Abstract
A unique chemoselective synthesis of α‐allenic alcohols is presented. Tetrabutylammonium fluoride (TBAF) mediated this transformation under mild reaction conditions. A range of functional groups is well‐tolerated in this reaction, while affording adducts in moderate to excellent yields (48–96 %, average 76 %). Mechanistic studies, including the use of tetrabutylammonium hydroxide (TBAH), revealed that the hydroxide ion can be the responsible for the observed rearrangement.
Two in one: Tetrabutylammonium fluoride serves as both desilation agent and base to promote a highly chemoselective allenylation of aldehydes under mild reaction conditions. The approach was excellent for a broad substrate scope. The versatility of the new α‐allenols makes them ideal in synthesis because they can be easily converted into synthetically useful heterocycles, as documented here.