转鼓
化学
烯丙基重排
反应性(心理学)
亲核细胞
卡宾
催化作用
醛
电泳剂
有机化学
组合化学
药物化学
医学
病理
替代医学
作者
Huifei Wang,Shuxian Qiu,Sasa Wang,Hongbin Zhai
标识
DOI:10.1021/acscatal.8b03814
摘要
Construction of sterically congested all-carbon quaternary centers represents a formidable challenge in synthetic chemistry. The method described herein provides direct and facile access to a series of structurally diverse and synthetically useful aliphatic aldehydes, bearing an all-carbon α-vinyl quaternary center and a 1,5-diene functionality, through Pd-catalyzed umpolung of vinylethylene carbonates (VECs). The reaction features electrophilic-to-nucleophilic reactivity reversal of the VEC-derived π-allyl-palladium intermediate via an unusual β-hydride elimination process, and the resultant enolate is chemoselectively coupled with allylic acetate to form an α-vinyl aldehyde embedded with an all-carbon quaternary center.
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