Intramolecular Aminocyanation of Alkenes by N[BOND]CN Bond Cleavage

Authors

  • Zhongda Pan,

    1. Department of Chemistry, University of Minnesota—Twin Cities, 207 Pleasant St. SE, Minneapolis, MN 55455 (USA)
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  • Sarah M. Pound,

    1. Department of Chemistry, University of Minnesota—Twin Cities, 207 Pleasant St. SE, Minneapolis, MN 55455 (USA)
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  • Naveen R. Rondla,

    1. Department of Chemistry, University of Minnesota—Twin Cities, 207 Pleasant St. SE, Minneapolis, MN 55455 (USA)
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  • Prof. Dr. Christopher J. Douglas

    Corresponding author
    1. Department of Chemistry, University of Minnesota—Twin Cities, 207 Pleasant St. SE, Minneapolis, MN 55455 (USA)
    • Department of Chemistry, University of Minnesota—Twin Cities, 207 Pleasant St. SE, Minneapolis, MN 55455 (USA)===

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  • We thank the National Institutes of Health for primary support of this work (R01 GM095559). C.J.D. thanks Research Corporation for Science Advancement for additional support through a Cottrell Scholar Award. We thank Dr. Joe Dalluge and Sean Murray for assistance with HRMS measurements. NMR spectra were recorded on an instrument purchased with support from the National Institutes of Health (S10OD011952).

Abstract

A metal-free, Lewis acid promoted intramolecular aminocyanation of alkenes was developed. B(C6F5)3 activates N-sulfonyl cyanamides, thus leading to a formal cleavage of the N[BOND]CN bonds in conjunction with vicinal addition of sulfonamide and nitrile groups across an alkene. This method enables atom-economical access to indolines and tetrahydroquinolines in excellent yields, and provides a complementary strategy for regioselective alkene difunctionalizations with sulfonamide and nitrile groups. Labeling experiments with 13C suggest a fully intramolecular cyclization pattern due to the lack of label scrambling in double crossover experiments. Catalysis with Lewis acid is realized and the reaction can be conducted under air.

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