Affiliation:
1. State Key Laboratory of Organometallic Chemistry Center for Excellence in Molecular Synthesis Shanghai Institute of Organic Chemistry Chinese Academy of Sciences University of Chinese Academy of Sciences 345 Lingling Road Shanghai 200032 China
2. Key Laboratory of Fluorine and Nitrogen Chemistry and Advanced Materials Shanghai Institute of Organic Chemistry Chinese Academy of Sciences University of Chinese Academy of Sciences 345 Lingling Road Shanghai 200032 China
Abstract
AbstractIn this study, we introduce a novel intramolecular hydrogen atom transfer (HAT) reaction that efficiently yields azetidine, oxetane, and indoline derivatives through a mechanism resembling the carbon analogue of the Norrish‐Yang reaction. This process is facilitated by excited triplet‐state carbon‐centered biradicals, enabling the 1,5‐HAT reaction by suppressing the critical 1,4‐biradical intermediates from undergoing the Norrish Type II cleavage reaction, and pioneering unprecedented 1,6‐HAT reactions initiated by excited triplet‐state alkenes. We demonstrate the synthetic utility and compatibility of this method across various functional groups, validated through scope evaluation, large‐scale synthesis, and derivatization. Our findings are supported by control experiments, deuterium labeling, kinetic studies, cyclic voltammetry, Stern–Volmer experiments, and density functional theory (DFT) calculations.
Funder
National Natural Science Foundation of China
Science and Technology Commission of Shanghai Municipality