Mizoroki-Heck Reaction

Schematic representation of the Mizoroki-Heck Reaction.

Mechanism of the Mizoroki-Heck Reaction

Mechanism of the Mizoroki-Heck Reaction

Original publication	J. Org. Chem.. 1972, 37, 2320. Bull. Chem. Soc. Jpn.. 1971, 44, 581. Angew. Chem. Int. Ed.. 1995, 33, 2379. J. Med. Chem.. 2015, 58, 8128.
Reviews	Angew. Chem. Int. Ed.. 1994, 33, 2379. Chem. Rev.. 2000, 100, 3009. Chem. Soc. Rev.. 1998, 27, 427. Chem. Soc. Rev.. 2011, 40, 5122. Org. React.. 1982, 27, 345.

Sample reactions

intermediate structure

HCO2H, PdCl2.2MeCN

DMF, Et3N

60 °C, 60 min, 93%

intermediate structure

intermediate structure

intermediate structure

i-Pr2NEt, Pd(OAc)2, Et3NBn+ Cl-

DMF

80 °C, , 45%

intermediate structure

intermediate structure

Et3N, Pd2(dba)3.CHCl3, Ag3PO4

THF

66 °C, 13 h, 70%

intermediate structure

intermediate structure

K2CO3, Pd(PPh3)4

MeCN

90 °C, , 46%

intermediate structure

intermediate structure

Et3N, Pd2(dba)3

DMF

140 °C, 5 h, 60%

intermediate structure

intermediate structure

Pd(CF3CO2)2(PPh3)2, 1,2,2,6,6-Pentamethylpiperidine

PhMe

120 °C, , 60%

intermediate structure

intermediate structure

Pd(OAc)2, dppp, Ag2CO3

PhMe

107 °C, 24 h, 91%

intermediate structure

intermediate structure

Pd(OAc)2, dppp, Ag2CO3

PhMe

107 °C, 4 h, 65%

"The yield was 74 % brsm."

intermediate structure

intermediate structure

Pd(OAc)2, Ph3P, Ag2CO3

PhMe

80 °C, 60 min, 66%

intermediate structure

intermediate structure

Et3N, Pd(OAc)2, Et3NBn+ Cl-

DMF

80 °C, 30 min, 66%

intermediate structure

intermediate structure

NaOAc, Pd(OAc)2, Ph3P, n-Bu4N+ Cl-

DMF, H2O

125 °C, 4 h, 84%

intermediate structure

intermediate structure

K2CO3, Pd(OAc)2, n-Bu4N+ Cl-

DMF

70 °C, 3 h, 74%

intermediate structure

intermediate structure

K2CO3, Pd(OAc)2, n-Bu4N+ Cl-

DMF

70 °C, 4 h, 68%

intermediate structure

intermediate structure

Pd(OAc)2, Ph3P

Et3N

90 °C, 2 h, 85%

intermediate structure

intermediate structure

Pd(OAc)2, Ph3P

Et3N

90 °C, 90 min, 53%

intermediate structure

intermediate structure

Pd(OAc)2, Ag2CO3, Me2PPh

DMSO

90 °C, 17 h, 87%

"Cristallized to >99:01 er (73 % yield)."

intermediate structure

intermediate structure

i-Pr2NEt, Pd(OAc)2, Ph3P

DMSO

80 °C, 90 min, 46%

intermediate structure

intermediate structure

K2CO3, Pd(OAc)2, Ph3P, n-Bu4N+ Cl-

DMF

70 °C, 30 min, 48%

intermediate structure

intermediate structure

NaHCO3, Pd(OAc)2, n-Bu4N+ Cl-

EtOAc

RT, 24 h, 58%

intermediate structure

intermediate structure

intermediate structure

HCO2H, Pd(OAc)2, Ph3P, Piperidine

DMF

70 °C, 6.5 h, 35%

intermediate structure

intermediate structure

Et3N, Pd(OAc)2

PhMe

Reflux, 6 h, 87%

intermediate structure

intermediate structure

Pd(OAc)2, Ph3P, TlOAc

DMF

130 °C, 24 h, 93%

intermediate structure

intermediate structure

AgNO3, Pd(OAc)2, n-Bu4N+ Cl-, HCO2Na

NMP

RT, 3 h, 93%

intermediate structure

intermediate structure

Pd(OAc)2, 1,2,2,6,6-Pentamethylpiperidine

PhMe

170 °C, 45 min, 87%

"99% ee"

intermediate structure