Department of Chemistry, University of Zürich, Winterthurerstrasse 190, 8057, Zürich, Switzerland.
Angew Chem Int Ed Engl. 2017 Feb 6;56(7):1881-1884. doi: 10.1002/anie.201609885. Epub 2017 Jan 18.
A redox-neutral, light-mediated functionalization of unactivated C(sp )-H bonds via iminyl radicals is presented here. A 1,5-H transfer followed by the functionalization of a C(sp )-H bond takes place in aqueous media producing a variety of elaborated fused ketones. Mechanistic investigations have revealed 1,5-H transfer as the reversible, rate-determining step in this transformation. Divergent scaffolds are also accessible via C(sp )-N bond formation upon a careful choice of the reaction additives.
本文报道了一种通过亚胺自由基实现的未活化 C(sp3)-H 键的氧化还原中性、光照介导的功能化反应。在水相介质中,通过 1,5-H 转移和 C(sp3)-H 键的功能化反应,生成了多种复杂的稠合酮。通过对反应添加剂的仔细选择,还可以通过 C(sp3)-N 键形成来获得不同的支架。机理研究表明,1,5-H 转移是该转化的可逆、速率决定步骤。