Copper‐Catalyzed Aminoazidation of Alkenes with NFC: One‐step Vicinal Functionalization for CuAAC and SuFEx Reactions

Abstract

CuAAC and SuFEx reactions are two major tools to connect molecules in click chemistry. An azide plays the pivotal role in the former, and a fluorosulfonyl group is the key functionality in the latter. While there are various synthetic methods to attach one of these two functionalities, the simultaneous attachment of both an azide and a fluorosulfonyl group to one molecule remains unexplored. We report the copper‐catalyzed aminoazidation of alkenes using neopentyl N‐fluoro‐N‐(fluorosulfonyl)carbamate (NFC), which incorporates an azide and a (fluorosulfonyl)amino group to an alkene in one step. Derivatization of a product via consecutive CuAAC and SuFEx reactions is also demonstrated, enabling rapid diversification of molecular structure.

Cobalt-Promoted Photoredox 1,2-Amidoamination of Alkenes with N-Sulfonamidopyridin-1-ium Salts and Free Amines

“…Mild and selective diamination of olefins is an important and longstanding goal in synthetic chemistry because it can simultaneously install two amino groups on the CC bond for the elaboration of privileged vicinal diamines, which are essential structural motifs widely existing in bioactive natural products, pharmaceuticals, molecular catalysts, and functional materials . Conventional methods are centered on transition-metal-catalyzed 1,2-diamination of olefins with various amino reagents, such as azides, diaziridines, N , N ′-disubstituted ureas and their derivatives, N -fluorobenzenesulfonimides, O -acylhydroxylamines, diamines, amides, and free amines, in an intramolecular or an intermolecular mode, allowing for the direct construction of vicinal diamine architectures. While these transition-metal-catalyzed intramolecular alkene 1,2-diamination methods can inlay two same or different amino groups across the CC bond by devising substrates to prepare the N -heterocyclic vicinal diamines, such intermolecular approaches are largely limited to the introduction of two same amino groups for the installation of symmetrical vicinal diamines.…”