Visible light bromide catalysis for oxazoline, pyrrolidine, and dihydrooxazine syntheses via Csp3-H functionalizations

A catalytic benzylic C(sp)3-H functionalization protocol is described here. This visible light-mediated process is centered on the utilization of a bromide catalyst and oxidant to generate a nitrogen (N)-centered radical for a site-selective hydrogen atom transfer (HAT) process. This strategy enabled the unconventional syntheses of a number of N-heterocycles dependent on the amide identity. We also discovered a nucleophilicity-dependent kinetic resolution for stereochemical differentiation of C(sp)3-H bonds that enabled the stereoselective synthesis of cis- and trans-oxazolines.

Automated summary

A catalytic benzylic C(sp)3-H functionalization protocol is described, utilizing a bromide catalyst and oxidant to generate a nitrogen (N)-centered radical for a site-selective hydrogen atom transfer (HAT) process under visible light-mediated condition. This strategy enabled unconventional syntheses of N-heterocycles based on the amide identity, and also discovered a nucleophilicity-dependent kinetic resolution for stereochemical differentiation of C(sp)3-H bonds, enabling the stereoselective synthesis of cis- and trans-oxazolines.