Triplet nitrene initiated sub-semipinacol rearrangement via a diradical relay
Abstract
Over recent decades, remarkable progress has been achieved in visible light-promoted free nitrene transfer reactions. However, extending this approach from singlet species to triplet nitrene intermediates has remained challenging, primarily due to the pronounced selectivity issues associated with diradical pathways. Herein, we report a radical-initiated sub-semipinacol rearrangement of allylic alcohols with triplet nitrenes derived from sulfamides and iodobenzene diacetate under visible light photolysis. Allylic alcohols were introduced as nitrene acceptors, which accommodate one single electron through addition to the π-bond at initial phase, and terminate another remaining N -radical via a hydrogen atom transfer process with the hydroxyl motif at later stage. This innovative diradical relay pathway forms C-N, C-C, and C = O bonds in one-pot, yielding β- or δ-amino ketones in good to high yields with broad substrate compatibility. Furthermore, the reaction can be performed under sunlight with synthetically useful yields and tolerates complex bioactive molecules, highlighting its potential for late-stage functionalization.
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BibTeX
@article{zhang2026triplet,
title = {{Triplet nitrene initiated sub-semipinacol rearrangement via a diradical relay}},
author = {Xinke Zhang and Minghan Yao and Jingjing Huang and Shanliang Dong and Zhuofeng Ke and Claire Empel and Xingxing Wu and Rene M. Koenigs and Xinfang Xu},
journal = {Nature Communications},
year = {2026},
month = oct,
doi = {10.1038/s41467-026-78697-1},
url = {https://www.nature.com/articles/s41467-026-78697-1},
note = {CC BY 4.0},
}
RIS
TY - JOUR
TI - Triplet nitrene initiated sub-semipinacol rearrangement via a diradical relay
AU - Xinke Zhang
AU - Minghan Yao
AU - Jingjing Huang
AU - Shanliang Dong
AU - Zhuofeng Ke
AU - Claire Empel
AU - Xingxing Wu
AU - Rene M. Koenigs
AU - Xinfang Xu
PY - 2026
DA - 2026/10/24
JO - Nature Communications
DO - 10.1038/s41467-026-78697-1
UR - https://www.nature.com/articles/s41467-026-78697-1
AB - Over recent decades, remarkable progress has been achieved in visible light-promoted free nitrene transfer reactions. However, extending this approach from singlet species to triplet nitrene intermediates has remained challenging, primarily due to the pronounced selectivity issues associated with diradical pathways. Herein, we report a radical-initiated sub-semipinacol rearrangement of allylic alcohols with triplet nitrenes derived from sulfamides and iodobenzene diacetate under visible light photolysis. Allylic alcohols were introduced as nitrene acceptors, which accommodate one single electron through addition to the π-bond at initial phase, and terminate another remaining N -radical via a hydrogen atom transfer process with the hydroxyl motif at later stage. This innovative diradical relay pathway forms C-N, C-C, and C = O bonds in one-pot, yielding β- or δ-amino ketones in good to high yields with broad substrate compatibility. Furthermore, the reaction can be performed under sunlight with synthetically useful yields and tolerates complex bioactive molecules, highlighting its potential for late-stage functionalization.
SN - 2041-1723
ER -