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. 2016 Feb 5;55(6):2239-42.
doi: 10.1002/anie.201510868. Epub 2016 Jan 6.

Spin-Selective Generation of Triplet Nitrenes: Olefin Aziridination through Visible-Light Photosensitization of Azidoformates

Spencer O Scholz  1 , Elliot P Farney  1 , Sangyun Kim  1 , Desiree M Bates  1 , Tehshik P Yoon  2
Affiliations

Spin-Selective Generation of Triplet Nitrenes: Olefin Aziridination through Visible-Light Photosensitization of Azidoformates

Spencer O Scholz et al. Angew Chem Int Ed Engl. .

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.

Keywords: azides; aziridination; chemoselectivity; nitrenes; photocatalysis.

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Figures

Scheme 1
Scheme 1
Photocatalytic activation of azides via visible light triplet sensitization.
Scheme 2
Scheme 2
Scope of oxazoline products available by photocatalytic activation. (R = –CH2CCl3)
Scheme 3
Scheme 3
Studies supporting a stepwise diradical mechanism for aziridination via a triplet nitrene.
Scheme 4
Scheme 4
Aziridination of 2 in flow.
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References

    1. Hu XE. Tetrahedron. 2004;60:2701–2743.
    2. Huang CY, Doyle AG. Chem Rev. 2014;114:8153–8198. - PubMed
    3. Yudin AK, editor. Aziridines and Epoxides in Organic Synthesis. Wiley-VCH; Weinheim, Germany: 2006.
    1. Kametani T, Honda T. Adv Heterocycl Chem. 1986;39:3373–3387.
    2. Botuha C, Chemla F, Ferreira F, Pérez-Luna A. In: Heterocycles in Natural Product Synthesis. Majumdar KC, Chattopadhyay SK, editors. Wiley-VCH; Weinheim, Germany: 2011. pp. 1–39.
    1. Sweeney JB. Chem Soc Rev. 2002;31:247–258. - PubMed
    2. Watson IDG, Yu L, Yudin AK. Acc Chem Res. 2006;39:194–206. - PubMed
    1. Müller P, Fruit C. Chem Rev. 2003;103:2905–2920. - PubMed
    2. Degennaro L, Trinchera P, Luisi R. Chem Rev. 2014;114:7881–7929. - PubMed

    1. For reviews, see: Katsuki T. Chem Lett. 2005;34:1304–1309.Fantauzzi S, Caselli A, Gallo E. Dalt Trans. 2009:5434.Driver TG. Org Biomol Chem. 2010;8:3831–3846.Lu H, Zhang XP. Chem Soc Rev. 2011;40:1899–1909.

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