Palladium-catalyzed hydrosilylation of ynones to access silicon-stereogenic silylenones by stereospecific aromatic interaction-assisted Si-H activation

• 作者: Jia-Le Xie Zheng Xu Han-Qi Zhou Yi-Xue Nie Jian Cao Guan-Wu Yin Jean-Philippe Bouillon Li-Wen Xu
• 来源期刊: 中国科学：化学（英文版）
• 年，卷（期）: 2021,（5）
• 所属期刊栏目: ARTICLES
• 页码范围: 761-769
• 页数: 9页
• 语种: 英文

摘要

Hydrosilylation is one of the most important reactions in synthetic chemistry and ranks as a fundamental method to access organosilicon compounds in industrial and academic processes.However,the enantioselective construction of chiral-at-silicon compounds via catalytic asymmetric hydrosilylation remained limited and difficult.Here we report a highly enantioselective hydrosilylation of ynones,a type of carbonyl-activated alkynes,using a palladium catalyst with a chiral binaphthyl phosphor-amidite ligand.The stereospecific hydrosilylation of ynones affords a series of silicon-stereogenic silylenones with up to 94％yield,＞20∶1 regioselectivity and 98∶2 enantioselectivity.The density functional theory (DFT) calculations were conducted to elucidate the reaction mechanism and origin of high degree of stereoselectivity,in which the powerful potential of aromatic interaction in this reaction is highlighted by the multiple C-H-π interaction and aromatic cavity-oriented enantioselectivity-determining step during desymmetric functionalization of Si-H bond.