Claisen Rearrangement

Schematic representation of the Claisen Rearrangement.

Mechanism of the Claisen Rearrangement

Mechanism of the Claisen Rearrangement

Original publication	Chem. Ber.. 1912, 45, 3157. J. Org. Chem.. 2014, 79, 3040.
Reviews	Acc. Chem. Res.. 1977, 10, 1423. Angew. Chem. Int. Ed.. 1996, 35, 936. Chem. Rev.. 1984, 84, 205. Chem. Rev.. 1988, 88, 1423. Chem. Rev.. 2004, 104, 293. Chem. Soc. Rev.. 1999, 28, 43. Comp. Org. Syn.. 1991, 5, 827. Org. React.. 1975, 22, 1.

Sample reactions

intermediate structure

VinylOEt, Hg(OAc)2

190 °C

intermediate structure

intermediate structure

Cl2CHCO2H

DMF

125 °C to Reflux, 90 min, 79% (2 steps)

intermediate structure

intermediate structure

HCl

H2O

74% (2 steps)

intermediate structure

intermediate structure

Sealed tube

187 to 200 °C, 6 h, 94% (2 steps)

intermediate structure

intermediate structure

VinylOEt, Hg(OAc)2

Sealed tube

Xylene(s)

250 °C, , 90%

intermediate structure

intermediate structure

μW

1,2-Dichlorobenzene

185 °C, 20 min, 86% (α), 83 % (β)

intermediate structure

intermediate structure

PhNEt2

Reflux, 60 min, 64%

intermediate structure

intermediate structure

Sealed tube

PhMe

180-190 °C, 12 h, 80%

intermediate structure

intermediate structure

PhMe

Reflux, 16 h

intermediate structure