Intramolecular photochemical [2 + 1]-cycloadditions of nucleophilic siloxy carbenes†

Amanda Bunyamin; Carol Hua; Anastasios Polyzos; Daniel L. Priebbenow

doi:10.1039/d2sc00203e

Intramolecular photochemical [2 + 1]-cycloadditions of nucleophilic siloxy carbenes†

Amanda Bunyamin, Carol Hua, Anastasios Polyzos, Daniel L. Priebbenow

Medicinal Chemistry

Research output: Contribution to journal › Article › Research › peer-review

44 Citations (Scopus)

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.

Original language	English
Pages (from-to)	3273-3280
Number of pages	8
Journal	Chemical Science
Volume	13
Issue number	11
DOIs	https://doi.org/10.1039/d2sc00203e
Publication status	Published - 21 Mar 2022

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10.1039/d2sc00203eLicence: CC BY

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title = "Intramolecular photochemical [2 + 1]-cycloadditions of nucleophilic siloxy carbenes†",

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.",

author = "Amanda Bunyamin and Carol Hua and Anastasios Polyzos and Priebbenow, {Daniel L.}",

note = "Funding Information: 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. Publisher Copyright: This journal is {\textcopyright} The Royal Society of Chemistry",

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doi = "10.1039/d2sc00203e",

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AU - Polyzos, Anastasios

AU - Priebbenow, Daniel L.

N1 - Funding Information: 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. Publisher Copyright: This journal is © The Royal Society of Chemistry

PY - 2022/3/21

Y1 - 2022/3/21

N2 - 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.

AB - 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.

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JO - Chemical Science

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Intramolecular photochemical [2 + 1]-cycloadditions of nucleophilic siloxy carbenes†

Abstract

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Metal-free strategies for sustainable light-driven synthesis

Australian Synchrotron

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Intramolecular photochemical [2 + 1]-cycloadditions of nucleophilic siloxy carbenes†

Abstract

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Projects

Metal-free strategies for sustainable light-driven synthesis

Equipment

Australian Synchrotron

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