ヒドロキシアルキルホスホニウム塩を用いたオキサホスホランの合成と反応

概要

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Triphenylvinylphosphonium salts were prepared by the reaction of triphenylphosphine with epoxide and acid, followed by the addition of acetyl chloride in one pot operation. These salts were also synthesized by the reaction of 2-hydroxyalkyltriphenylphosphonium salts with acetyl chloride or oxalyl chloride. Other synthetic methods of these salts were also described. Optically active 3-hydroxyalkyl triphenyl phosphonium salts were synthesized by the reaction of phospho-rus ylides with epoxides. The reaction of these salts with 2 eq of BuLi gave the corresponding γ-oxidephosphonium ylides, which further reacted with aldehydes to give the corresponding E-rich homoallylic alcohols. 2, 2, 2-Tripheny1-1, 2λ5-oxaphospholanes were easily prepared by the reaction of 3-hydroxylalkylphosphonium salts with sodium hydride. The reaction with aldehydes afforded Z-rich homoallylic alcohols almost quantitatively. Thus, high selectivity for Z- or E-homoallylic alcohols was available depending on the particular circumstances. The syntheses of optically active methylenecyclopropylacetic acid and recifeiolide were succeeded by this method.
社団法人有機合成化学協会の論文
2000-06-01