Wittig Reaction

Mechanism of the Wittig Reaction

Original publication	Chem. Ber.. 1954, 87, 1318. J. Am. Chem. Soc.. 2014, 136, 5783.
Reviews	Angew. Chem. Int. Ed.. 1977, 16, 429. Chem. Rev.. 1989, 89, 863. Chem. Soc. Rev.. 1988, 17, 1. Org. React.. 1965, 14, 270. Top. Stereochem.. 1994, 21, 1.

Sample reactions

TMS2NK, Ph3P+CH2OMe Cl-

THF

-78 °C to RT, ON, 75% (2 steps)

Ph3P

THF

Reflux, 3 h, 81%

KOt-Bu, Ph3P+CH3 Br-

THF

0 °C to RT, 13 h, 73% (2 steps)

Dimsyl sodium

DMSO

80% (3 steps)

DME

Reflux, , 79%

Ph3P=CH2

THF

0 °C to RT, , 92%

n-BuLi, Ph3P+CH3 Br-

THF

-78 °C to RT, 3.5 h, 95%

i-Pr2NLi, Ph3P(CH2)6CO2H+ Br-

THF

-78 °C to RT, 7.5 h, 67%

TMS2NK, Ph3P+CH2O(CH2)2TMS Cl-

THF

-78 °C to RT, 45 min

TMS2NNa

DME

-78 to 0 °C, 85 min, 76% (2 steps)

Ph3P+CH3 Br-, TMS2NNa

THF

36% (2 steps)

Ph3P=CH2

THF

85% (2 steps)

Ph3P=CMe2

THF

0 °C, 14 h, 57% (3 steps)

TMS2NNa, Ph3P+CH3 I-

THF

-78 to 0 °C, 90 min

Ph3P=CH2

THF

-78 to 0 °C, 25 min, 77%

TMS2NK, Ph3P+CH2OMe Cl-

THF

-78 °C to RT, 85 min, 91%

n-BuLi

THF

-78 °C to RT, ON, 89%

"Ratio of the cis-cis, cis-trans, trans-cis and trans-trans isomers, respectively."

n-BuLi, Ph3P+CH3 Br-

DMSO, THF

80 °C, 3.5 h

Ph3P=CH2

DMSO

75 °C, 16 h

TMS2NK, Ph3P+CH2OMe Cl-

PhMe

0 to 120 °C, 4 h

PhH

90 °C, 90 min, 98%

MeOH

0 °C to RT, 12 h, 74% (2 steps)

n-BuLi, Ph3P+CH3 Br-

THF

0 °C, 3 h, 96%

LiOEt

CH2Cl2, EtOH

71% (2 steps)

TMS2NNa

THF

-78 °C to RT, ON, 59% (2 steps)

"Aqueous HCl work-up cleaves the THP."

TMS2NNa

THF

-78 °C to RT, ON, 80% (2 steps)

PhH

80 °C, 15 h, 81% (2 steps)

CH2Cl2

40 °C, 60 min, 89 % (3 steps)

CH2Cl2

3.5 h, 86%

n-BuLi

Et2O, THF

RT to Reflux, 2 d, 96%

Ph3P+CH3 Br-, NaOt-Amyl

PhMe

RT, 90 min, 88%

n-Bu3P, NaBH(OAc)3

CH2Cl2

RT, 17 h, 79%

n-BuLi, Ph3P+CH3 Br-

THF

RT, 95 min, 96%

n-BuLi, Ph3P+CH3 Br-

THF

70 °C, 15 h, 77%

TMS2NK

PhMe

RT, 12 h, 80%

n-BuLi, Ph3P+CH3 Br-

THF

66% (2 steps)

n-BuLi, Ph3P+CH3 Br-

THF

TMS2NNa

THF

-78 °C to RT, 4 h, 92%

TMS2NK, Ph3P+CH2OMe Cl-

CH2Cl2, THF

-30 °C to RT, 15.5 h, 95%

TMS2NK, Ph3P+CH2OMe Cl-

CH2Cl2, THF

-50 °C to RT, 15 h, 74% (2 steps)

KOt-Bu, Ph3P+CH3 Br-

THF

65 °C, 2 h, 76%

n-BuLi

Et2O

0 °C to RT

(COCl)2, DMSO, Et3N, Ph3P=CHCO2Et

CH2Cl2

-65 °C to RT, 5 h

Ph3P+CH3 Br-, NaOt-Amyl

PhH

80 °C, 60 min, 92%

Ph3P+CH3 Br-, NaOt-Amyl

PhH

RT, 2 h, 92%

Ph3P=CH2

DMSO

70%

Ph3P+CH3 Br-, NaOt-Amyl

PhMe

RT to Reflux, 3 h, 84%

Ph3P=CH2

"No yield reported."

KOt-Bu, Ph3P+CHBr2 Br-

THF

RT, 12 h, 78% (2 steps)

Ph3P+CH3 Br-, NaOt-Amyl

PhMe

RT to reflux, 4 h, 80%

TMS2NNa

THF

-78 °C to RT, ON, 61%

PhH

RT to Reflux, 6 h, 81%

TMS2NK, Ph3P+CH3 Br-

THF

0 °C to RT, 30 min, 86%

KH, Ph3P+CH3 Br-

PhH, t-BuOH

RT to Reflux, 6 h, 93%

n-BuLi, Ph3P+CH3 Br-

Et2O

RT to Reflux, 90 min, 82%

KOt-Bu, Ph3P+CH2OMe Cl-

PhH

RT, 24 h

KOt-Bu

THF

0 °C, 30 min, 81% (2 steps)

TMS2NLi, Ph3P+CH2I I-

HMPA, THF

-78 °C to RT, 60 min

KOt-Bu, Ph3P+CH3 Br-

PhH

RT to Reflux, 21.5 h, 36% (2 steps)

KOt-Bu

PhH

Reflux, 24.5 h, 50%

Ph3P=CHOMe

THF

71%

KOt-Bu

PhH

50 to 70 °C, 7 h, 65%

Ph3P=CHCN

PhMe

80 °C, 2 h, 73% (3 steps)

Reflux, 24 h

NaH

DMSO

RT to 75 °C, 16 h, 62%

n-BuLi, Ph3P+CHMe2 Br-

THF

0 to 10 °C, 60 min, 86%

PhLi

Et2O, THF

-70 to -30 °C, 10 min

CH2Cl2

0 °C, 3 h, 76% (2 steps)

KOt-Bu, Ph3P+CH3 Br-

PhMe

0 °C to reflux, 3 h, 87%

H2O, H2SO4, KOt-Bu, Ph3P+CH2OMe Cl-

THF

0 °C to RT, 3.5 h, 68%

KOt-Bu, Ph3P+CH3 Br-

PhH, t-BuOH

RT to Reflux, 90 min, 63%

CH2Cl2

Reflux, 4 d, 97%

"93:07 E/Z"

Ph3P+CH3 Br-, TMS2NNa

THF

0 °C to RT, 13 h, 60%

Ph3P, CBr4

CH2Cl2

0 °C, 35 min, 94%

Ph3P=CHCO2Me

CH2Cl2

RT, 12 h, 82% (2 steps)

KOt-Bu, Ph3P+CH3 Br-

THF

0 °C to RT, 2 h, 87%

KOt-Bu, Ph3P+CH3 Br-

PhMe

reflux, 20 min, 96%

n-BuLi, Ph3P+CH3 Br-

THF

0 °C to RT, 2.5 h, 53%

n-BuLi, Ph3P+CH3 Br-

-15 to 0 °C, 95 min, 72%

CH2Cl2

0 °C, 12 h, 93%