Vicinal, Double C-H Functionalization of Alcohols via an Imidate Radical-Polar Crossover Cascade.

Journal of the American Chemical Society
Allen F PrusinowskiDavid A Nagib

Abstract

A double functionalization of vicinal sp3 C-H bonds has been developed, wherein a β amine and γ iodide are incorporated onto an aliphatic alcohol in a single operation. This approach is enabled by an imidate radical chaperone, which selectively affords a transient β alkene that is amino-iodinated in situ. Overall, the radical-polar-crossover cascade entails the following key steps: (i) β C-H iodination via 1,5-hydrogen atom transfer (HAT), (ii) desaturation via I2 complexation, and (iii) vicinal amino-iodination of an in situ generated allyl imidate. The synthetic utility of this double C-H functionalization is illustrated by conversion of aliphatic alcohols to a diverse collection of α,β,γ substituted products bearing heteroatoms on three adjacent carbons. The radical-polar crossover mechanism is supported by various experimental probes, including isotopic labeling, intermediate validation, and kinetic studies.

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Citations

Jan 9, 2021·Chemical Record : an Official Publication of the Chemical Society of Japan ... [et Al.]·James M WoodEufrânio N da Silva Júnior
Feb 6, 2021·Science·Tao Shen, Tristan H Lambert
Oct 1, 2021·Chemistry : a European Journal·Yong XiaArmido Studer
Nov 9, 2021·Journal of the American Chemical Society·Chunngai HuiAndrey P Antonchick

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