title: Spin-Selective Generation of Triplet Nitrenes: Olefin Aziridination through Visible-Light Photosensitization of Azidoformates.
abstract: Azidoformates are interesting potential nitrene precursors, but their direct photochemical activation can result in competitive formation of aziridination and allylic amination products. Herein, we show that visible-light-activated transition-metal complexes can be triplet sensitizers that selectively produce aziridines through the spin-selective photogeneration of triplet nitrenes from azidoformates. This approach enables the aziridination of a wide range of alkenes and the formal oxyamination of enol ethers using the alkene as the limiting reagent. Preparative-scale aziridinations can be easily achieved under continuous-flow conditions.
authors.affiliation: Department of Chemistry, University of Wisconsin-Madison, 1101 University Avenue, Madison, WI, 53706, USA.
authors.forename: Spencer O
authors.initials: SO
authors.lastname: Scholz
authors.affiliation: Department of Chemistry, University of Wisconsin-Madison, 1101 University Avenue, Madison, WI, 53706, USA.
authors.forename: Elliot P
authors.initials: EP
authors.lastname: Farney
authors.affiliation: Department of Chemistry, University of Wisconsin-Madison, 1101 University Avenue, Madison, WI, 53706, USA.
authors.forename: Sangyun
authors.initials: S
authors.lastname: Kim
authors.affiliation: Department of Chemistry, University of Wisconsin-Madison, 1101 University Avenue, Madison, WI, 53706, USA.
authors.forename: Desiree M
authors.initials: DM
authors.lastname: Bates
authors.affiliation: Department of Chemistry, University of Wisconsin-Madison, 1101 University Avenue, Madison, WI, 53706, USA. tyoon@chem.wisc.edu.
authors.forename: Tehshik P
authors.identifier: http://orcid.org/0000-0002-3934-4973
authors.initials: TP
authors.lastname: Yoon
mesh_terms: D000475:Alkenes / Q000737:chemistry*; D001386:Azides / Q000737:chemistry*; D005561:Formates / Q000737:chemistry*; D007097:Imines / Q000138:chemical synthesis* / Q000737:chemistry*; D008027:Light; D015394:Molecular Structure; D017319:Photosensitizing Agents / Q000737:chemistry*
chemical_list: D000475:Alkenes; D001386:Azides; D005561:Formates; D007097:Imines; D017319:Photosensitizing Agents; C017621:phenylnitrene
keywords: azides; aziridination; chemoselectivity; nitrenes; photocatalysis