Trost Barry M, Ball Zachary T, Laemmerhold Kai M
Department of Chemistry, Stanford University, Stanford, California 94305-5080, USA.
J Am Chem Soc. 2005 Jul 20;127(28):10028-38. doi: 10.1021/ja051578h.
Alkynes bearing propargylic, homopropargylic, and bishomopropargylic hydroxyl groups are shown to serve as precursors for ketone or alpha-hydroxy ketone functionality. The approach hinges on the intermediacy of vinylsilanes created through regioselective hydrosilylation catalyzed by the complex [Cp*Ru(MeCN)3]PF6. Several oxidative pathways of linear and cyclic vinylsilanes are studied, and the possibility of diastereoselective epoxidation of cyclic vinylsilanes is demonstrated. The sequences constitute the equivalent of stereoselective aldol, homo-aldol, and bishomo-aldol type processes. The method is applied to a short synthesis of the piperidine alkaloid, spectaline.
带有炔丙基、高炔丙基和双高炔丙基羟基的炔烃被证明可作为酮或α-羟基酮官能团的前体。该方法基于由配合物[Cp*Ru(MeCN)3]PF6催化的区域选择性硅氢化反应生成的乙烯基硅烷中间体。研究了线性和环状乙烯基硅烷的几种氧化途径，并证明了环状乙烯基硅烷非对映选择性环氧化的可能性。这些序列相当于立体选择性羟醛、高羟醛和双高羟醛类型的反应过程。该方法应用于哌啶生物碱斯佩塔林的简短合成。
