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Exo-Selective Reductive Macrocyclization of Ynals
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    Exo-Selective Reductive Macrocyclization of Ynals
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    Department of Chemistry, University of Michigan, 930 North University Avenue, Ann Arbor, Michigan 48109-1055, United States
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    Organic Letters

    Cite this: Org. Lett. 2015, 17, 6, 1493–1496
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    https://doi.org/10.1021/acs.orglett.5b00381
    Published March 6, 2015
    Copyright © 2015 American Chemical Society

    Abstract

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    A general protocol for the highly exo-selective macrocyclization of ynals using a nickel/N-heterocyclic carbene catalyst system has been developed. A series of 10- to 21-membered macrocycles bearing an exomethylene substituent was synthesized in good yields with excellent regioselectivity (exo/endo >95:5). Very high levels of long-range diastereocontrol can also be achieved for some classes of macrocycles. Complementary to previously reported endo-selective macrocyclizations, this method provides accesses to exoalkylidene macrocycles from simple ynals in high selectivity.

    Copyright © 2015 American Chemical Society

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    Synthetic details, spectral data, and CIF file for the X-ray crystallographic data. These materials are available free of charge via the Internet at http://pubs.acs.org.

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    Cited By

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    This article is cited by 28 publications.

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    Organic Letters

    Cite this: Org. Lett. 2015, 17, 6, 1493–1496
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.orglett.5b00381
    Published March 6, 2015
    Copyright © 2015 American Chemical Society

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