Semi-Pinacol Rearrangement

Schematic representation of the Semi-Pinacol Rearrangement.

Mechanism of the Semi-Pinacol Rearrangement

Mechanism of the Semi-Pinacol Rearrangement

Original publication	0. 0, 0, 0.
Reviews	Chem. Rev.. 2011, 111, 7523. Chem. Soc. Rev.. 2007, 36, 1823. Comp. Org. Syn.. 1991, 3, 777.

Sample reactions

intermediate structure

AlMe3

CH2Cl2

-78 °C, 60 min, 75% (2 steps)

intermediate structure

intermediate structure

BF3.OEt2

THF

92%

intermediate structure

intermediate structure

LiBr, HMPA

PhMe

Reflux, 35 min

intermediate structure

intermediate structure

LiBr, HMPA

PhMe

Reflux, 2 h

intermediate structure

intermediate structure

intermediate structure

BF3.OEt2, mCPBA

CH2Cl2

RT, 80 min, 71%

"62:38 Trans:Cis"

intermediate structure

intermediate structure

AlMe3

CH2Cl2

-10 to 4 °C, 72 h, 90%

intermediate structure

intermediate structure

n-Bu3P, Pd(OAc)2

t-BuOH

reflux, 90 min, 81%

intermediate structure