Distal Amidoketone Synthesis Enabled by Dimethyl Benziodoxoles via Dual Copper/Photoredox Catalysis
Yuanyuan Ge, Yingbo Shao, Shuang Wu, Pan Liu, Junzhao Li, Hanzhang Qin, Yanxia Zhang, Xiao‐Song Xue, Yiyun Chen
Abstract
Herein, we report distal amidoketone and nitrogen-functionalized ketone syntheses from alcohols and N–H nucleophiles enabled by hypervalent iodine dimethyl benziodoxoles, BI m . Dimethyl benziodoxoles BI m dually activate alcohols and various N–H nucleophiles by forming key BI m –O and BI m –N complexes in which the BI m –N complex is characterized by X-ray crystallography and computationally investigated. Readily available N–H nucleophile imides, sulfonamides, carbamates, triazoles, indazoles, and sulfoximines engage in photoredox/copper catalysis to synthesize distal amidoketones and nitrogen-functionalized ketones with excellent regioselectivity and chemoselectivity. This reaction scales up to grams, applies to late-stage complex molecule modification, and streamlines synthetic routes.