Sharma Akashdeep, Vaid Himani, Kotwal Riya, Mughal Zuhaib N, Gurubrahamam Ramani
Department of Chemistry, Indian Institute of Technology Jammu, NH-44, PO Nagrota, Jagti, Jammu and Kashmir 181221, India.
Org Lett. 2024 Jun 14;26(23):4887-4892. doi: 10.1021/acs.orglett.4c01345. Epub 2024 Jun 6.
The first insertion of an alkynyl carbene into N-H bonds under Rh-catalysis is developed. Alkynyl hydrazone carboxylates are used as donor-acceptor carbene precursors and are exquisitely inserted into the N-H bonds of various amines, amides, and 1,2-diamines. A wide variety of 3-alkynyl 3,4-dihydroquinoxalin-2(1)-ones and densely functionalized α-alkynyl α-amino esters are obtained in good to excellent yields. Further, chemoselective N-H insertion reactions, mechanistic studies, and various synthetic transformations for obtaining valuable heterocycles are demonstrated.
首次实现了在铑催化下炔基卡宾插入N-H键的反应。炔基腙羧酸盐用作供体-受体卡宾前体，并能精准地插入到各种胺、酰胺和1,2-二胺的N-H键中。以良好至优异的产率得到了多种3-炔基-3,4-二氢喹喔啉-2(1)-酮和功能密集化的α-炔基-α-氨基酯。此外，还展示了化学选择性N-H插入反应、机理研究以及用于获得有价值杂环的各种合成转化。
