Sarkar Rahul, Mukherjee Santanu
Department of Organic Chemistry, Indian Institute of Science Bangalore 560 012 India
Chem Sci. 2021 Jan 15;12(8):3070-3075. doi: 10.1039/d0sc06208a.
The first iridium-catalyzed enantioselective olefinic C(sp)-H allylic alkylation is developed in cooperation with Lewis base catalysis. This reaction, catalyzed by cinchonidine and an generated cyclometalated Ir(i)/phosphoramidite complex, makes use of the latent enolate character of an α,β-unsaturated carbonyl compound, namely coumalate ester, to introduce an allyl group at its α-position in a branched-selective manner in moderate to good yield with good to excellent enantioselectivities (up to 98 : 2 er).
首次实现了铱催化的对映选择性烯烃C(sp)-H烯丙基烷基化反应，并与路易斯碱催化协同作用。该反应由辛可尼定和生成的环金属化Ir(i)/亚磷酰胺配合物催化，利用α,β-不饱和羰基化合物（即香豆酸酯）的潜在烯醇盐特性，以支链选择性方式在其α位引入烯丙基，产率中等至良好，对映选择性良好至优异（对映体过量高达98:2）。
