Conceived as a model study for the enantioselective synthesis of the natural product (S)-bakuchiol, the deoxygenation of a recently described trishomoallyl alc. was attempted using the Kabalka modification of the Wolff-Kishner method after prior oxidn. of the alc. to the ketone. However, an unprecedented succession of homoallyl/cyclopropyl ring closure and ring opening altered the carbon skeleton profoundly. The crucial intermediates are assumed to be radicals although carbanions cannot yet be definitely ruled out. [on SciFinder (R)]
Title
Two homoallyl/cyclopropylalkyl rearrangements accompanying a Wolff-Kishner type reduction
Published in
Tetrahedron Letters
Volume
42
Issue
34
Pages
5863-5865
Date
2001
ISSN
0040-4039
Note
CAN 135:331212
25-2
Benzene, Its Derivatives, and Condensed Benzenoid Compounds
Section de Chimie de l'Universite (BCh),Lausanne,Switz.
Journal
written in English.
357979-06-7; 369365-08-2 Role: RCT (Reactant), RACT (Reactant or reagent) (homoallyl/cyclopropylalkyl rearrangements accompanying a Wolff-Kishner type redn.); 369365-10-6P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (homoallyl/cyclopropylalkyl rearrangements accompanying a Wolff-Kishner type redn.); 369365-09-3P Role: SPN (Synthetic preparation), PREP (Preparation) (homoallyl/cyclopropylalkyl rearrangements accompanying a Wolff-Kishner type redn.)
Record creation date
2006-03-03