Litcius/Paper detail

Copper catalyzed late-stage C(sp3)-H functionalization of nitrogen heterocycles

Zhe Chang, Jialin Huang, Si Wang, Geshuyi Chen, Heng Zhao, Rui Wang, Depeng Zhao

2021Nature Communications47 citationsDOIOpen Access PDF

Abstract

Abstract Nitrogen heterocycle represents a ubiquitous skeleton in natural products and drugs. Late-stage C(sp 3 )-H bond functionalization of N-heterocycles with broad substrate scope remains a challenge and of particular significance to modern chemical synthesis and pharmaceutical chemistry. Here, we demonstrate copper-catalysed late-stage C(sp 3 )-H functionalizaion of N-heterocycles using commercially available catalysts under mild reaction conditions. We have investigated 8 types of N-heterocycles which are usually found as medicinally important skeletons. The scope and utility of this approach are demonstrated by late-stage C(sp 3 )-H modification of these heterocycles including a number of pharmaceuticals with a broad range of nucleophiles, e.g. methylation, arylation, azidination, mono-deuteration and glycoconjugation etc. Preliminary mechanistic studies reveal that the reaction undergoes a C-H fluorination process which is followed by a nucleophilic substitution.

Topics & Concepts

CatalysisNucleophileChemistrySurface modificationSubstrate (aquarium)Combinatorial chemistryNitrogenNucleophilic substitutionCopperOrganic chemistryBiologyPhysical chemistryEcologyCatalytic C–H Functionalization MethodsSynthesis and Catalytic ReactionsAsymmetric Hydrogenation and Catalysis