摘要/Abstract

研究了1，4-烯炔衍生物与二芳基膦氧化物在银介导下发生的炔酰化反应.该反应利用自由基引发的1，2-炔基迁移策略合成了一系列γ-酮膦氧化物，产率适中.该反应机理可能涉及膦中心自由基与乙烯基的加成、3-exo-dig环化和1，2-炔基迁移等连续的过程，一步形成了C-P、C-C键等化学键，实现了非活性烯烃的双官能化.
关键词: 1,4-烯炔衍生物, 炔膦酰化反应, γ-酮膦氧化物, 炔基迁移, 自由基化学
A silver-mediated alkynylphosphonation of 1,4-enynes with diarylphosphine oxides has been developed, by which a wide range of γ-ketophosphine oxides with moderate to good yields were synthesized through radical 1,2-alkynyl migration. The transformation proceeded with sequential P-centered radical addition to vinyl unit, 3-exo-dig cyclization and 1,2-alkynyl migration, resulting in the bond-forming events including C-P and C-C bonds to realize difunctionalization of unactivated olefins.
Key words: 1,4-enynes, alkynylphosphonation, γ-ketophosphine oxides, alkynyl migration, radical chemistry


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