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    Decarboxylative Benzylations of Alkynes and Ketones

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    Issue Date
    2010-07-14
    Author
    Torregrosa, Robert Ryan P.
    Ariyarathna, Yamuna Kumari
    Chattopadhyay, Kalicharan
    Tunge, Jon A.
    Publisher
    American Chemical Society
    Type
    Article
    Article Version
    Scholarly/refereed, author accepted manuscript
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    Abstract
    Utilization of palladium π-benzyl complexes in cross-coupling reactions is becoming increasingly important in organic synthesis.1 However, methods for benzylic cross-couplings typically rely on the use of basic reagents or preformed organometallics. For example, Buchwald reported the cross-coupling of benzyl halides with alkynes using stoichiometric Cs2CO3; unfortunately, the basic reaction conditions often induce isomerization of the product benzylic alkynes to isomeric allenes.2 Negishi reported the benzylic cross-coupling with acetylides via stoichiometric alkynyl zinc bromides that must be prepared from ZnBr2.3 Not only do these methods require stoichiometric bases or organometallics, but they also utilize benzyl halides that are expensive, hazardous, and more difficult to handle than related benzyl alcohol derivatives.

    Legros, Kuwano and others have reported catalytic benzylation of stabilized nucleophiles using activated benzylic alcohol derivatives.4 While benzylations of highly stabilized enolates (pKa ~ 10-13),4a-d phenols (pKa ~ 10),4e and arene sulfinates (pKa ~ 7)4f have been successful, the reaction of less stabilized nucleophiles has proven difficult.5 Since we have previously developed decarboxylative coupling strategies that allow allylation of nonstabilized nucleophiles without the use of an external base or organometallic, we hypothesized that a similar strategy might allow decarboxylative coupling of benzylic esters with nonstabilized nucleophiles (eq. 1).5-7
    Description
    This document is the Accepted Manuscript version of a Published Work that appeared in final form in the Journal of the American Chemical Society, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://doi.org/:10.1021/ja1035557.
    URI
    http://hdl.handle.net/1808/24374
    DOI
    https://doi.org/10.1021/ja1035557
    Collections
    • Chemistry Scholarly Works [552]
    Citation
    Torregrosa, R. R. P., Ariyarathna, Y., Chattopadhyay, K., & Tunge, J. A. (2010). Decarboxylative Benzylations of Alkynes and Ketones. Journal of the American Chemical Society, 132(27), 9280–9282. http://doi.org/10.1021/ja1035557

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    Contact KU ScholarWorks
    785-864-8983
    KU Libraries
    1425 Jayhawk Blvd
    Lawrence, KS 66045
    785-864-8983

    KU Libraries
    1425 Jayhawk Blvd
    Lawrence, KS 66045
    Image Credits
     

     

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