Stateman Leah M, Nakafuku Kohki M, Nagib David A
Department of Chemistry and Biochemistry, The Ohio State University, Columbus, Ohio, 43210, USA.
Synthesis (Stuttg). 2018 Apr;50(8):1569-1586. doi: 10.1055/s-0036-1591930. Epub 2018 Feb 12.
The selective functionalization of remote C-H bonds via intramolecular hydrogen atom transfer (HAT) is transformative for organic synthesis. This radical-mediated strategy provides access to novel reactivity that is complementary to closed-shell pathways. As modern methods for mild generation of radicals are continually developed, inherent selectivity paradigms of HAT mechanisms offer unparalleled opportunities for developing new strategies for C-H functionalization. This review outlines the history, recent advances, and mechanistic underpinnings of intramolecular HAT as a guide to addressing ongoing challenges in this arena.
通过分子内氢原子转移(HAT)实现远程C-H键的选择性官能团化对有机合成具有变革性意义。这种自由基介导的策略提供了获得与闭壳层途径互补的新型反应性的途径。随着温和产生自由基的现代方法不断发展,HAT机制固有的选择性模式为开发C-H官能团化新策略提供了无与伦比的机会。本综述概述了分子内HAT的历史、最新进展和机理基础,以此作为应对该领域当前挑战的指南。