Duke University , Department of Chemistry , Box 90346, Durham , North Carolina 27708-0354 , United States.
Org Lett. 2019 Aug 2;21(15):6089-6095. doi: 10.1021/acs.orglett.9b02234. Epub 2019 Jul 17.
Alcohol-anchored sulfamate esters guide the alkylation of tertiary secondary aliphatic C(3)-H bonds. The transformation proceeds directly from N-H bonds with a catalytic oxidant, a contrast to prior methods which have required preoxidation of the reactive nitrogen center, or employed stoichiometric amounts of strong oxidants to obtain the sulfamyl radical. These sulfamyl radicals template otherwise rare 1,6-hydrogen-atom transfer (HAT) processes via seven-membered ring transition states to enable C(3)-H functionalization during Giese reactions.
醇锚定的磺酰胺酯引导三级、二级脂肪族 C(3)-H 键的烷基化。与之前需要预先氧化反应性氮中心或使用化学计量的强氧化剂来获得磺酰基自由基的方法不同，这种转化可以直接从 N-H 键进行，使用催化氧化剂。这些磺酰基自由基通过七元环过渡态模板化否则很少见的 1,6-氢原子转移 (HAT) 过程，以在 Giese 反应中实现 C(3)-H 官能化。
