180 Organometallic & Miscellaneous reagents

PRACTICE SET
Pd(PPh3)4
H3CO Br + H2C CHCH2Sn(n-Bu)3 H3CO CH2CH CH2
(1) 120ºC, 20 h
96%
Pd(PPh3)4
O2N Br + H2C CHSn(n-Bu)3 O2N CH CH2
(2) 105ºC, 4 h
80%
PdCl2(PPh3)2
H3CO SnBu3 + F3CO2SO NO2 H3CO NO2
(3) LiCl2, DMF
48%

Br
Pd(PPh3)4, 10 mol %
+
(4) AgO, 1 equiv,
N Sn(n-Bu)3 N N 70%
DMF, 100ºC
N

O OCH(CH3)2 PhCH2Pd(PPh3)2Cl, 5 mol % O OCH(CH3)2

Cul, 10 mol %
+ I OCH3
DMF
(5) O Sn(n-Bu)3 O
80%
OCH3

PdCl2(CH3CN)2
PhHC CHI + H2C CHSn(n-Bu)3 PhHC CHCH CH2
(6) 25ºC, 0.1 h
85%
H
H3C CH3 CH3
(H3C)3Sn H H3C C Si(CH3)3
Pd(PPh3)4 C
(7) OSO2CF3 + C C
H Si(CH3)3
CH3 CH3H 100%

O O
Pd(CH3CN)2Cl2 CH3
I
5 mol %
(8) + (n-Bu)3Sn CH3
Ph3As, 10 mol %
CH3 CH3
NMP, 100ºC

CH3 Pd(PPh3)4 CH3

Sn(n-Bu)3 + I CH2OH THF, DMF
(9) O O CH2OH
OTBDMS CH3 OTBDMS CH3 42%
Pd2(dba)3, 5 mol %
O3SCF3 CO2CH3 Ph3As, 10 mol % CO2CH3
+
(10) Ph (n-Bu)3Sn NHCO2C(CH3)3 DMF NHCO2C(CH3)3

Ph
4.6.6. Suzuki reaction :
Coupling with Organoboron Reagents. The Suzuki reaction is a palladium-catalyzed cross-coupling reaction
in which the organometallic component is a boron compound. The organoboron compounds that undergo
coupling include boronic acids, boronate esters, and boranes. The overall mechanism is closely related to that
of the other cross-coupling methods. The aryl halide or triflate reacts with the Pd(0) catalyst by oxidative
addition. The organoboron compound serves as the source of the second organic group by transmetallation,
and
Organometallic & Miscellaneous reagents 181

O
PhCH2PdCl/PPh3
O2N COCl + (H3C)3Sn O2N C
18 h
97%
O
PhCH2PdCl/PPh3
COCl + (H3C)3SnC CC3H7 CC CC3H7
23 h
70%
O
PdCl2, PPh3
(H3C)2C CHCOCl + (n-Bu)3Sn (H3C)2C HCC

85%

O O O
PhCH2PdCl/PPh3
CH3CNHCH(CH2)5COCl + (CH2=CH)4Sn CH3CNHCH(CH2)5CCH CH2

CO2C2H5 CO2C2H5 70%

O PhCH2Pd(PPh3)2Cl O
CO2C2H5 0.7 mol %
O2N CCl + (n-Bu)3Sn O2N C
CO
CO2C2H5
80%

Pd(PPh3)2Cl2, O
PhCHSn(n-Bu)3 + PhCOCl CuCN PhCHCPh
76ºC
CO2CH3 CO2CH3 78%
The disubstituted Pd(II) intermediate then undergoes reductive elimination. It appears that either the oxidative
addition or the transmetallation can be rate determining, depending on reaction conditions. With boronic acids
as reactants, base catalysis is normally required and is believed to involve the formation of the more reactive
boronate anion in the transmetallation step.

ArX  Pd 0 
 Ar Pd II  X
 [ArB(OH)3 ]
ArB(OH) 2   OH 
[ArB(OH)3 ]  Ar  Pd II X 
 Ar Pd II  Ar  B(OH)3  X 
Ar  Pd II Ar 
 Ar  Ar  Pd 0
One of the potential advantages of the Suzuki reaction, especially when boronic acids are used, is that the boric
acid is a more innocuous by-product than the tin-derived by-products generated in Stille-type couplings.
Alkenylboronic acids, alkenyl boronate esters, and alkenylboranes can be coupled with alkenyl halides by
palladium catalysts to give dienes.
R H R' H R H
Pd(PPh3)4 H
H BX2 H Y H
H R'
X = OH, OR, R
Y = Br, I
These reactions proceed with retention of double-bond configuration in both the boron derivative and the
alkenyl halide. The oxidative addition by the alkenyl halide, transfer of an alkenyl group from boron to palla-
dium, and reductive elimination all occur with retention of configuration.
Both alkenyl disiamylboranes and B-alkenylcatecholboranes also couple stereo-specifically with alkenyl bro-
mides.