Aluminum-Catalyzed Enantio- and Diastereoselective Carbonyl Addition of Propargylsilanes. A New Approach to Enantioenriched Vinyl Epoxides

A new pathway involving a Lewis acid-catalyzed carbonyl addition reaction of propargylsilanes and its subsequent development into a general enantio- and diastereoselective process are described. Aliphatic propargylsilanes with both saturated and unsaturated sidechains were effective nucleophiles affording highly functionalized chiral vinyl epoxides in good enantioselectivities (85−94% ee), excellent diastereoselectivities (>99:1 E:Z; >99:1 anti:syn) and in moderate to good yields (49−97%).

本文报道了一条涉及路易斯酸（Lewis acid）催化的炔丙基硅烷（propargylsilanes）羰基加成反应的全新路径，并将其进一步开发为一种通用的对映选择性与非对映选择性合成方法。带有饱和与不饱和侧链的脂肪族炔丙基硅烷均为有效的亲核试剂，可合成得到高度官能化的手性乙烯基环氧化物（vinyl epoxides），产物具备良好的对映选择性（对映体过量值85−94% ee）、极佳的非对映选择性（E:Z >99:1；anti:syn >99:1），且产率处于中等至良好水平（49−97%）。