Mitra Sankash, Sarkar Rahul, Chakrabarty Aditya, Mukherjee Santanu
Department of Organic Chemistry, Indian Institute of Science Bangalore 560 012 India
Chem Sci. 2022 Oct 13;13(42):12491-12497. doi: 10.1039/d2sc03966d. eCollection 2022 Nov 2.
Hydroxy-directed iridium-catalyzed enantioselective formal β-C(sp)-H allylic alkylation of kojic acid and structurally related α,β-unsaturated carbonyl compounds is developed. This reaction, catalyzed by an Ir(i)/(,olefin) complex, utilizes the nucleophilic character of α-hydroxy α,β-unsaturated carbonyls, to introduce an allyl group at its β-position in a branched-selective manner in good to excellent yield with uniformly high enantioselectivity (up to >99.9 : 0.1 er). To the best of our knowledge, this report represents the first example of the use of kojic acid in a transition metal catalyzed highly enantioselective transformation.
开发了羟基导向的铱催化曲酸及结构相关的α,β-不饱和羰基化合物的对映选择性形式β-C(sp)-H烯丙基烷基化反应。该反应由Ir(i)/(烯烃)配合物催化，利用α-羟基α,β-不饱和羰基的亲核特性，以支链选择性方式在其β位引入烯丙基，产率良好至优异，对映选择性均很高(高达>99.9:0.1 er)。据我们所知，本报告是曲酸在过渡金属催化的高对映选择性转化中应用的首个实例。
