Yuan Yuan, Zhang Xue, Qian Hui, Ma Shengming
Research Center for Molecular Recognition and Synthesis, Department of Chemistry, Fudan University 220 Handan Lu Shanghai 200433 P. R. China
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences 345 Lingling Lu, Shanghai 200032 P. R. China
Chem Sci. 2020 Jul 22;11(34):9115-9121. doi: 10.1039/d0sc03227a.
A protocol of highly regio- and enantioselective copper-catalyzed hydroacylation of the non-terminal C[double bond, length as m-dash]C bond in 1,1-disubstituted terminal allenes with anhydrides has been developed. Both aromatic and aliphatic carboxylic anhydrides are applicable to the efficient construction of all carbon quarternary centers connected with a versatile C[double bond, length as m-dash]C bond and a useful ketone functionality. The synthetic potentials of the enantioenriched products have also been demonstrated. Density functional theory (DFT) calculations were performed to explain the steric outcome of the products: the hydroacylation proceeds through a six-membered transition state and the ligand-substrate steric interactions account for the observed enantioselectivity although the chiral ligand is far away from the to-be-genetated chiral center.
已开发出一种高度区域和对映选择性的铜催化方法，用于1,1-二取代末端丙二烯中与酸酐相连的非末端C=C键的氢酰化反应。芳族和脂肪族羧酸酐均可用于高效构建与通用C=C键和有用的酮官能团相连的全碳季碳中心。还展示了对映体富集产物的合成潜力。进行了密度泛函理论（DFT）计算以解释产物的空间结果：氢酰化反应通过六元过渡态进行，尽管手性配体远离即将生成的手性中心，但配体-底物空间相互作用解释了观察到的对映选择性。
