Heck reaction - 1
I
PdCl2, AcONa
+
CO2Me
CO2Me
97%
MeOH
CO2Me
CO2Me
I
+
Pd(OAc)2
CO2Me
, Et3N
Pd(OAc)2, P(o-tol)3
Et3N
Br
Br
Ph
Cl
+
OMe
Pd(OAc)2, dippb, AcONa
DMF, 1500, 24 h
PhCO
OMe
COPh
36
97%
Heck reaction - 2
Pd(OAc)2, K2CO3
+
CO2Me
I
C4H9
Br
CO2Me
Pd(OAc)2, K2CO3, DMF
+
I
70%
+ Bu4N Br , rt
CHO
+
C4H9
+ Bu4N Cl , 18 oC, 5 h
Pd(OAc)2,PPh3
CO2Me
Et3N
CHO
CO2Me
+
CO2Me
37
90%
Heck reaction - 2
C6H13
I
Ph
38
Cl
+
+
Pd(OAc)2, K2CO3
CO2Me
+ Bu4N Cl , DMF
Pd(OAc)2
CO2Et
Bu3N
CO2Me
C6H13
Ph
CO2Et
55%
65%
Heck reaction - 3
O
OTf
N
O
CO2Me
+
DMF, 60 0C
N
+
PhN2 BF4
Ph
-
+
I Ph
OTs
39
+
+
O
PdCl2 / Et3N / PPh3
Ph
Ph
NaHCO3, rt
94%
Ph
MeCN / H2O
CO2Me
96%
N
O
Pd2(dba)3
Pd(OAc)2, DMF
CO2Me
N
Ph
CO2Me
75%
Heck reaction - 3
COCl
+
Br
Pd(OAc)2
CO2Me
BnMe2N
CO2Me
Br
SO2Cl
+
Cl
40
CO2Bu
PdCl2(PhCN)2, K2CO3
CO2Bu
+ (C8H17)3BnN Cl , 140 0C
79%
Cl
90%
Heck reaction - 4
OEt
OTf
+
Pd(OAc)2, DMSO
OEt
97%
Et3N, 65 0C
OBu
Br
+
41
Pd(OAc)2
OBu
dppp, TlOAc
97%
Heck reaction - 5
Pd(OAc)2, Bu4NCl, AcOK
PhI
Pd(OAc)2, PPh3, Ag2CO3
+
Pd(OAc)2, PPh3
Bu4NCl, AcOK
I
+
O
Pd(OAc)2(PPh3)2
NEt3
42
Ph
99%
Ph
99%
Mixture of isomers
O
Ph
63%
Heck reaction - 6
Br
OH
+
Pd(OAc)2, PPh3
OH
NEt3, MeCN
CHO
82%
I
MeO
+
HO
OH
Pd(OAc)2, BnEt3NBr
OH
AcOK
CHO
OMe
MeO
O
OH
43
89%
Heck reaction - 6
OH
Br
Pd(OAc)2 / P(o-tol)3
+
OH
N
Ts
+
C6H13
44
I
OH
97%
Et3N, CH3CN
100 0C, 5 h
Pd(OAc)2 / Ag2CO3
DMF
N
Ts
C6H13
99%
OH
Heck reaction - 7
Ar
ArI
+
8
8
Pd(OAc)2, Bu4NCl, LiCl
OH
CHO
91%
+
LiOAc, DMF, 50 0C,
3 days
Ar
8
CHO
linear : branched = 88 : 12
PhI
+
PdCl2(PPh3)2
N
K2CO3
PhMe
Ph
N
85%
Ph
DMF
Ph
N
CHO
72%
45
Heck reaction - 8
OMe
I
N
MeS
N
+
O
Me
I
O
I
46
+
O
O
83%
N
OBn
PhSO2O
OMe
Pd(OAc)2, PPh3
O
HCO2Na
Et3N, 120 0C
MeS
N
OBn
PdCl2(MeCN)2
Bu4NCl, DMF
Me
O
O
PhSO2O
O
71%
Heck reaction - 9
nBu
O
+
+
I
HCO2Na
iPr
OH
91%
NH2
99%
2NEt
Me
Me
O
HN
nBu
Pd(OAc)2, Bu4NCl
+
+
HCO2Na
Pd(OAc)2
Bu4NCl
O
I
E/Z=2:1
OMe
O
+
+
I
47
Zn
PdCl2(PPh3)2
Et3N
OH
OMe
95%
Heck reaction - 10
I
MeO
Br
+
Pd(OAc)2, PPh3
SiMe3
Et3N, DMF
Pd(OAc)2, (o-tol)3P
+
60%
MeO
+
MeCN, 20 psi
34%
54%
Br
48
+
SiMeCl2
PdCl2(PPh3)2
Et3N
SiMeCl2
76%
Heck reaction - 11
HO
I
+
Pd(OAc)2, H2O
CN
HO
K2CO3, 90 0C
CN
94%
E/Z=4:1
Br
Br
Br
+
Br
Br
Br
Pd(OAc)2, LiCl, DMF
K2CO3, Bu4NBr
Ph
Ph
Ph
Ph
+
Ph
Ph
Ph
Ph
Ph
49
Ph
Ph
79% ‫עד‬
Ph
Heck reaction - 12
Ph-OTf
Pd(OAc)2, base
+
O
O
(R)-BINAP, C6H6
+
Ph
71%
( S ) 67% ee
Pd(dba)2, L
+
C6H6, 30 0C, 3 days, iPr2NEt
O
O
98%
( R ) 99% ee
L=
O
PPh2 N
50
tBu
Ph
7%
( R ) 96% ee
OTf
O
Heck reaction - 13
Ac
N
Me
OAc
Br
N
OAc Ac
Pd(OAc)2, PPh3
NR3
CO2Et
EtO2C
Ac
N
Me
OAc
76%
N
OAc Ac
EtO2C
CO2Et
Pd(OAc)2, PPh3
Br
K2CO3, MeCN
TBSO
TBSO
OTBS
OTBS
CO2Me
CO2Me
Pd(PPh3)4, Et3N
I
51
MeCN
81%
Heck reaction - 14
MeO
MeO
Pd(OAc)2, PPh3, AcOK
NCOCF3
Pr4NBr, DMF
I
I
OH
MeO
NCOCF3
MeO
OH
Pd(OAc)2, K2CO3
80 0C, 46 h
O
92%
80%
O
O
O
MeO2C
N
I
52
N
Me
CO2Me
OMe
OMe
Pd(OAc)2, Bu4NCl
MeO2C
80 0C
N
N
Me
Co2Me
OMe
OMe
89%
Heck reaction - 15
O
O
PdCl2(MeCN)2
I
55%
MeCN, rt, 10 h
high dilution
O
O
O
O
O
O
O
I
Pd(OAc)2, PPh3
O
O
0
Ag2CO3, THF, 66 C
H
O
O
53
H
O
NHCO2Me
O
O
NHCO2Me
73%
Heck reaction - 16
CO2Me
CO2Me
54%
91% ee
Pd(OAc)2, (R)-BINAP
OTf
K2CO3, toluene
Pd(OAc)2, (R)-BINAP
MeO
OTf
OTBDPS
54
K2CO3
MeO
Me
87%
93% ee
OTBDPS
Heck reaction - 17
Cl
ClPd
Pd(PPh3)4, NEt3
MeCN, 5 h
PdCl
57%
I
O
O
Pd(OAc)2, Ag2CO3
H
PPh3, THF, 65
0C
TBAF
O
H
O
OH
TBSO
83%
55