Journal article
Intramolecular photochemical [2 1]-cycloadditions of nucleophilic siloxy carbenes†
A Bunyamin, C Hua, A Polyzos, DL Priebbenow
Chemical Science | ROYAL SOC CHEMISTRY | Published : 2022
DOI: 10.1039/d2sc00203e
Open access
Abstract
Visible light induced singlet nucleophilic carbenes undergo rapid [2 + 1]-cycloaddition with tethered olefins to afford unique bicyclo[3.1.0]hexane and bicyclo[4.1.0]heptane scaffolds. This cyclopropanation process requires only visible light irradiation to proceed, circumventing the use of exogenous (photo)catalysts, sensitisers or additives and showcases a vastly underexplored mode of reactivity for nucleophilic carbenes in chemical synthesis. The discovery of additional transformations including a cyclopropanation/retro-Michael/Michael cascade process to afford chromanones and a photochemical C-H insertion reaction are also described.
Grants
Awarded by Australian Research Council
Funding Acknowledgements
D. L. P. acknowledges the support of the Australian Research Council (DE200100949). A. P. acknowledges the University of Melbourne and CSIRO for the joint Establishment Grant and the Australian Research Council (IC1701000020). This research was undertaken in part using the MX1 and MX2 beamlines at the Australian Synchrotron, part of ANSTO, and made use of the Australian Cancer Research Foundation (ACRF) detector.