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dc.contributor.authorTorregrosa, Robert Ryan P.
dc.contributor.authorAriyarathna, Yamuna Kumari
dc.contributor.authorChattopadhyay, Kalicharan
dc.contributor.authorTunge, Jon A.
dc.identifier.citationTorregrosa, 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.
dc.descriptionThis 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
dc.description.abstractUtilization 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
dc.publisherAmerican Chemical Societyen_US
dc.titleDecarboxylative Benzylations of Alkynes and Ketonesen_US
kusw.kuauthorTorregrosa, Yamuna
kusw.kuauthorKalicharan, Chattopadhyay
kusw.oaversionScholarly/refereed, author accepted manuscripten_US
kusw.oapolicyThis item meets KU Open Access policy criteria.en_US

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