Controlled Allylic Transformations via the Meisenheimer Rearrangement

Publisher Website
Google Scholar
Abstract
Described are synthetic sequences which effect allylic transformations I and II. Sequence I involves (1) conversion of a primary allyl alcohol into the corresponding N, N‐dimethyl‐amine oxide, (2) [2,3]‐rearrangement to give an N, N‐dimethylhydroxylamine and (3a) reduction to give the ‘rearranged’ secondary or tertiary allyl alcohol [e.g. 36 → 35 → 37 → 40]. Sequence II involves the same steps (1) and (2), followed by (3b) N‐methylation of a secondary N, N‐dimethyl‐hydroxylamine and (4) Hofmann elimination to give a vinyl ketone [e.g. 11 → 12 → 13 → 14 → 15].