Photoinduced Remote Functionalization of Amides and Amines Using Electrophilic Nitrogen Radicals
作者:Sara P. Morcillo、Elizabeth M. Dauncey、Ji Hye Kim、James J. Douglas、Nadeem S. Sheikh、Daniele Leonori
DOI:10.1002/anie.201807941
日期:2018.9.24
here is a photoinduced radical cascade strategy for the divergent functionalization of amides and protected amines. The process is based on the oxidative generation of electrophilic amidyl radicals and their subsequent transposition by 1,5‐H‐atom transfer, resulting in remote fluorination, chlorination and, for the first time, thioetherification, cyanation, and alkynylation. The process is tolerant
远端位置的 C(sp 3 )−H 键与官能团的选择性官能化是合成化学中的一项具有挑战性的任务。这里报道了一种用于酰胺和受保护胺的不同官能化的光诱导自由基级联策略。该过程基于亲电酰胺自由基的氧化生成以及随后通过 1,5-H 原子转移进行的转位,从而实现远程氟化、氯化,并首次实现硫醚化、氰化和炔基化。该过程能够容纳最常见的功能组,并提供可以进一步详细说明的有用构建块。通过氨基酸和二肽的后期功能化证明了该策略的实用性。