对映选择合成
化学
异构化
钯
烯丙基重排
亲核细胞
催化作用
亲核取代
立体选择性
砜
组合化学
对称化
手性(物理)
立体化学
药物化学
有机化学
手征对称破缺
物理
量子力学
Nambu–Jona Lasinio模型
夸克
作者
Shaozi Sun,Qinglong Zhang,Weiwei Zi
标识
DOI:10.1021/acscatal.3c03650
摘要
Transition-metal-catalyzed hydrofunctionalization of vinylarenes via a hydrometalation–nucleophilic trapping pathway is a particularly attractive yet challenging transformation in asymmetric catalysis. Herein we report a Pd-catalyzed enantioselective hydrosulfonylation of vinylarenes with sodium sulfinates in the presence of a Bro̷nsted acid, providing rapid access to chiral benzylic sulfones. The reaction is initiated by stereoselective migratory insertion of Pd–H into the vinylarene, followed by isomerization from a σ-benzylic-Pd species to an η3-benzylic-Pd species, which then undergoes a pseudo-allylic substitution reaction with the nucleophilic sulfinate anion with stereoinversion to produce the chiral benzylic sulfone product. This mechanism was confirmed by experimental and computational studies, and the origin of the enantioselectivity was elucidated.
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