Direct α-alkylation of primary aliphatic amines enabled by CO₂ and electrostatics.

ABSTRACT: Primary aliphatic amines are important building blocks in organic synthesis due to the presence of a synthetically versatile NH₂ group. N-functionalization of primary amines is well established, but selective C-functionalization of unprotected primary amines remains challenging. Here, we report the use of CO₂ as an activator for the direct transformation of abundant primary aliphatic amines into valuable γ-lactams under photoredox and hydrogen atom transfer (HAT) catalysis. Experimental and computational studies suggest that CO₂ not only inhibits undesired N-alkylation of primary amines, but also promotes selective intermolecular HAT by an electrostatically accelerated interaction between the in situ-generated negatively charged carbamate and the positively

SUBMITTER: Ye J 

PROVIDER: S-EPMC6150826 | biostudies-literature | 2018 Oct

REPOSITORIES: biostudies-literature