reagents have proven to be highly useful
reactions of organoaluminum, zinc, and zirconium as nucleophiles for the cross-coupling reaction, e.g.,
organolithiums by Murahashi,6 organostannans by
f
Present address: Kurashiki University of Science and the Arts, Migita7 and Stille,® l-alkenylcopper(I) by Normant,9
Kurashiki 712, Japan. organosilicon compounds by Hiyama.10 These reac-
0009-2665/95/0795-2457$15.50/0 © 1995 American Chemical Society
2458 Chemical Reviews, 1995, Vol. 95, No. 7 Miyaura and Suzuki

tions are mechanically and synthetically closely + --

HjO-
ArMgX B(OMe)3 ArB(OH)2 (2)
related to the present article; however, the reactions,
mechanism, and their synthetic utility have been
—=si
extensively reviewed elsewhere.11 CH2=CHMgBr +B(OMe)3 CH2=CHB(OR)2 (3)

Organoboron compounds are highly electrophilic,

CH3 B(OH)2
but the organic groups on boron are weakly nucleo- CH3 Br Mg 1. B(OCH^3
(4)
philic, thus limiting the use of organoboron reagents >=< 2. H30*
>=<
H H CHj
CH3
for the ionic reactions. The coordination of a nega-
tively charged base to the boron atom has been
recognized to be an efficient method of increasing its aryl-, 1-alkynyl-, and 1-alkenylboronic esters in high
nucleophilicity to transfer the organic group on boron yields, often over 90% (eq 5).23 Triisopropyl borate
to the adjacent positive center (1,2-migration reac- is shown to be the best of available alkyl borates to
tion).12 However, intermolecular transfer reaction
avoid such multiple alkylation of the borates.
such as the Grignard-like reaction are relatively rare. HCI
RLi +
B(OPr)3 -
R-B(OPr)3 R-B(OPrj2 (5)
Fortunately, organoboron compounds, even orga-
noboronic acids and esters, have sufficiently enough R =
alkyl, aryl, 1-alkenyl, and 1-alkynyl
reactivity for the transmetalation to other metals.
Transmetalations to silver®,13 magnesium(II),14 zinc-
Very recently, arylboronic esters have been directly
ill),15 aluminum(II),16 tin(IV),17 copper®,18 and mer- obtained from aryl halides via the cross-coupling
cury®)19 halides have been extensively studied. In reaction of (alkoxy)diboron (eq 6).24 The reaction
1978, Negishi reported that iodobenzene selectively tolerates various functional groups such as ester,
couples with the 1-alkynyl group on lithium 1-hex- nitrile, nitro, and acyl groups.
ynyl(tributyl)borate through a palladium-catalyzed
addition-elimination sequence (Heck-type process);51 (RO)2B-B(OR)2
(6)
however, the cross-coupling reaction of organoboron PdCfefdppf)
compounds, which involves the transmetalation to
KOAc
DMSO, 80°C
palladium®) halides as a key step, was found to
proceed smoothly .when these were activated with B. Hydroboration of Alkenes and Alkynes
suitable bases and have proven to be a quite general
technique for a wide range of selective carbon—carbon The addition of dialkylboranes such as 9-borabicyclo-
bond formation.20 Many organometallic reagents [3.3.1]nonane (9-BBN), disiamylborane, or dicyclo-
undergo similar cross-coupling reactions, but much hexylborane to 1-alkenes gives mixed alkylboron
attention has recently been focused on the use of compounds.25 The reaction is essentially quantita-
organoboronic acids in laboratories and industries tive, proceeds through cis anti-Markovnikov addition
since they are convenient reagents, which are gener- from the less hindered side of double bond, and can
ally thermally stable and inert to water and oxygen, tolerate various functional groups. The 9-alkyl-9-
thus allow their handling without special precau- BBN derivatives thus obtained are particularly use-
tions. This review summarizes the palladium- ful for the transfer of primary alkyl groups by the
catalyzed cross-coupling reaction of organoboron palladium-catalyzed cross-coupling reaction since the
compounds with organic halides or triflates, the 9-alkyl group exclusively participates in a catalytic
reaction mechanism, the scope of synthetic applica- reaction cycle (eq 7).
tions, and other related catalytic processes with
transition-metal complexes are discussed.20 9-BBN /
R'CH=CH2 --
R'CH,CH2-B R-B (7)

II. Synthesis of Organoboron Reagents 1 : 9-R-9-BBN

A. Synthesis from Organolithium or Magnesium

The use of the hydroboration reaction is especially
Reagents valuable for the synthesis of stereodefined or func-
The classical synthesis of aryl- and 1-alkenylbo- tionalized alkenylboronic acids and their esters. The
ronic acids or their esters from Grignard reagents or general and most convenient method is the hydrobo-
lithium reagents and trialkyl borates is an efficient ration of a terminal alkyne with catecholborane (2a)
method for making relatively simple boron com- to produce 1-alkenylboronic ester (eq 8).25,26 The
pounds in large quantities (eqs 2 and 3).21 The first hydroboration with 2a can also be carried out under
stereocontrolled synthesis of alkenylboronic acids and milder conditions by using palladium, rhodium, or
esters involves the reaction of a (Z)- or CE)-2-buten- nickel catalysts.27 The hydroboration of alkynes with
2-ylmagnesium bromide with trimethyl borate (eq dihaloboranes (HBCl2‘SMe2 or HBBr2-SMe2), fol-
4).22 lowed by hydrolysis to vinylboronic acids or alcoholy-
However, the application of these classical proce- sis to boronic esters (3b) have been used for the same
dures for organoboronic acid or ester synthesis may purpose.25,28 However, a recent and more convenient
suffer from the contamination of small mount of the variant is the in situ preparation of HBC12 in a
opposite stereoisomers, or bis-alkylation leading to hydrocarbon solvent from BCI3 and HSiEt3.29 The
the borinic acid derivatives and the formation of reagent exhibits extremely high reactivity to alkenes
trialkylboranes. A recent useful variant utilizes and alkynes allowing the hydroboration to proceed
organolithium reagents and triisopropyl borate, fol- at —78 °C. Disiamylborane (2c) is also one of the
lowed by acidification with HC1 to give directly alkyl-, mildest and selective hydroboration reagents for
Reactions of Organoboron Compounds Chemical Reviews, 1995, Vol. 95, No. 7 2459

functionalized alkynes, but their use for the cross- X

coupling can be more difficult than that of boronic r'c=c-x

1.HBBrj.SMe2
,

(10)
acids or their esters. Hydroboration of terminal 2. r-PrOH RY^B(OPr)2
H
4a: X= Br
alkynes with 9-BBN leads to the formation of sig- 4b: X= I
nificant quantities of dihydroboration products. How-
ever, dihydroboration of 1-alkynes, followed by de- B(OPr)2
boration with benzaldehyde provides 9-[(£)-l-al-
kenyl]-9-BBN derivatives (3d) in high yields with
4 + KHB(OPr)3 R1^ H (11)
H
high trans selectivity.30 5

H B(OPr)2
R'.
4 + R2Li (12)

Cl^dfPPh* (13)
2 4b + R2ZnX
2b: V2= Br2*SMe2 R0H> 3b: y2 =
(OR)2

2e: Y2 =
(-CH -
CHCH3)2 =(Sla)2 3c R2= alkyl, aryl, 1-alkenyl, and 1-alkynyl

CKj CH3
which are not available by conventional hydrobora-
2d: Y2- 3d tion of internal alkynes (eq 13).36

C. Haloboration of Terminal Alkynes

These reactions work well with terminal and sym- Terminal 2,2-diorgano-l-alkenylboronates (9) are
metrical internal alkynes, but the difficulties are made by bromoboration of a terminal alkyne to
often encountered by the lack of regiochemistry or /3-bromo-l-alkenylboronic ester (8) (eq 14),37 followed
chemoselectivity (e.g., reduction of functional groups) by the palladium-catalyzed displacement of the /?-
upon addition to general internal alkynes or func- halogen with organozinc reagents which proceeds
tionalized alkynes. Diisopinocampheylborane has strictly with retention of configuration (eq 15).38
been used as a reagent for asymmetric hydroboration,
and additionally it has attractive features as a H

hydroboration reagent for alkynes, e.g., the inertness R'CsCH

1. BBr3 R!
'B(OPr)2 (14)
to many functional groups except aldehyde and 2. top Br
ketone carbonyls, the high regioselectivity resulting 8

from its bulkiness, and ease of dealkylation to boronic H

esters under neutral conditions.31 The hydroboration
PdCfe(PPh3)2
of propargyl chloride and ethyl propiolate provides 8 + R2ZnX -
B(OPr)2 (15)
terminal boron derivatives with excellent regiochem- R2 9
istry,32 whereas the hydroboration with catecholbo-
rane or disiamylborane (2c) gives an inseparable Haloboranes add to terminal alkynes via a cis anti-
mixture of internal and terminal boron adducts (eq Markovnikov manner; however, the bromoboration
9). of acetylene itself exceptionally provides a trans-
adduct which gives the corresponding CE)-l-al-
H
1. HB(lpc)a R1.
kenylborates (10) by the reaction with organozinc
R1C=CH B(OEt)2 (9) halides (eq 16).39 The addition of tribromoborane to
2. CH3CHO
H acetylene first gives a czs-adduct, which then isomer-
izes to the trans-isomer during its isolation.40
R’ =
CH2CI (73%); C02Et (70%); CH(OSiMe3)CH3 (74%)
CH(OEt)2 (52%); SPh (52%) H

1. BBr3 Br-
HC=CH
Terminal and internal (Z)-l-alkenylboronates are 2. to20
B(OPr)2
H
prepared from (Z)-(haloalkenyl)boronic esters (4) H

which can be readily obtained by hydroboration of (16)

B(0 Pr)2
1-halo-l-alkyne (eq 10).28’32’33 The internal Sn2 like R1ZnX/PdCI2(PPh3)2
H
displacement of the halogen with KHB(OPri)333-34 or 10

organolithiums35 takes place with complete inversion These two-step procedures are useful to achieve a
of configuration at the sp2 carbon (eqs 11 and 12).
formal carboboration of alkynes with a variety of
The reaction is almost quantitative and highly selec-
tive (inversion >99%). Thus, the boron derivatives organic groups.
prepared in situ can be directly used for the following D. Miscellaneous Methods
cross-coupling reaction without further purification.
On the other hand, alkylation of 4b with organozinc An efficient route to (-E)-l-alkenylboronates from
reagents in the presence of a palladium catalyst carbonyl compounds is achieved by the reaction with
stereospecifically provides (E)-1 -alkenylboronates (7) lithio(boryl)methanes. The (E)/(Z) isomeric ratio is
2460 Chemical Reviews, 1995, Vol. 95, No. 7 Miyaura and Suzuki

reported to be ~20:1 (eq 17).41 On the other hand, a esters of boronic acids are reported to be isolated by
trimethylsilyl analog gives a czs-rich isomer (~70:30) flash chromatography on silica gel.50
on reaction with aldehydes (eq 18).42 The reaction
of lithiotriborylmethane with aldehydes or ketones III. Palladium-Catalyzed Reactions of
yields 1,1-alkenyldiborates (eq 19).43 Organoboron Compounds and Their Mechanism
H
A. Cross-Coupling Reaction
BuLi R!sJns
O0^
1.
10
r~\ 2. R’CHO
-

r (17) A general catalytic cycle for the cross-coupling

°'m'° H
reaction of organometallics, which involves oxidative
addition-transmetalation—reductive elimination se-
quences, is depicted in Figure 1. Although each steps
p- _
I.LiNRa * involves further knotty processes including ligand
MeaSiCH-B,
0"
—
2. R'CHO nWB'° exchanges, there is no doubt about the presence of
those intermediates (11 and 12) which have been
0 characterized by isolation or spectroscopic analy-

401.
1.

2.
BuLi

O o-C A. ,
(19)
ses.11,51 It is significant that the great majority of
cross-coupling reactions catalyzed by Ni(0), Pd(0),
and Fed) are rationalized in terms of this common
catalytic cycle.
Oxidative addition11,52 of 1-alkenyl, 1-alkynyl, allyl,
Alkynylboronates are attacked by many electro-
benzyl, and aryl halides to a palladium(O) complex
philes at the position /3 to the boron atom. The affords a stable irazzs-a-palladium(II) complex (11).
following rearrangement gives a variety of function- The reaction proceeds with complete retention of
alized 1-alkenylboranes (eq 20).12’44 The stereochem-
istry can be either E or Z, or a mixture of the two in configuration for alkenyl halides and with inversion
for allylic and benzylic halides. Alkyl halides having
most cases.
/3-hydrogen are rarely useful because the oxidative
addition step is very slow and may compete with
R1—B-C=CR2 + EX (20) /3-hydride elimination from the a-organopalladium-
(II) species. However, it has been recently shown
that iodoalkanes undergo the cross-coupling reaction
EX= CISnMej, NCCHjl, EtO^CCH-Br, oxirane with organoboron compounds (sections IV.F and
VI).53
Allylboration of 1-alkynes proceeds at room tem- Oxidative addition is often the rate-determining
perature to give cis addition products in high yields step in a catalytic cycle. The relative reactivity
decreases in the order of I > OTf > Br » Cl. Aryl
(eq 21).45 The Diels-Alder reaction between 2-(di-
and 1-alkenyl halides activated by the proximity of
alkoxyboryl)-l,3-butadiene and dienophiles at 50 °C
provides cyclic 1-alkenylboronates (eq 22).46 electron-withdrawing groups are more reactive to the
oxidative addition than those with donating groups,
CH2=CHCH2 B(OMs)2 thus allowing the use of chlorides such as 3-chlo-
R CsCH + (C3H5)3B —-

2 MeOH
)=( (21) roenone for the cross-coupling reaction. A very wide
r H
range of palladium(O) catalysts or precursors can be
used for cross-coupling reaction. Pd(PPhs)4 is most
commonly used, but PdCl2(PPhs)2 and Pd(OAc)2 plus
PPI13 or other phosphine ligands are also efficient
since they are stable to air and readily reduced to
the active Pd(0) complexes with organometallics or
phosphines used for the cross-coupling.54 Palladium
The addition of diboron compounds to alkynes is complexes that contain fewer than four phosphine
an excellent method for the synthesis of czs-diboryl ligands or bulky phosphines such as tris(2,4,6-tri-
alkenes (eq 23).47 The reaction is catalyzed by Pt-
(PPhs)4 at 80 °C and works well with terminal and
internal alkynes. The addition of the Si—B48 or Sn—
B49 bonds to alkynes gives mixed-metal alkenylboron
reagents which have potential ability for use in the
stepwise double cross-coupling reaction at the both
metalated carbons.

R1 R2
(RO)2B-B(OR)2
R1-C=C-R2
Pt-catalyst
)=< (23)
(RO)2B B(OR)2
•12 v 11

Organoboronic acids or their esters are generally

stable to air and thermal treatment. Thus, the
R'M
boronic esters can be isolated by distillation, and MX
acids, by crystallization. Alternatively, the pinacol Figure 1. A general catalytic cycle for cross-coupling.
Reactions of Organoboron Compounds Chemical Reviews, 1995, Vol. 95, No. 7 2461

methoxyphenyl)phosphine are, in general, highly Na2PdCl4 catalyst (eq 27),61 although it still remains
reactive for the oxidative addition because of the obscure whether the reaction indeed proceeds through
ready formation of coordinate unsaturated palladium the transmetalation or other processes.
species.55
Reductive elimination of organic partners from 12 BuCH=CHB(OH)2 +
Pd(OAc)2 + CH2=CHC02Et
reproduces the palladium(O) complex.56-58 The reac-
tion takes place directly from cis-12, and the trans- -
BuCH=CHCH=CHC02Et (26)
12 reacts after its isomerization to the corresponding
ds-complex (eqs 24 and 25). The order of reactivity 2 PhB(OH)2 + Na2PdCI4- Ph-Ph (27)
is diaryl- > (alkyl)aryl- > dipropyl- > diethyl- >
dimethylpalladium(II), suggesting participation by In spite of these previous reports, organoboron
the jr-orbital of aryl group during the bond formation
compounds are quite unlikely to participate in the
(eq 24).58b Although the step of 1-alkenyl- or 1-alky-
nylpalladium(II) complexes is not studied, the similar catalytic cycle of cross-coupling reaction since they
are inert to the organopalladium(II) halides (11) such
effect is observed in the reductive elimination of
as PdCl2, PdCl2(PPh3)2, or PhPdI(PPh3)2.62 There is
related platinum(II) complexes.59
some experimental evidence for the transmetalation
to the transition metals. The reaction of organobo-
ranes with organomercurials proceeds under neutral
conditions when Hg(OAc)2, Hg(OR)2, or HgO is used.63
It has also been reported that the addition of sodium
hydroxide or other bases exerts a remarkable effect
on the transmetalation rate of organoboron reagents
with metallic halides, such as mercuric,19 63 silver,13
The thermolysis of cjs-(dialkyl)palladium(II)-L2, auric,64 and platinic halides.64 Thus, the transmeta-
which is an intermediate on the alkyl—alkyl coupling, lation with transition-metal complexes appears to
is inhibited by excess phosphine (L), hence it is proceed well indeed, but the choice of suitable bases
considered to be initiated by the rate-determining and ligands on transition-metal complexes is es-
dissociation of phosphine ligand (L) producing a sential.
three-coordinated ds-(dialkyl)palladium(II)*L com- Preliminary successful results have reported that
plex (dissociative mechanism, eq 25).57 Thus, the CE)-l-hexenyl-l,3,2-benzodioxaborole couples with
effect of phosphine ligands is comparable to the order iodobenzene in the presence of Pd(PPhs)4 and bases
of ease of their dissociation: dppe « PEt3 < PEt2Ph to produce a mixture of desired and undesired
< PMePh2 < PEtPh2 < PPI13. coupling products depending on the base and the
catalyst used (eq 28).65
\ -L V
Me-Pd-Me Pd-catlyst / bass
Me-Pd-Me .
+ Ph-I -
3a(R1="Bu)
L
"Bu +
^"y?
Ph
(28)

Me .
|_
Me 13 14
‘
L-Pd-Me « L—Pd-Me —Me-Me + Pd(0)*L2 (25)
L The formation of normal coupling product 13
predominates when sodium hydroxide or alkoxides
On the other hand, cis-alkenyl- and cis-arylpalla- are used, whereas a combination of triethylamine and
dium(II) complexes, which are intermediates in most a palladium catalyst without phosphine ligands leads
of cross-coupling reactions discussed here, directly almost exclusively to an abnormal head-to-tail cou-
eliminate organic partners from the four-coordinated pling product 14 (Table l).65b
complex (nondissociative—nonassociative mechanism, The formation of the abnormal coupling product 14
eq 24).58 can be best understood by the mechanism of Heck
Although the mechanism of oxidative addition and reaction66 for vinylic metal compounds, that often
reductive elimination sequences are reasonably well predominates on the cross-coupling reaction of weakly
understood and are presumably fundamentally com-
mon processes for all cross-coupling reactions of Table 1. Reaction Conditions for Head-to-Head and
organometallics, less is known about the transmeta- Head-to-Tail Cross-Coupling (Eq 28)°
lation step because the mechanism is highly depend- base yield,%
ent on organometallics or reaction conditions used catalyst solvent (equiv) time, h (13/14)
for the couplings. Pd(PPh3)4 benzene none 6 0
The transmetalation between 1-hexenylboronic Pd(pph3)4 benzene NaOEt (2) 2 99 (100/0)
acid and palladium(II) acetate was first reported by Pd(pph3)4 benzene NaOH (2) 2 99 (100/0)
Heck.60 The in situ preparation of (E)- or (Z)-l- Pd(pph3)4 DMF Et3N (5) 20 54 (10/90)
PdCl2(PPh3)2 DMF Et3N (5) 20 66 (8/92)
alkenylpalladium(II) species and its addition to ethyl Pd black DMF Et3N (5) 20 94 (4/96)
acrylate readily proceeds at room temperature while Pd black DMF NaOH (2) 6 86 (56/44)
retaining their original configurations (eq 26).38 “
All reactions were carried out at 80 °C by using Pd catalyst
Before this observation, Davidson and Triggs re-
(3 mol %), Phi (1 equiv), base, and 3a (1.1 equiv).
ported the dimerization of phenylboronic acid with
2462 Chemical Reviews, 1995, Vol. 95, No. 7 Miyaura and Suzuki

negatively charged bases giving the corresponding

“ate” complexes.12 In fact, it is reported that such
ate complexes undergo a clean coupling reaction with
organic halides.51 The reaction of iodobenzene with
representative ate complexes prepared from tribu-
tylborane and butyl-, 1-propenyl-, 1-hexynyl-, or
phenyllithium is summarized in eq 30 and Table 2.73
C.Hs,
Pd-catalyst
R—B-C4H9 R-Pb C4H9-Ph (30)
THF, reflux
c4h9
16 19

R= n-C4H9, CH3CH=CH, C4H9OC, Ph

Figure 2. Addition—elimination mechanism for head-to- During such a transmetalation, it is conceivable

tail coupling.
that the coordination of palladium(II) species to the
carbon-carbon multiple bond constitutes the initial
nucleophilic organometallics, such as 1-alkenylmer-
step for the interaction of both species and probably
curials,67 -silanes,68 and -tin compounds.69 this jr-interaction serves to accelerate the ligand
Organopalladium(II) halides add mainly to the exchanges.74 Thus, the 1-hexynyl group exclusively
electron-deficient carbon of unsymmetrical alkene66
to give 15, which readily isomerizes to 16 via a couples with iodobenzene, but it is surprising that
the transfer of primary alkyl group occurs quite
sequence of elimination and readdition of the hydri-
smoothly compared with 1-alkenyl or phenyl groups.
dopalladium(II) iodide. Finally, the elimination of Thus, the quaternization of trialkylboranes ac-
iodoborane with the aid of triethylamine gives the
celerates indeed the transmetalation to the palla-
head-to-tail cross-coupling product. A deuterium-
dium(II) halides. Although there is no direct evi-
labeling study proves the addition-elimination mech- dence that the boronate anions, such as RB(OH)3 ',
anism where a /3-hydrogen transfers to the terminal are capable of effecting the transmetalation, it is
carbon (Figure 2).70
The cross-coupling reaction of organoboron com- quite reasonable to assume the similar effect of base
for the transmetalation of organoboronic acids. The
pounds with organic halides or triflates selectively cross-coupling reaction of arylboronic acids with aryl
reacts in the presence of a negatively charged base, halides at pH 7-8.5 is retarded relative to the
=

such as sodium or potassium carbonate, phosphate, reaction at pH 9.5-11.75 The p.Ka of phenylboronic
=

hydroxide, and alkoxides.20-65 The bases can be used acid is 8.8, thus suggesting the formation of the
as aqueous solution, or as suspension in dioxane or
DMF. In contrast, the cross-coupling reaction with hydroxyboronate anion [RB(OH)3_] at pH > pifA and
its transmetalation to the palladium(II) halides. The
certain electrophiles, such as allylic acetates,656 1,3- formation of ArB(OH)3~ at pH 11-12 has been =

butadiene monoxide,71 and propargyl carbonates,72

occurs under neutral conditions without any as- recently reported.76
sistance of base. The transmetalation of organoboron Recently, fluoride salts have been found to effect
to the cross-coupling reactions of 1-alkenyl- and
compounds with palladium halides under basic or arylboronic acids (eq 31).77 The species that under-
neutral conditions can be considered to involve the
goes transmetalation is assumed to be organo(tri-
following three processes: eqs 29, 32, and 39. fluoro)borate ion.
RPdX
R1—B-OR F.
R2
R2
+ 3 CsF _k_
I
I
ArB(OH)2 Ar-^-F Ar-Pd(ll)-R (31)
1 F
R'-R2 (29)
Pd
1
Pd
|

R1
VPd(0)
An alternative transmetalation process found dur-
X
ing our investigations is that organoboron compounds
readily transfer their organic groups to (alkoxo)-
It is apparent that the transmetalation between palladium(II) complexes under neutral conditions (eq
organopalladium(II) halides and organoboron com- 32).
pounds does not occur readily due to the low nucleo-
R2
philicity of organic group on boron atom. However, R2 R’-BX2
the nucleophilicity of organic group on boron atom I
I

-sr- R’-R2 02)

can be enhanced by quaternization of the boron with Pd
I
T
ROBX2
Pd
I

R1
)
Pd(0)
OR
Table 2. Cross-Coupling Reaction of “Ate” Complexes
(Eq 30) 20

yield, % (18/19)
R
Although the cross-coupling reaction with organic
Pd(PPh3)4 PdCl2(dppf) halides generally requires the assistance of bases,
c4h9 81 82 allylic phenoxides and cinnamyl acetate react with
ch3ch=ch 85 (45/55) 95 (53/47)
1-alkenylborates under neutral conditions to yield the
c4h9c=c 98 (71/29) 81 (95/5)
Ph 79 (38/62) 92 (53/47) corresponding 1,4-dienes, 75% and 12%, respectively
(eq 33).656’78 Thus, the (.T-allylphenoxo)- and (71-
Reactions of Organoboron Compounds Chemical Reviews, 1995, Vol. 95, No. 7 2463

allylacetoxo)palladium(II) intermediates generated

by oxidative addition may undergo transmetalation
without bases. The isolated complexes of (?/3-CaHo)-
22
o-O 24 (R’=Ph)

22: R=Me (78%), Et (76%), 'Bu (47%), Ph (12%)

(37)

PdX react with 1-alkenylborates to give the coupling

products when the ligand X is OAc or acetylacetonato
(acac).65b The another piece of evidence for this
unique ligand effect of the Pd-0 bond is also
22 (R=Me) +
XHQ-< y -- 24 (R1= p-XCsH4) (38)

observed on the alkenyl-alkenyl coupling reaction Rel. rale: MeO (0.7), Me (0.9), H (1.0), F (1.7), MeCO (2.6)
(eq 34). The (alkoxo)palladium(II) complexes are
stable enough to be isolated if substituted with
ing that electron-withdrawing substituents accelerate
electron-withdrawing groups (21b), otherwise 13- the reaction (eq. 38 and Figure 3).
elimination occurs very quickly to give the hydri- These electronic effects are consistent with the Se2
dopalladium(II) species and carbonyls.79 The isolated (coord) mechanism involving a coordination of the
21b easily reacts with 1-alkenylborates precipitating
alkoxy ligand to the boron atom at the the rate-
palladium black, whereas the corresponding chloro determining step. As a result of complex formation,
complex (21a) is quite inert even at the refluxing the transfer of an activated organic group from boron
temperature of THF.65b The (hydroxo)palladium to palladium then takes place82 (Figure 4). Such
complex recently reported by Alper80 also gives a complexation prior to migration is one of the crucial
cross-coupling product (70%) together with biphenyl steps essential in all ionic reactions of organoboron
(15%) (eq 35).
compounds; namely, the well-known intramolecular
1,2-migration from the organoborane/electrophile
3a(R'="Bu)
RCH=CHCH2OX
—-
"BuCH=CHCH2CH=CHR (33) complex.
Pd(PPh3)4 For the transmetalation between optically active
benzene, reflux
(l-phenylethyl)silicate10d,e or -tin83 and palladium(II)
X=COMe; R=Ph (12%), X=Ph; R=H (75%) halides, the Se2 (cyclic) or Se2 (open) mechanism
which takes place with retention or inversion of the
Cl Cl configuration at benzylic carbon atom is proposed.
3a (R1="Hex) CU Unfortunately, these stereochemical features have
PdX(PPh;j)2 _-i y^
^
"Hex (34) not yet been established for organoboron compounds
Cl Cl because their coupling reactions are still limited to
21a: X=CI
21 b- X=OMe X=CI (0%), X=OMe (79%) primary alkylboranes.
Finally, it is of interest to note the possibility of
involvement of the (alkoxo)palladium intermediate

OO"
/=\ /=\ 20 in the palladium/base-induced cross-coupling re-
?ph3 p-MeOCeH48(OH)2
Ph-Pd-OH/,2 -
(35)
THF, rt action (eq 39).
70%
It is known that the halogen ligand on organopal-
ladium(II) halide is readily displaced by alkoxy,
hydroxy, or acetoxy anion to provide the reactive Pd-
Tsuji and co-workers have shown that propargylic OR complexes (20),84 which have been postulated as
carbonate 22 oxidatively adds to the palladium(O)
complex to provide an (alkoxo)palladium intermedi-
ate 23 with elimination of carbon dioxide (eq 36).81
Thus, the reaction of 22 with alkylboranes, 1-al-
kenyl-, 1-alkynyl and arylboronic acids or their esters
gives 24 in high yields under neutral conditions.72

Pd(0)
Me Hex Bu
A
Hex—(—CsC-Bu
0C02R
22
T Me
23
Pd-OR

R1BX2
Hex Bu Hex Bu
_1_ H=< Pd-R',-^sT* )=*=<R1, (36)

T
robx2
Me >
Pd(0)
Me

24 Figure 3. Linear free energy relationship for the cross-

coupling reaction of para-substituted phenylboronate with
The reaction offers other direct evidence for such 22 (R =
Me).
a boron-palladium transmetalation process through Hex Bu
an (alkoxo)palladium(II) species. The reaction of the
phenylboronate with various carbonates indicates Me Pd-- OR
that less hindered and more nucleophilic alkoxy Iff
groups accelerate the cross-coupling (eq 37). o'/ •BC
A series of the competitive reaction rate between
para-substituted phenylboronates and 22 (R = Me) 25

gives a slightly positive p value (+ 0.73), demonstrat- Figure 4. Se2 (coord) transition state.
2464 Chemical Reviews, 1995, Vol. 95, No. 7 Miyaura and Suzuki

& NaOR
R2
r1bx2
R2

| 1

Pd
-^p N*
Pd
1

OR
ROBX2
rj
1

R1
T" Pd(0)
(39)

20

reaction intermediates85 or isolated79,80 from the

reaction of organopalladium(II) halides with sodium AcOB(OR)2
hydroxide or methoxide. It is not yet obvious in many
reactions which process shown in eq 29 or 39 is ~Ar-Pd(ll)-OAc

predominant; however, the formation of alkoxo-, (RO)2BB(OR)2

hydroxo-, or acetatopalladium(II) intermediate should Figure 6. Cross-coupling with (alkoxy)diboron (eq 6).
be considered to be one of the crucial transmetalation
processes in the base/palladium-induced cross-cou- the diboron is proposed as a key step. The acetoxy
pling reactions. anions do not act as a base to coordinate with boron
The reaction of 1-alkenylboronates with haloenones atom under the given reaction conditions. The
shows a characteristic feature for the (alkoxo)palla- catalytic cycle is shown in the Figure 6.
dium mechanism (eq 40).86 The cross-coupling reac- A similar (methoxo)platinum intermediate has
tion with haloenones is accelerated by exceptionally been recently reported for the transmetalation be-
weak bases such as NaOAc or even EtaN, when tween a cationic platinum(II) complex and potassium
methanol is used as a solvent. The results cannot teraphenylborate (eq 42).89
be explained by the ate-complex mechanism shown
Me
in eq 27, and can be best understood by the formation
of (alkoxo)palladium(II) intermediate (28) since 27 Ls + /,°Me PhB< k + ,
V- U+
Pt -
Pt Pt (42)
readily exchanges the halogen ligand with methanol . / ,
/
Ph
i
/ SPh
due to its strong trans effect of the electron-poor
alkenyl group (eq 41).
B. Other Catalytic Process by Transition-Metal
Complexes
Recently, transition-metal complexes have been
reported as efficient catalysts for the addition of
metal reagents, including magnesium, aluminum,
silicone, zinc, germanium, and tin compounds to
alkenes and alkynes.90 Although the related reac-
tions of boron compounds are not yet well developed,
the Rh-, Pd-, or Ni-catalyzed hydroboration of al-
kenes91 and alkynes27 (eqs 43—46) has been exten-
sively studied since the catalyst allows the reaction
under very mild conditions and often can direct the
The palladium-catalyzed cross-coupling reaction of course of the addition of borane to a different
(alkoxy)diboron derivatives provides the first one-step selectivity than the uncatalyzed reaction (eq 43).91m
procedure for arylboronic esters from aryl halides (eq Asymmetric hydroboration of styrene is achieved
6).87 Potassium acetate is one of the best bases to using a bidentate chiral ligand (eq 44).911 Hydrobo-
achieve a selective cross-coupling, and stronger bases ration of 1,3-butadiene stereoselectively affords a (Z)-
such as potassium carbonate or phosphate give biaryl crotylboronate with a palladium(O) complex (eq 45).91k
byproducts arising from further coupling of the The PdCl2(dppf) and NiCl2(dppe) or -(dppp) complexes
product with aryl halides. afford good results for the hydroboration of alkynes
The treatment of the phenylpalladium(II) bromide (eq 46).27b
with KOAc gives a £rcms-PhPdOAc(PPh3)2 (29)87,88 The Pd(0)-catalyzed addition of the B—S bond to
which exhibits high reactivity toward (alkoxy)diboron terminal alkynes regio- and stereoselectively pro-
derivatives selectively giving the phenylboronate at duces (Z)-2-(organothio)-1 -alkenylboron reagents (eq
room temperature (Figure 5). Thus, the transmeta- 47) 92 addition of (alkoxy)diboron to alkynes to
lation involving formation of 29 and its reaction with give cis-bis(boryl)alkenes (diboration) is catalyzed by
a platinum(O) catalyst47 (eq 23).
PtiBr The additions proceed regioselectively in favor of
terminal boron adducts to produce (Z)-l-alkenylboron
Pd(PPh3)«
compounds through a syn addition of the X-B bond
(RO)2BB{OR)2 to 1-alkynes. The mechanism is fundamentally dif-
ferent from the uncatalyzed process and is postulated
fPh3
Ph-Pd-Br
KOAc (j>Ph3
Ph-Pd-OAc _L_ to proceed through the oxidative addition of the X-B
PPh3
DMSO
r.t PPh3
benzene
r.t T
Pd(0)
PhB(OR)2
bonds (X= H, RS, Y2B) to the transition-metal
29 complex [M(0)] to form X-M—BY2 species (32), fol-
Figure 5. Formation of palladium(II) acetate and its lowed by the migratory cis insertion of alkenes or
transmetalation. alkynes into the X-M bond, and finally the reductive
Reactions of Organoboron Compounds Chemical Reviews, 1995, Vol. 95, No. 7 2465

OSifBu)Ph2 Pd(OAc)2
3c

Vr (48)
—

hbx2 10] R’CH=CH2

BnO THF, r.t.

Pd(0)
OSi('Bu)Ph2 OSi('Bu)Ph2
H transfer from
BnO' 'Y' 'Y' 'OH + BnO^rN^CIH (43)
solvent
R
Pd(ll)B(Sia), Pd(ll)H

HBX2 = 9-BBN 35:65

2a / RhCI(PPh3)3 90:10

Rh(BINAP)* PhCH=CH2
PhCH=CH2 + 2a -

96%ee
Ph-CH
’•vU (44) ArB(OH)2
Pd(OAo)2 / NaOAc
AoOH, 25 “C
PhCH=CHPh

34
(49)

Pd(0)

ch2=chch=ch2 +
„
2a --
Pd(PPh3)4
\=/ /"OCD (45)
PhCH=CH2
81% [ Ar-Pd(ll)-B(OH)2]
R2
NlCfe(dppo) The mechanism for the carbonylative cross-cou-
R’SCsCR2 + 2a
R’s'A!P'lf*! (46)
pling reaction for synthesis of ketones is discussed
30 in section VI. The mechanisms for alkoxycarbon-
ylation and dimerization of organoboron compounds,
R’CsCH + R2s *=*- which require a reoxidant of palladium similar to the
-<D R„r 31
<D
(47)
Wacker process, is discussed in section VII.

IV. Cross-Coupling Reaction

elimination of alkenylboron compounds from 33
regenerates the M(0) complex, as shown in Figure A. Coupling of 1-Alkenylboron Derivatives:
7 27d,47,92
Synthesis of Conjugated Dienes
The oxidative adducts such as B-Rh-H and The stereo- and regioselective syntheses of conju-
B-Ir-H intermediates275 in the catalytic hydrobo- gated alkadienes are of great importance in organic
ration, and the B-Pt-B intermediate93 in the dibo- chemistry by themselves, as well as their utilization
ration have been isolated and fully characterized by in other reactions such as the Diels-Alder reaction.
X-ray analyses, and by observing its insertion reac- A number of new methods for the preparation of
tion to alkynes. Since the catalytic cycle is a very conjugated dienes and polyenes have been developed
powerful and fundamentally common process with a by utilizing various organometallic reagents. Among
group 10 transition metal, the further uses of this these procedures, the most promising ones are per-
type of reaction will certainly be exploited in the haps those based on the direct cross-coupling reaction
future. of stereodefined alkenylmetals with stereodefined
The oxidative addition of the C-Hg bond to Pd(0) haloalkenes in the presence of a catalytic amount of
complex is involved in the catalytic carbonylation and a transition-metal complex.5 810 Although the rep-
the homo coupling of aryl- or vinylmercurials.94 resentative 1-alkenylmetal reagents undergo a simi-
Similar reaction type such as dimerization,95 proto- lar type of coupling reactions with haloalkenes, there
nolysis of the C—B bonds (eq 48),96 and Heck-type are several limitations when one wishes to obtain
addition (eq 49)97 of aryl- or alkenylboronic acids take unsymmetrical dienes without homocoupling, highly
place in moderate yields. The reactions can be functionalized dienes, or stoichiometric conditions
catalyzed by palladium(O) catalysts without phos- relative to metal reagents and halides. Thus, much
phine ligands. The mechanism has not yet been attention has been recently been focused on the use
elucidated in detail, but it is reasonable to speculate of 1-alkenylboronic acids or their esters,20 because a
the oxidative addition of the C-B bond to palladium- variety of 1-alkenylboron derivatives are now readily
(0) complex. available, as discussed in the section II.
The first observation to prepare conjugated dienes
is shown in eq 50.65'98-100 The high yield of diene is
obtained when relatively strong bases such as sodium
ethoxide and hydroxide are used together with a
phosphine-based Pd complex, e.g., Pd(TPh3)4 and
PdCl2(PPh3)2. In general, a combination of Pd(PPh3)4
and sodium ethoxide works satisfactorily for the
coupling with 1-bromo-l-alkenes, and PdCl2(PPh3)2
and aqueous sodium hydroxide for 1-iodo-l-alkenes.
The use of palladium catalyst without phosphine
ligand or weak bases (KOAc or Et3N) has a tendency
to be contaminated by undesired head-to-tail coupling
product (36).70 The reaction can be carried out in
M= Ni, Pd, Rh
aqueous media by using water-soluble phosphine
Figure 7. A general catalytic cycle for additions. palladium catalyst.101
2466 Chemical Reviews, 1995, Vol. 95, No. 7 Miyaura and Suzuki

Pd-catalyst / base Table 3. Reaction of (Z)-BuCH=CHBX2 with Phl°

3a (R’^Bu) +

-bx2 yield, %b isomeric purity, %

-B(Sia)2 58 >94
|S01
49 >83
35 36
\ /2
-B(OPri)2 98 >97
Although disiamyl- or dicyclohexylborane is a
selective and efficient hydroboration reagent of a
A mixture of Pd(PPh3)4 (3 mol %), 2 M NaOEt in EtOH (2
alkynes, 1-alkenyldialkylboranes thus obtained give equiv), Phi (1 equiv), and (Z)-BuCH=CHBX2 (1.1 equiv) in
benzene was refluxed for 3 h. b Yields of (Z)-BuCH=CHPh.
relatively poor yields of coupling products (~50%)
with low stereoselectivity.102 The difficulty appears
to be due to side reactions arising from the protode- the coupling are prepared by starting from two
boronation with water or alcohols and the transfer alkynes. The stereoselective syntheses of (E)- and
of secondary alkyl group to the palladium(II) halide. (Z)-l-alkenylboronic acids or esters are discussed in
Some loss of the reagent decreases the yields of the previous section (eqs 8 and 11). Halogenation of
coupling products and the transfer of secondary alkyl the corresponding alkenylboronic acids with iodine
group forms an undesirable palladium(II) hydride or bromine provides (E)- and (Z)-haloalkenes from the
species which induces isomerization of the double same starting material (eqs 56 and 57).107 The
bond. The protodeboronation of 1-alkenylboron com- palladium and base-assisted coupling of each five and
pounds with alcohols is faster than with water, and 11 units stereoselectively provides bombykol and its
it decreases in the following order: 9-BBN > B(cy- three geometrical isomers (eqs 58-61).108
clohexyl)2 > B(Sia)2 » B(OR)2.103 Thus, the high
yields and high isomeric purity exceeding 99% can Eq. 8
be achieved by using 1-alkenylboronic acids or their c^h/:=ch (53)

esters. Yields and stereoselectivity on the cross-

coupling of (Z)-l-hexenylboron reagents with iodo-
benzene are shown in Table 3." Eqs. 10 and 11

Thus, the oxidation of the two boron-sp3 carbon C^7C=CBr- (54)

bonds with triethylamine N-oxide prior to the cou-

pling solves the difficulty arising from the B—C bond
protonolysis and the contamination of the coupling hoioh^coh (55)
product with alkyl group (eq 51).104,105
39
R R
F2C=c' + Me3NO -
F2C=C Iz / NaOH
HO(CH2)s^^ (56)
BR2 B(OR)2
40
Arl
-
F2C=C (51) 1. Brz
PdC^PPh3)2 *
(57)
THF, reflux 2. NaOMe H°(CH2)9^J
41
The absence of a convenient route to 9-vinyl-9-BBN 80 %
has severely limited the use of 9-BBN derivatives in 37 + 40 c3h7. (58)
(CH^sOH
this coupling. However, the reagents are now avail-
able under very mild conditions by a sequence of (CH2)9OH
91 %
dihydroboration of terminal alkynes and dehydrobo- 37 + 41 (59)
rylation with an aromatic aldehyde. The cross-
coupling with organic halides readily undergoes in
the refluxing THF in the presence of Pd(PPh3)4 and 82%
38 + 40
an aqueous NaOH (eq 52).30,106 (60)

MejSiCsCH
9-BBN
MejSiCHjCH
0 ArCHO 36 + 41
69 %
(61)

(Z,E)- or (2?,Z)-dienic structures are rather common

in the sex pheromones of insects. The procedure has
(Z)-1 -bromo-1 -hexene been successfully applied to the syntheses of Euro-
M 03Si
MeuSi (52)
Pd(PPh3)<
THF, aq. NaOH
pean grape wine moth,109,110 red bollworm moth,109
reflux 85% and Egyptian cotton leafworm109,111 sex pheromones.
Since a variety of 1-alkenylboron reagents includ-
Bombykol is a well-known pheromone, first isolated ing (E)- and (Z)-isomers are now available, their
from Bombyx mori L. Bombykol and the related three cross-coupling with 1-halo-l-alkenes affords various
isomers were synthesized by the cross-coupling reac- stereodefined alkadienes and trienes.98-100 Many
tion. Three alkenylboronates or boronic acids (37— syntheses of alkadienes and trienes such as unsatur-
39) and two vinylic halides (40 and 41) required for ated fatty acid amides,112 alkenylsilanes,106,113 gem-
Reactions of Organoboron Compounds Chemical Reviews, 1995, Vol. 95, No. 7 2467

Table 4. Synthesis of Dienes and Trienes

Entry Alkenylboron Reagent Alkenyl Halide Reaction Conditions, Product Yield/% Ref
_catalyst/base/solvenlAemp._
Pd(PPh3)4/NaOEt 86 (>98) 98
C,He^<0 /benzene/reflux

CeH„
2
Br-^j Pd(PPh3)4/NaOEt X = Sia 49 (>98) 102
C4H„
C«Hi3 /benzene/reflux

3 X = OPt' 97 (>99) 99

4 Pd(PPh3)4/aq. KOH °H 70 (>99) 100

C4HS-^YB(0P^ /benzene/reflux
C4H»^Yr
CHj CH3 CHj

Bu' Bu' CeH13

*paH,3
^^BfBu'b Pd(PPh3)4/aq.NaOH 87 (>99) 105
/THF/reflux

Br^YCH3 ('Pr)3SI^Y^YCH3 85 (-) 106a

('PrbSi^A)) CHj
Pd(PPh3)4/aq.NaOH
/THF/reflux CHa CH3
CH3

SiMej ch3 SiMej

C3H7v^kB(c_Hx)j
Br^* Pd(PPh3)4/aq.NaOH 40 (-) 113a,b
/THF/reflux
ch3

Ph ch3 Ph
C4Hj
\
Br'Y Pd(PPh3)4/NaOEt
/benzene/reflux
87 (-) 117
Q" CHj

Pd(PPh3)4/aq. NaOH
Br"^SPh benzene, reflux
91 (>98) 118
Si

10 Br' 89 (>94) 115

Pd(PPh3)4/NaOEt
/benzene/reflux

O,

11 PdfPPh^aOEt 52 (-) U6
/benzene/reflux
B(Sia)2
OBn

difluoroalkenes,104,113 cyclic alkenes,114 (ClO)-allofar- 5,8,10,14-icosatetraenoic acid [(12R)-HETE],122 and

nesene,115trisporol B,116 and vinylsulfides118 are a macrolide antibiotic rutamycin B123 (Figure 9).
reported by application of Pd-catalyzed cross-cou- This modification of base has been realized on the
pling. The representative syntheses and reaction assumption that the transmetalation involves a pal-
conditions summarized in Table 4.
are ladium(II) alkoxide or hydroxide intermediate (20 in
The coupling rate enhancement was realized by eq 39); namely, thallium base may accelerate the
Kishi by using an aqueous TlOH in place of sodium formation of 20 by forming water-insoluble thallium
or potassium alkoxide or hydroxide. The cross- salts instead of NaX. However, another process, i.e.,
coupling between (E)-l-alkenylboronic acid and (Z)- the transmetalation of alkenylboronic acids to thal-
iodoalkene stereoselectively furnished the C75—C76 lium salts giving an alkenylthallium(I) or -(III) spe-
bond formation of palytoxin at room temperature cies, has not yet been investigated.124
(Figure 8).119 Hydroboration of enynes provides 1,3-alkadienyl-
Roush, Nicolaou, and Evans have also demon- boron derivatives. The coupling of dienylboron com-
strated the efficiency of thallium hydroxide on the pounds with haloalkenes allows a short-step synthe-
synthesis of an aglycone of antibiotic kijanimicin,120 sis of conjugated trienes; for example, the synthesis
chlorothricolide,121 (5Z,8Z,10E,12/?,14Z)-12-hydroxy- of leukotriene B4 shown in eq 62.125,126 Due to the
2468 Chemical Reviews, 1995, Vol. 95, No. 7 Miyaura and Suzuki

this combination for synthesis of the conjugated

pentaene (eq 63).127

Figure 9. The coupling reactions induced by T10H. /3-Halo-a,/?-unsaturated ketones and esters are
highly susceptible to Sn2 displacement at the carbon
difficulty of purification of a geometrical mixture, the attached to halogen, thus strong bases are undesir-
stereodefined syntheses might be essential for such able for such substrates.86’128-131 However, relatively
trienes. As discussed previously, the coupling reac- weak bases, such as sodium acetate and even tri-
tion is carried out more efficiently by 1-alkenylbo- ethylamine, are effective when the reaction is con-
ronic acids or esters; however, l-alkenyl(disiamyl)- ducted in alcohol solvents (eqs 40 and 64).86 Sodium
boranes have been often used as a coupling reagent acetate suspended in methanol, and aqueous or solid
since hydroboration of alkynes having allylic or carbonate in ethanol give best results for ha-
loenones86 and haloesters,129 respectively. PdCl2-
propargylic hydroxy functional groups does not afford
good results with catecholborane. Aqueous lithium (PPli3)2 or a combination of Pd(OAc)2 plus PPI13 (4
hydroxide is shown to be one of the best bases that equiv) is desirable to achieve high yields. The cis/
avoids the C—B bond breaking during the cross- trans isomerization is rarely observed in the pal-
coupling (eq 62).126 ladium-catalyzed cross-coupling, but the reaction
with (Z)-yd-bromoacrylate gives a mixture of stereo-
A reverse combination of 1-alkenylboronates and isomers. PdCl2(dppf) is effective for carrying out the
1-halo-1,3-alkadienes is expected to lead to the same reaction at room temperature in order to depress the
trienes, but this combination is generally not recom- isomerization during the coupling (eq 65).129
mended because of the synthetic problems of unstable Conjugated enynes are of importance in them-
dienyl halides and the side reaction eliminating selves, as well as in their utilization for synthesis of
hydrogen halides with bases to produce the corre- conjugated dienes. The cross-coupling reaction of
sponding enyne. However, the thallium base allows l-alkenyl(disiamyl)boranes (3c) with 1-bromo-l-
Reactions of Organoboron Compounds Chemical Reviews, 1995, Vol. 95, No. 7 2469

O dure for the synthesis of benzo-fused heteroaromatic

Me PdCte(PPh3)2 compounds.136 Although numerous modifications of
3a(R1='Bu) +
NaOAc
(64) this general method have been studied, the major
MeOH, reflux
97%
Bu
difficulty seems to be the lack of a general method
for the required ori/io-functionalized areneethanals.
COjEt
3 EtOCsCH + BH3 --
(EtOCH=CH)3B (69)
3a (R1=rBu)
Br-^ 42
(65)
Pd-catalyst R
Na2C Os / EtOH
EtOCaCR + 2a --
<70)
catalyst temp/°C time/h yield/% (2E/2Z)
43
Pd(OAc)2»2PPh3 reflux 5 70 (37/63)

PdlOAcfe'dppe reflux 5 80 (80/20)

Pd(OAc)2*dppf reflux 5 86 (23/77)

Pd(OAc)2*dppf 20 24 73 ( 5/95)

alkynes provides conjugated enynes in high yields (eq

66).65 The enynes thus obtained can be readily
converted into the corresponding dienes by hydrobo-
ration—protonolysis sequence.132
Pd(PPh3)4
The cross-coupling reaction of tris(2-ethoxyeth-
3c + BrC=CR2 (66) enyl)borane (42)137 or 2-(2-ethoxy-l-alkenyl)-l,3,2-
NaOMe-MeOH
benzene, reflux R2 benzodioxaboroles (43) with iodoarenes produces
styryl ethers in high yields in the presence of Pd-
R’ R2 yield/% (PPh.3)4 and powdered NaOH suspended in THF.138,139
Since 42 and 43 have a tendency to undergo base-
98
C4H9 c6h13 induced decomposition on prolonged heating, it is
c4h9 Ph 74 desirable to use iodoarene derivatives as a substrate
Ph C6H,3 95 or an excess boron reagent for relatively unreactive
haloarenes. Removal of the MOM protecting group,
ch3 Ph 93
followed by cyclization gives benzo[6]furans in high
The cross-coupling reaction of 1-alkenylboronates yields by treatment with HC1 in methanol (presum-
is useful for alkenylation of haloarenes (eq 67).133,134 ably to give cyclic acetals first), followed by dealkoxy-
lation with polyphosphoric acid (PPA) at 100 °C (eq
Pd(PPha)4 71).138
3aJj + ArX
NaOEt
Ar (67) Conversion of haloarenes to areneethanal precur-
benzene, reflux sors also can be carried out by the cross-coupling
reaction of (2-organothio-l-alkenyl)boron derivatives
The relative reactivity appears to be Phi > which will be discussed in the section IV.E.
p-ClC6H4Br > PhBr > o-MeC6H4Br > o-MeOC6H4-
Br.133 The order of reactivity is in good agreement B. Coupling of Arylboron Derivatives: Synthesis
with substituent effect in the oxidative addition of of Biaryls
aryl halides to the palladium(O) complex,52 and The first observed method to prepare biaryls is
presumably the substituents accelerate the trans- shown in eq 72.140 After this discovery, various
metalation rate in the same order. The procedure, modifications have been made for the reaction condi-
involving a hydroboration-coupling sequence, gives tions. A combination of Pd(PPh3)4 or PdCl2(PPhs)2
a new access to HGM-CoA reductase inhibitor NK-
and aqueous Na2C03 in dimethoxyethane (DME)
104 (eq 68).135
works satisfactorily in most cases.141,142

0^-B(OHfe +x-0 I
Z
benzene, reflux
OO
Z
I
<72>

The combination with other bases such as EtsN,143

NaHC03,141 Cs2C03,144 T12C03,145 and KgPO,146 with
or without Bu4NC1147 and 18-crown-6144 also have
been used. The reaction is successful for aryl triflates
and iodo- and bromoarenes. Chlorobenzene deriva-
tives are generally quite inert to oxidative addition,
but some of jr-difficient heteroaryl chlorides gives
coupling products.148 The reaction proceeds more
rapidly in homogeneous conditions (aqueous base in
Cyclodehydration of 2-hydroxy- or 2-aminobenze- DME), but the reasonable yields are also obtained
neethanal derivatives is known as a general proce- under heterogeneous conditions. For example, K2-
2470 Chemical Reviews, 1995, Vol. 95, No. 7 Miyaura and Suzuki

C03 suspended in toluene works well for base- boronic acid) 2,6-dimethoxy (125), 2-F (77), 2-C1 (59),
sensitive reactants.149 The coupling is also carried 2-MeO (11), 4-MeO (4.2), 2-Me (2.5), 3-F (2.3), 3-Me
out in an aqueous medium by using water-soluble (2), 4-F (1.7).155 For example, the coupling of
phosphine ligand (/n-Na03SC6H4PPh2).101 Although 2-formylphenylboronic acid with 2-iodotoluene at 80
the conditions using such bases are not entirely °C using an aqueous Na2C03 in DME gives only 54%
compatible with the functional groups present in the of biaryl with benzaldehyde (39%). The yield can be
desired reactants, the extremely mild conditions improved to 89% by using the corresponding ester of
using CsF or BU4NF (eq 31) allow the synthesis of boronic acid and anhydrous K3PO4 suspended in
various functionalized biaryls (eq 73).77 DMF (eq 76).151 However, Negishi’s coupling using
corresponding arylzincs5 or Stille’s coupling using
Ph-B(OH)2 + Br C HjCOCHj arylstannanes8e is perhaps a more general alternative
in such cases.
Pd(PPh3)4
An aryl-aryl exchange between the palladium
CsF/DME at 100 °C
CHjCOCHj (73) center and phosphine ligands in palladium(II) com-
85% plexes is enhanced by electron-donating substitu-
ents.156 The synthesis of biaryls substituted with
Phosphine-based palladium catalysts are generally electron-donating groups results in contamination of
used since they are stable on prolonged heating; the coupling product with the aryl group on phos-
however, extremely high coupling reaction rate can phine ligand. Tris(2-methoxyphenyl)phosphine is
be sometimes achieved by using palladium catalysts effective in reducing the formation of such by-product
without a phosphine ligand such as Pd(OAc)2, [(??3- while maintaining a high yield of the desired product
C3H5)PdCl]2, and Pd2(dba)3-C6H6.75’150 Phosphine- (eq 77).157
free palladiums are approximately 1 order of mag-
nitude more active than ArPdIII*PPh3)2, both of which +
Pd(PArj)4
Br
are in turn markedly more active than Pd(PPh3)4 (eq B(OH)2
aq. Na2C 03
DME
74). MeO OMe

catalyst
PhB(OH)2 + I N02 (74) (77)
aq. K2C O3
acetone
65 °C MeO OMe

catalyst:
Pd(PPha)4 (8 h, 23%); PhPdl(PPh3)2 (0.33 h, 53%); Pd(OAc)2 (0.75 h, 98%) Ar = Ph 54% 27%

Ar=o-MeOC6H5 79% 3%
Although steric hindrance of aryl halides not a
major factor for the formation of subsituted biaryls, The cross-coupling reaction of arylboronic acids is
low yields are resulted in when using ortAo-disub-
largely unaffected by the presence of water, tolerating
stituted arylboronic acids. For example, the reaction a broad range of functionality, and yielding nontoxic
with mesitylboronic acid proceeds only slowly because
of steric hindrance during the transmetalation to byproducts. The reaction offers an additional great
advantage of being insensitive to the presence of
palladium(II) halide. The addition of strong bases, (W/io-functional groups or heteroaromatic rings.
e.g., aqueous NaOH or Ba(OH)2, both in benzene and Gronowitz has shown that unsymmetrically substi-
DME exerts a remarkable effect on the acceleration tuted bithienyls141158 and thienylpyridines159 can be
of the coupling rate (eq 75).151-153 Although weak
bases give better results for less hindered arylboronic
regioselectively synthesized by the cross-coupling
reaction of thienylboronic acids (eq 78). Arylation of
acids, the order of reactivity for mesitylboronic acids 5-bromonicotinates is demonstrated by Thompson160
corresponds to the basic strength: Ba(OH)2 > NaOH (eq 79). Diethyl(3-pyridyl)borane synthesized by
> > >
K3PO4 Na2C03 NaHCOg.151 Terashima147 is a unique air-stable reagent for the
heteroarylation (eq 80).

-q
Pd(PPfr)4
B{OH)2 + Ar-X
aq. 8a(OH)2
DME, 80 °C
0"Ar (75)

ArX: 2-MeOC6H4I (80%), (78)

2-CIC^I (94%), 2-bromonaphthalene (86%)

Q"0 CHO
* *x
PflPPha),
KaP04
DMF, 80 "C
CHO
(76)

(79)

ArX: iodomesitylene (73%), 2-MOMOC9H4l (85%), 2-MeOjC C9H4Br (63%)

reflux

Even if there is no great steric hindrance, the MeCO .N=\ MeCO

reaction under aqueous conditions gives undesirable
results due to competitive hydrolytic deboronation.154
0“ 2
”
)=N
(80)
PdtPPhj),
The rate for the cleavage of XC6H4B(OH)2 with water aq. NaOH / BU4NCI
at pH 6.7 is shown as follows: (relative to phenyl- THF, reflux 77%
Reactions of Organoboron Compounds Chemical Reviews, 1995, Vol. 95, No. 7 2471

The ready availability of ort/io-functionalized aryl-

boronic acids by directed ort/io-metalation-borona-
tion sequence provides a synthetic link to the cross-
coupling protocol. Snieckus has amply demonstrated
that the sequence has considerable scope for the
synthesis of unsymmetrical biaryls, heterobiaryls,
and terphenyls161 (eq 81). The utility of the sequence
has recently shown by the industrial-scale synthesis
of a nonpeptide angiotensin II receptor antagonist162
(eq 82).

3. H+
Ar-Br

Pd(PPh3)4
aq. Na20O3
<> (81)

H00c
ME, reflux Planar Poly(p-phenylene)

Water-Soluble Poly(p-phenylene)

Figure 11. Aromatic rigid-rod polymers.

high-performance engineering materials, conducting

polymers, and nonlinear optical materials. The cross-
coupling reaction of aryldiboronic acids and diha-
loarenes for the synthesis of polyfp-phenylenes) was
first reported by Schluter.174 The method has been
As a consequence, the reaction has been used extensively applied to monodisperse aromatic den-
drimers,175 water-soluble poly(p-phenylene),176 planar
extensively in the synthesis of natural and unnatural
poly(p-phenylenes) fixed with the ketoimine bonds,177
products and pharmaceuticals such as saddle-shaped
host compounds,163 ferrocene derivatives,164 bis-cy- poly(phenylenes) fused with polycyclic aromatics,178
and nonlinear optical materials179 (Figure 11).
clometalating N—C-N hexadentated ligands,165 heli-
cally chiral ligands,166 michellamine,153 biphenomy- Arylboronic acids are also efficient reagents for
cine A,167 vancomycin,168 receptor molecules for oxo arylation of 1-alkenyl halides and triflates. Arylation
of various haloalkenes such as a-iodo-a,/3-unsatur-
acids,169 leukotriene B4 receptor antagonist,170 hemi-
ated lactams,180 6-[(alkoxycarbonyl)amino]-l-bromocy-
spherand,171 l,l'-bi-2-naphthols,161r fascaplysin and
clohexene,181 l-iodo-3,4,6-tri-0-(triisopropylsilyl)-D-
streptonigrin alkaloids,172 ungerimine and hippadine
glucal182 (eq 83), and the bromoalkene precursor for
alkaloids,1611 and other biaryls.173 Some of examples
are summarized in Figure 10.
(Z)-tamoxifen synthesis183 are achieved by the cross-
Aromatic, rigid-rod polymers play an important coupling reaction of arylboronic acids. Arylcycloal-
kenes are prepared by the cross-coupling with cor-
role in a number of diverse technologies including
responding triflates184 (eq 84). For the arylation of
Me OBn triflates, higher yields can be obtained in the pres-
ence of LiCl or LiBr (see: section IV.D).

PfaSiO'
1-naphthylB(OH)2
Pr,SiO' (83)
PdCfe(PPh3)2
aq. NasC O3
THF, reflux
75%

3-02NC6H4B(0H)2
(84)
Pd(PPt*)4
aq. Na^ 03/ LiCl
DME, reflux

C. Coupling of Alkylboron Derivatives

Although alkylmagnesium, -zinc, -tin, and -alumi-
Ar num reagents have been successfully used for the
Fe
cross-coupling reaction with organic halides,1-11 the
i—Ar reaction of alkylborane derivatives is particularly
useful when one wishes to start from alkenes via
hydroboration.
,V-Bis(aryl)ferrocene
Also, the base as well as palladium catalyst is
1

essential for the success of the coupling reaction.185-188

A combination of PdCLidppf) and aqueous NaOH in
THF works nicely for most cases. Although strong
bases accelerate the coupling reaction, more weak
Figure 10. Synthesis of biaryls. bases and aprotic conditions are desirable for func-
2472 Chemical Reviews, 1995, Vol. 95, No. 7 Miyaura and Suzuki

tionalized alkylboranes or organic halides. The reac- tion of 9-alkyl-9-BBN with a-iodoenones. It is rec-
tion can be carried out by powdered K2CO3 or K3PO4 ognized that cesium carbonate in the presence of
suspended in DMF at 50 °C in the presence of PdCl2- water extremely accelerates the coupling reaction
(dppf) catalyst.185’186 Pd(PPh3)4 catalyst works well carried out at room temperature (eq 86).194
when aqueous NaOH in benzene or K3PO4 in dioxane
are used.185 The characteristic features of both
catalysts are that PdCUidppf) is used well in polar .(M.02C(CH2)e).9.BBN
solvents (e.g., THF and DMF), but Pd(PPh3)4 gives QT1 PdCla(dppf)/P^As
good results in nonpolar solvents, such as benzene TBDMSO-'
DMF/THF/H2O
TBDMStf
and dioxane. M.
0
One of primary alkyl groups in trialkylboranes
,(CH2)6C02H
participates in the coupling, and the reaction with J (86)
secondary alkyl is very slow.185 Thus, representative
hydroboration reagents, such as 9-BBN, disiamylbo-
rane, dicyclohexylborane, and borane, can be used as
hydroboration reagents for terminal alkenes. How-
ever, 9-BBN is most accessible due to its ease of use, 9-Methyl and 9-[(trimethylsilyl)methyl]-9-BBN are
high selectivity on hydroboration, and high reactivity easily synthesized by the reaction of the correspond-
on the cross-coupling reaction. ing lithium reagents with 9-methoxy-9-BBN. Un-
The hydroboration coupling approach for the con- fortunately, such derivatives are spontaneously flam-
mable in air, making them particularly hazardous
struction of carbon skeletons affords several advan- to handle for isolation. However, selective oxidation
tages (eq 85).185 The high stereoselectivity of hy- with anhydrous trimethylamine AT-oxide converts
droboration provides a stereodefined alkyl center on them to air stable borinate esters (eq 87) which are
boron. The hydroboration occurs chemoselectively at efficient reagents for methylation195196 of haloalkenes
the less hindered C19-C20 double bond. In addition, or syntheses of allylic and propargylic silanes197 (eq
the alkyl group thus constructed can be readily cross-
88).
coupled with alkenyl or aryl halides under mild
conditions. R
/
B
Me3NO
(87)

45a: R=Me
45b: R=CH2SiMe3

Pd(PPh3>4
45b + C3H7 Br [ c^|7 CH2SiMe3
\=J aq. NaOH \=/ (88)
THF, reflux 97%

The intramolecular cross-coupling proceeds espe-

cially smoothly when the cyclization results in the
formation of either five- or six-membered rings.185198199
The procedure has been used in a variety of The hydroboration of the terminal double bond with
syntheses of natural products;189
190
for example, in 9-BBN is faster than that of the halogenated double
the synthesis of dihydroxyserrulatic acid (Figure bond, e.g., (the relative rate), 2-methyl-l-pentene
12),191 the aggregation pheromone of Cathartus quad- (196); 1-hexene (100); (Z)-l-bromo-l-butene (0.011).
ricollis (quadrilure),192 and aza-C-disaccharides.193 Thus, hydroboration coupling approach provides a
A three-step, three-component synthesis of PGEi new route for stereodefined exocyclic alkenes (eq 89).
is achieved by utilization of the cross-coupling reac-
OTBS OTBS
1. 9-BBN
(89)
2. PdCI2(dppf)
aq. NaOH
THF, reflux 60%

Although alkylboronic acids or their esters are

quite inert under above conditions, the organobor-
onates are more convenient to use, since they are
stable in air and are handled easily for isolation. The
cross-coupling of alkylboronates with 1-alkenyl or
aryl halides proceeds in moderate yields in the
presence of TI2CO3 and PdCl2(dppf), although the
reaction is limitedly used for activated halides having
an electron-withdrawing group. A sequence of the
Rh(I)-catalyzed hydroboration273 of ally! acetone and
the cross-coupling with haloenones produces dike-
Figure 12. Synthesis of dihydroxyserrulatic acid. tones in 62—69% yields (eq 90).200
Reactions of Organoboron Compounds Chemical Reviews, 1995, Vol. 95, No. 7 2473

»
2a precursors. The ready availability of triflates from
Me-C-CH2CH2CH=CH2 Mb-C-(CH2)4b'
carbonyl compounds now offers a valuable tool for
o RhCI(PPh3)3 C
Q
toluene, 0 °C annulation of ketones (eq 93).206 Since the synthesis
of the compounds having a metal and a leaving group
Br-
C 02M 8 in the same molecule is rather difficult by other
Me-C-(CH2)4
PdCI2(dppf)
O
C 02M 0 (90) methods, the hydroboration-coupling approach pro-
TI2C03 68% vides an efficient way for such cyclization via the
THF, 50 "C
intramolecular coupling.
The coupling with triflates often fails to proceed
D. Coupling with Triflates due to the decomposition of catalysts, precipitating
Although the cross-coupling reaction with organic palladium black at the early stage of reaction.206’207
halides have been studied predominantly, it has been Presumably, triphenylphosphine used as a ligand of
most recently discovered that trifluoromethane- palladium reacts with triflates to give phosphonium
sulfonates (triflates) undergo a clean coupling with salts (eq 94).208 Addition of 1 equiv of lithium or
organoboron compounds, similar to organostan- potassium bromide is effective in preventing such a
nanes8,201 aluminum202 and zinc203 compounds. The decomposition of the catalyst, which is known to
triflates are valuable as partners for the cross- convert the labile cationic palladium(II) species to
coupling reaction, in part due to the easy access from organopalladium(II) bromide.209 Lithium chloride or
phenols or carbonyl enolates which allow the selective potassium chloride is less effective, though LiCl has
formation of aryl and 1-alkenyl electrophiles.204 The been used in most cases.184’207
cross-coupling reaction of organic triflates is previ-
LiBf
ously reviewed.205 R0Tf (R-Pd(l)] p~fO]'»Ln -
R-Pd-8r»L2 (94)
Although relatively strong bases such as aqueous
NaOH and NaOEt in ethanol have been used for the PhaP

reaction with halides, powdered K3PO4 suspended in

[PhaPR]* [TfO]" + Pd(0)
THF or dioxane is sufficient enough to accelerate the
coupling of 9-alkyl-9-BBN, 1-alkenyl-, and arylbor- The order of reactivity of halides and triflates for
onates or boronic acids with the triflates.206 Pd-
the cross-coupling reaction of boron reagents is I >
(PPh3)4 in dioxane at 65 °C is less effective than Br > OTf » Cl. Thus, the sequential cross-coupling
PdCLidppf) in refluxing THF, but it may give a reaction of 4-bromophenyl triflate with two 9-alkyl-
comparable yield by carrying out the reaction at 80 9-BBN derivatives, obtained from two different al-
°C (eqs 91 and 92). The choice of suitable boron
kenes, furnishes the unsymmetrically disubstituted
reagents effects high yields of products. For arylation benzenes. However, an alternative and presumably
of triflates, boronic acids afford better results than
reliable method to introduce two different organic
the corresponding boronic esters (eq 92), and 9-alkyl-
9-BBN derivatives are recommended as the best groups to benzene rings is a stepwise double cross-
couplings with iodophenol derivatives (eq 95).151’206
reagents for alkylation. The catechol esters of 1-al-
kenylboronic acids usually work more effectively than
the corresponding boronic acids and disiamyl or
dicyclohexyl derivatives (eq 91).206
COjEt
+

OTf •9-0ctyl-9-BBN/PdCl2(dppf)/K3P04 in THF, reflux. bHO/MeOH,

CsH,, cNaH/Tf20.'*9-[MeC(02C2H4)(CH2)4]-9-BBN/PdCl2(dppfyK3P04
in THF, reflux

(91)
Ready availability of cycloalkenyl triflates from
ketone precursors is superior to the synthesis of
corresponding halides. The syntheses of arylated
cycloalkenes184’210 and 2-substituted carbapenem (eq
96)211 have been achieved in excellent yields by the
(92)
reaction with triflates.

-CP
1. 9-BBN

2. Pd(PPh3)4
(93)
K3PO4
CO^e dioxane, 85 °C 76% CQ2Me

Although good yields are achieved for five- and six-

E. Synthesis of Vinylic Sulfides
membered cyclization by the intramolecular cross- 1-Alkenyl sulfides are valuable intermediates for
coupling reaction of haloalkenes (eq 89), the scope of the synthesis of ketones or aldehydes by hydrolysis
the reaction is still limited by the availability of with mercury(II) chloride,212 the synthesis of 1-al-
haloalkenes, particularly due to the lack of a simple kenyl sulfoxides213 which can serve as dienophiles in
method for preparing cyclic haloalkenes from ketone the Diels-Alder reaction or as Michael acceptors, and
2474 Chemical Reviews, 1995, Vol. 95, No. 7 Miyaura and Suzuki

the synthesis of a variety of alkenes and dienes via R’

the nickel-catalyzed cross-coupling reaction214 of the RSCsCR' 2a

NlClj(dppe) RS^ ^B'
+ (100)
C—S bond with Grignard reagents. However, there H
are only a few stereoselective syntheses of 1-alkenyl
sulfides. The coupling reactions of 1-alkenyl halides R=Me, Et, Ph; R’=H, alkyl, aryl, vinyl, SR 48

with thioalkoxides in the presence of a transition-

"Bu
metal catalyst provide vinylic sulfides in excellent
Of
yields with high stereoselectivity.6
cc
215
Another route ^'NHAc
to vinylic sulfides involves cross-coupling reactions 48 (R=Me, R'="Bu)
Pd(PPh3)4
between (/3-alkylthio)alkenyl halides and alkyl, aryl, aq. KOH
benzene, reflux
and 1-alkenylmagnesium halides.214 Wittig and re- 80%
lated methods unfortunately provide a mixture of
stereoisomers.216
(101)
The cross-coupling reaction of 9-(organothio)-9-
BBN derivatives (46) with 1-alkenyl and aryl halides
proceeds in excellent yields (eq 98).217 The reaction
can be carried out under milder conditions than those The hydroboration of thioalkynes with diorganobo-
of analogous reactions using lithium or tin thioalkox- ranes predominantly gives vinylborane intermediates
ides. by the addition of boron atom at the carbon adjacent
to the organothio group. However, the catalytic
hydroboration of thioalkynes with catecholborane in
RSH + 9-BBN RS-B (97) the presence of NiCl2(dppe) or PdfPPhah allows a
complete reversal of the regiochemical preference
providing 48, the regioselectivity of which is over 98%
46 +
'^>h
PdClj(dppf) —
RS'^VPh (98) (eq 100).27b The reaction is synthetically complemen-
K3P04
DMF, 50 °C 93% (R=*Bu)
tary to the catalytic hydrostannylation of thioalkynes
providing l-(organothio)-l-alkenylstannanes.219 A
vinylic sulfide is synthetically equivalent to a carbo-
(E)- and (Z)-l-bromo-2-(phenylthio)alkenes (47) are nyl compound. Thus, the cross-coupling products
efficient building blocks for the synthesis of stereo- obtained from o-iodoacetoanilide derivatives are
defined 1-alkenyl sulfides by the cross-coupling reac-
readily converted into indoles by treatment with
tion with organoboron compounds (eq 99).118,218 The aqueous mercury(II) chloride (eq 101).27c
sulfides 47 have several advantages in terms of their When a solution of terminal alkyne and 9-RS-9-
practical use for cross-coupling reaction. (E)- and (Z)- BBN in THF is heated at 50 °C for 3 h in the presence
47 are readily available and most importantly, both of Pd(PPhs)4 (3 mol %), the cis addition of the B-S
stereoisomers are readily separable by chromatog- bond to alkyne proceeds regio- and stereoselectively
raphy. The rate of coupling with the carbon- (eq 102).92 Although the adduct 49 is too susceptible
bromine bond is reasonably faster than that with the to C—B bond breaking or stereochemical isomeriza-
carbon—sulfur bond, which completely avoids the tion during isolation, its in situ preparation and
formation of the symmetrical coupling product. subsequent cross-coupling reaction with organic ha-
lides gives a variety of alkenyl sulfides retaining their
original configuration of alkenylboron reagents (eq
104).92

"BuCsCH + PhS
o Pd(PPh3)4 "0(j
y^i
PhS
49
(102)

Me2CsCHMgBr "Bu
_

(99) r.L
NiCls(dppp)
ether, rt
kJk, 49 + MeOH
PhS
>= (103)
'
87% (3Z)/(3E)=87/13
Pd(PPha)4 "Bu>
49 + BrCsCBu" (104)
The sequential double cross-coupling of vinylbor- aq. KOH PhS Bu"
onates and vinylmagnesium reagents provides an THF, 50 “C
70%
alternative method for synthesis of conjugated poly-
enes (eq 99).118 Unfortunately, a mixture of stereo-
isomers is given on the latter nickel-catalyzed reac-
49 + C5H,,CHO THF
H2O
w
PhS OH
reflux
tion.214 The possibility of improving catalytic con- 80%
ditions has not yet been explored. HgCfe "Bu,
(105)
The ready availability of 2-(organothio)-l-alkenyl- CH3CN/ HjO v^x"^A5^11
O
boron compounds obtained by catalytic hydroboration 85%
of l-(organothio)-l-alkynes (eq 100)27b or thiobora-
tion92 of 1-alkynes (eq 102) now offers more flexible The vinylborane 49 has unusually high nucleophi-
and reliable routes to such stereodefined alkenyl licity due to the activation by an electron-donating
sulfides in combination with the cross-coupling reac- /?-organothio group. Consequently, protodeborona-
tion with organic halides. tion proceeds instantaneously with methanol to
Reactions of Organoboron Compounds Chemical Reviews, 1995, Vol. 95, No. 7 2475

provide the thiol adducts regioselectively92 (eq 103). Pd(PPIb)4

Although ketones are quite inert to 49, the addition Me-I + MeOi>C(CH2),o-B
K3PO4
MeQ2C(CH2)ioCH3 (107)
to aldehydes at 50 °C, followed by the mercury(II)- dioxane, 50 c
°
71%
induced hydrolysis gives an enone (eq 105).220
Pd(PPb3)4
CH3(CH2)gl + Ph-B (CH2)9CH3 (108)
F. Coupling with Iodoalkanes: Alkyl-Alkyl k3po4
dioxane, 50 °C
55%
Coupling
Although a wide variety of organic electrophiles, It is reported that the cycloalkylpalladium(II)
such as aryl, 1-alkenyl, benzyl, allyl, and 1-alkynyl bromide intermediate, which is produced by Heck
halides, have been utilized for the palladium-cata- reaction of norbornene with bromoarenes, couples
lyzed cross-coupling reactions, it has been considered with tetraphenylborate (eq 109).224 However, the
that such reactions cannot be extended to alkyl reaction with secondary iodoalkanes does not provide
halides with sp3 carbon having /3-hydrogens due to
the slow rate of oxidative addition of alkyl halides to coupling products, presumably due to a very rapid
/3-hydride elimination.
palladium(O) complexes and the fast /3-hydride elimi-
nation from cr-alkylpalladium intermediates in the
catalytic cycle. Thus, the use of alkyl halides as PdBr«L, NaBPh4 Ph
(109)
coupling partners is a challenging problem in several anisole, 80°C
Ar
recent publications. Although Castle and Widdow- H H
son221 had recently reported that Pd(dppf), formed in
situ by the reduction of PdCl2(dppf) with DIBAL, The cross-coupling with inactivated alkyl halides
effectively catalyzes the cross-coupling reaction of is still difficult to achieve in high yields with pal-
iodoalkanes with Grignard reagents, this unique ladium-catalyst, but the potentiality and synthetic
reaction has been denied most recently by Yuan and utility thus suggested should be explored in the
Scott.222 future. The coupling reaction with alkyl halides by
Among the catalysts we examined for the cross- a LiCuCU catalyst is perhaps a more general alter-
coupling reaction between 9-alkyl-9-BBN with pri- native, although the reaction is still limited to Grig-
mary iodoalkanes, the palladium complex with tri- nard reagents.3b,e
phenylphosphine as ligand is recognized to be most
effective (eq 106).223 The best yield is obtained when G. Coupling with Other Organic Halides and
Boron Reagents
C ,0H21I8%
decane 27% Hydroboration of alkynes with disiamylborane,
Pd(PPh3)4 t°l decene 9% followed by cross-coupling with allylic or benzylic
c10h2,-i c4h,-b
t
CmHm 50% (106)
<3> tC,P04 butane 3% halides in the presence of Pd(PPh3)4 and aqueous
dioxane, 50 °C butene 3%
butanol 28%
NaOH produces 1,4-alkadienes or allylbenzenes in
high yields.96’225 In the reaction with l-bromo-2-
butene, the bond formation occurs at two positions
the reaction is conducted at 60 °C for 24 h by using
(the ratio of straight to branched is 72:28) in ac-
3 mol % ofPd(PPh3)4 and KsP04 (3 equiv) in dioxane. cordance with a mechanism involving jr-allyl pal-
Although PdCl2(dppf) is reported as a selective ladium intermediate.225 The reaction has been ap-
catalyst to avoid /3-hydride elimination for alkyl plied in a short step synthesis of humulene (eq
couplings, the complex does not act as an efficient 110).226 The cross-couplig reaction of 1,3-disubsti-
catalyst in the present reaction. Other bidentate tuted allyllic carbonates with aryl- and alkenylbo-
ligands such as dppe, dppp, and dppb also give low rates are catalyzed by NiC^ldppf), and the reaction
yields of coupling products. Such bidentate ligands proceeds with inversion for the cyclic carbonate (eq
may retard the step of reductive elimination because HD 227 The stereochemistry indicates the process
the reductive elimination from dialkylpalladium(II)
involving the oxidative addition with inversion and
proceeds from an unsaturated, three-coordinated the arylation from the same face of the palladium.
species (eq 25), in contrast to the coupling with aryl
or vinyl derivatives which can proceed through a
four-coordinated saturated complex (eq 24).57
Pd(PPh3)4
The difficulty of alkyl-alkyl coupling reaction is (110)
aq. NaOH
mainly due to the formation of alkane at the step of benzene, reflux
oxidative addition of iodoalkane to Pd(0) complex.
The /3-elimination druing the steps of transmetalation
and reductive elimination is a minor process. The
formation of reduction products (decane in eq 106) ^q^"B(OM9)3U
(111)
can be mainly due to the involving radical oxidative NiCIgdppf)
addition process (see section VI).53
The available results indicate that the cross-
coupling reaction of 9-alkyl-, 9-phenyl-, or 9-(l- 1-Alkenylboranes react with 3,4-epoxy-l-butene in
alkenyl)-9-BBN gives 50—60% yields of products the presence of palladium or nickel complexes to form
when using 50% excess of primary iodoalkanes and internal and terminal coupling products with high
higher yields around 80% when using iodomethane regioselectivity in same cases (eq 112).71 The ratio
(eqs 107 and 108).223 of two dienols can be reversed by changing the metal
2476 Chemical Reviews, 1995, Vol. 95, No. 7 Miyaura and Suzuki

complexes. The reaction proceeds under neutral V. Head-to-Tail Coupling

conditions in good agreement with the mechanism
The reaction of phenyl or 1-alkenyl iodides with
through an (alkoxo)palladium(II) complex (20 in eq
32). 1-alkenylboronic esters produces the unusual “head-
to-tail” cross-coupling products in good yields (eqs 28
A and 117)70’232 through the mechanism shown in
Pd(0)-catalyst .

ch2=ch-ch-ch2 -- o Figure 2.
Pd*

"Bu
Pd(0Ac);/BH3
3a + ICH=CHPh
EtsN (5 equiv)
>= (117)
PhCH=CH
DMF, 80 °C
61%
As discussed in the previous section, propargylic
carbonates couple with aryl, 1-alkenyl-, 1-alkynyl-, The reaction is catalyzed by palladium black pre-
or alkylboron compounds under neutral conditions pared in situ by the reduction of Pd(OAc)2 in the
using palladium catalyst to provide allenes in high presence of an excess of triethylamine in DMF. The
yields (eq A similar coupling reaction of
36).72 use of phosphine-based palladium complexes and
organoboron compounds with 2,3-alkadienyl carbon- strong bases such as NaOEt, NaOH, and NaOAc may
ates produces 2-substituted 1,3-butadiene derivatives improve the formation of “head-to-head” coupling
in the absence of base (eq 113).228 The coupling may product (Table 1).
occur through an (alkoxo)palladium(II) intermediate The intramolecular reaction affords a convenient
formed via oxidative addition by Sn2' type displace- method for the synthesis of (exomethylene)cycloal-
ment with Pd(0), thus allowing the reaction under kenes (eqs 118 and 119).233
neutral conditions.

1 *naphthylB(OH)2
(113)
Pd(PPhs)4
benzene, reflux

Allylic, benzylic, and propargylic boron derivatives

are considered to be not useful for the cross-coupling
reaction because these reagents are highly sensitive
to protodeboronation with water or alcohols. How-
ever, it is interesting to note that these boron
reagents provide the coupling products in high yields
even in an aqueous medium. The Pd(PPh3)4-cata-
lyzed reaction of tri(crotyl)borane with iodobenzene
in the presence of aqueous NaOH in refluxing THF
gives two coupling products in a 87% total yield (eq VI. Carbonylative Coupling
114) .229 The cross-coupling reaction of propargylbo-
rates, prepared in situ from alkyl-1,3,2-benzodiox- Carbonylative cross-coupling reactions of organic
aboroles and (a-lithiomethoxy)-l,2,3-butatriene, pro-
halides with organometallic compounds, such as
236
duces the allene product through the 1,3-rearrange- organotin,234 boron,235 aluminum,237 and zinc238
ment, presumably at the step of transmetalation (eq reagents have been extensively studied and reported
to provide excellent methods for the synthesis of
115) .230
unsymmetrical ketones or aldehydes. The general
Ph catalytic cycle for this carbonylative coupling reaction
Ph-I
Phv^ss/ is analogous to the direct coupling except that carbon
(CH3CH=CHCH2)3B + (114)
Pd(PPh3)4
monoxide insertion takes place after the oxidative
74% 13%
aq. NaOH
THF, reflux
addition step and prior to the transmetalation step
(Figure 13).
OMe MeO Me
I Phi
Me 0=0 “
C“* C ^1 ^3
Pd(PPh3)4
)=•=< (115)
aq. NaOH C^13 Ph

*£o THF, reflux

Only one example is reported for the cross-coupling

reaction of 1-alkynylboron compounds. Methoxy-
(alkynyl)borates in situ prepared by addition of
9-methoxy-9-BBN to alkynyllithiums undergo ef-
ficient cross-coupling with aryl or 1-alkenyl halides
to produce various alkynes (eq 116).231

RC^Li MeQ,-/V\ AfX

RC=C-Ar
MeO-B
_

(116)
RCsC '\J/ Pd(PPh3)4
THF, reflux Figure 13. Mechanism for carbonylative cross-coupling.
Reactions of Organoboron Compounds Chemical Reviews, 1995, Vol. 95, No. 7 2477

Among a variety of organometallics, organoboron ficiently slower than that of carbon monoxide inser-
compounds were first used by Kojima for the syn- tion by changing the organometallic reagents. The
thesis of alkyl aryl ketones (eq 120).235 The action reaction of organoboron reagents can be controlled
of Zn(acac)2 in this reaction is ascribed to the forma- by choosing an appropriate base and a solvent to
tion of RCOPdn(acac) species (eq 121) which under- permit the selective coupling even under an atmo-
goes transmetalation without assistance of bases (eq spheric pressure of carbon monoxide (eq 126).240
32).
PhB(OH)2/CO(1 atm)

CO ArX
PdCl2(PPh3)2 R-C-Ar PdCI2(PPh3)2 / base, anisole, 80 °C
1 + + (120)
Zn(acac)2 O
THF-HMPA, SO °C
Me-C C-Ph (126)
6 O
53
51 + Zn(acac)2 (121)
Base (53*4)= K2C03 (88/12), CsjC03 (75/25), KjPO* (65/35)

The use of organic iodides is essential to achieving

A general carbonylative cross-coupling can be
high yields. Organic bromides provide appreciable
readily carried out using K2CO3 or K3PO4 as a base. amounts of direct coupling products since the trans-
Alkyl 1-alkenyl and alkyl aryl ketones are synthe- metalation of 50 (X = Br) with organoboron reagents
sized by the reaction of 9-alkyl-9-BBN with 1-alkenyl
is faster than the corresponding iodides (path A in
or aryl iodides in the presence of Pd(PPh3)4 and K3-
Figure 13). In all of these reactions, some of the
PO4 (eq 122).239 For the synthesis of biaryl ketones,
the cross-coupling reaction between arylboronic acids, carboxylic acid derivatives formed from path B can
be commonly observed.239 240
carbon monoxide, and iodoarenes in anisole takes The cross-coupling reaction has been currently
place at 80 °C in the presence of PdCl2(PPh3)2 and developed; however, such reactions are limitedly
K2CO3 (eq 123).240 The hydroboration-carbonylative
applicable to 1-alkenyl, 1-alkynyl, aryl, allyl, and
coupling sequence is extended to intramolecular benzyl halides and not being extended to alkyl
reaction to afford cyclic ketones (eq 124).239 The ate halides with sp3 carbon containing /3-hydrogen, as
complexes obtained from a-lithioindoles and trieth- discussed in the previous section. The problem of
ylborane are carbonylated and coupled with aryl /3-hydride elimination is not serious in the carbon-
iodides, alkenyl iodides, or cycloalkenyl triflates to
ylation reaction because the insertion of carbon
provide a simple route to 2-indolyl ketones (eq 125).241 monoxide converts them to the acylpalladium(II)
CO (3 atm)
halides. Thus, various iodoalkanes including pri-
CH3(CH2)7B mary, secondary, and tertiary iodides are carbony-
'(D (CH2),CH3 (122)
lated and coupled with 9-R-9-BBN in the presence
dioxane
of K3PO4 and a catalytic amount of Pd(PPh3)4 yielding
unsymmetrical ketones in good yields (eq 127).242 The
reaction is extremely accelerated by irradiation of
(123)
CO (1 atm) sunlight.
PdCtelPPtvjte
I^COj, anisole, 80°C 86%

OMOM OMOM
(127)

cx
1. 9-BBN C02Me
(124)
2. CO (1 atm) \
PdOj(PPh3)2
benzene, rt 74% a9-[Me02CCMe2(CH2)3]-9-BBN / CO (1 atm) /
Pd(PPh3)4 / K3P04 / benzene, rt under irradiation of light

A particularly interesting feature in this transfor-

mation is that oxidative addition proceeds through
the radical process; presumably, it is initiated by an
electron transfer from palladium(O) complex to io-
Although the reaction works well for iodoarenes doalkanes to form a radical pair (Pd’X + R*).53 Thus,
and 1-iodo-l-alkenes having electron-donating groups, the iodoalkenes provides cyclized ketones via a
the application to the electron-deficient iodides is sequence of radical cyclization, carbon monoxide
severely limited due to the side reaction forming insertion, and the coupling with 9-R-9-BBN (eqs 128
direct coupling products without carbon monoxide and 129).243 The cyclization is generally not stereo-
insertion (Figure 13, path A). Namely, the presence selective, but the reaction of 55 proceeds with high
of an electron-withdrawing group retards the inser- endo selectivity due to the anomeric effect which
tion of carbon monoxide into the RPd(II)X intermedi- prefers the transition state (56) shown in eq 129.244
ates, and it reversely accelerates the rate of trans- As isocyanides are isoelectronic with carbon mon-
metalation to generate the R—Pd11—R' species. The oxide, they might be expected to exhibit a similar
use of carbon monoxide under high pressure is a insertion reaction. However, they have not been used
general method for suppressing such a side reac- for the cross-coupling reaction. The difficulty is
tion.234 Another efficient procedure involves the mainly due to its tendency to cause multiple inser-
control of the rate of transmetalation to be suf- tions to transition metal complexes leading to poly-
2478 Chemical Reviews, 1995, Vol. 95, No. 7 Miyaura and Suzuki

ou
SiMe3 CO {1 atm) SiMe3
9-BU-9-BBN MeOH
(128) 'Buvs^ls (131)
CO (1 atm) CO,Ms
PdCfe
Pd(PPh3)4 O' NaOAc
K3PO4
"Bu
55 p-benzoquinone / UCI 87%
benzene, rt
under irradiation of light 77% (E/Z=8/92)
eqs. 14 and 15
CaCH
f^B(OH)2
Ph
CO (1 atm)
MeOH
'4^u02Me (132)
PdCfe
NaOAc Ph
70% (Z>94%)
p-benzoquinone / UCI

Pd(OAc)2«4PPh3
3a or 3c R1 (133)
(129) Cu(OAc)2

In the presence of a catalytic amount of Pd(OAc>2

and Cu(OAc)2 as a reoxidant, 1-alkenylboronates
isocyanides. The 9-alkyl-9-BBN reacts with isocya- readily dimerize in methanol to give symmetrical
nide to form a relatively stable 1:1 complexes which dienes (eq 133).95 Although the blank test indicates
readily participates in the cross-coupling reaction that the dimerization proceeds to some extent in the
catalyzed by palladium. The complexes are success- absence of palladium catalyst, a few mole percent of
fully used for the iminocarbonylative cross-coupling Pd(OAc>2 may greatly improve the yield of diene.
reaction of 9-alkyl-9-BBN derivatives with haloare- Symmetrical biaryls can also be obtained from aryl-
nes (eq 130).245 boronic acids.

+ ArX
Pd(PPha)4
R-C-Ar
VIII. Conclusion
B' (130)
1^04 II
The cross-coupling reaction of organoboron re-
.

CN'Bu dioxaneTTHF CN'Bu

agents with organic halides or related electrophiles
50 °C

represents one of the most straightforward methods

VII. Alkoxycarbonylation and Dimerization for carbon-carbon bond formation. The reaction
proceeds under mild conditions, being largely unaf-
Unlike the cross-coupling reaction discussed above, fected by the presence of water, tolerating a broad
the palladium-catalyzed alkoxycarbonylation of or-
range of functionality, and yielding nontoxic byprod-
ganoboron compounds proceeds through the trans- ucts. Consequently, the cross-coupling reaction of
metalation of organic group on boron to palladium(II)
organoboron reagents has been realized in significant
atom, CO insertion into the C-Pd bond, and finally and diverse applications not only in academic labo-
the reductive elimination to the products and Pd(0). ratories but also in industries. In view of retrosyn-
Thus, suitable reoxidants of palladium(O) to pal- thetic analysis, the reaction is conceptually basic and
ladium (II) are required to recycle the palladium
important for construction of carbon framework of
catalyst (Figure 14). p-Benzoquinone in the presence target molecules. The scope of the palladium-
of LiCl selectively oxidizes the palladium(O) complex
in the presence of aryl- or 1-alkenylboronic esters.246 catalyzed cross-coupling reaction of the representa-
tive organoboron compounds with organic halides are
Under atmospheric pressure of carbon monoxide, summarized in Figure 15.
1-alkenylboronates are carbonylated at 50 °C in the A very wide range of aryl- and 1-alkenylboron
presence of PdCL, NaOAc, p-benzoquinone, and LiCl reagents undergo the palladium(0)-catalyzed reac-
in methanol (eqs 131 and 132).247 The stereochem- tions with alkyl, allylic, 1-alkenyl, aryl, and 1-alkynyl
istry of 1-alkenylboronates can be retained over 99%. substrates. Allylic halides react with aryl- and
The hydroboration-carbonylation sequence cleanly
1-alkenylboron reagents, but alkyl- and allylboron
provides terminal esters in contrast to the direct reagents fail to give the corresponding coupling
alkoxycarbonylation of terminal alkynes with carbon products; presumably because the reductive elimina-
monoxide and alcohol in the presence of transition- tion from CT-alkyl-."r-allyl-
metal catalyst.
or di-jr-allylpalladium(II)
complexes is very slow to develop the catalytic

o 15. Scope of palladium(0)-catalyzed cross-coupling

Figure
Figure 14. A catalytic cycle for carboalkoxylation. reaction.
Reactions of Organoboron Compounds Chemical Reviews, 1995, Vol. 95, No. 7 2479

cycle.248 Since the palladium-catalyzed cross-cou- Organic Synthesis; Harwood Academic Pub.: Amsterdam, 1983.
Pelter, A.; Smith, K.; Brown, H. C. Borane Reagents; Academic:
pling reaction of allylic metals or halides often suffers New York, 1988.
from poor regioselectivity, the corresponding cross- (13) Gardner, J. H.; Borgstrom, P. J. Am. Chem. Soc. 1929, 51, 3375.
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1938, 60, 105. Johnson, J. R.; Van Campen, M. G.; Grummitt,
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for the carbonylative cross-coupling. The cross- Radinov, R. N. Helv. Chim. Acta 1992, 75, 170. Oppolzer, W.;
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A. ; Srebnik, M. J. Organomet. Chem. 1993, 444, 15. Langer, F.;
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Chim. Acta 1973, 56, 1192. Giacomelli, G.; Menigagi, R.; Ca-
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