Synthesis 2010(5): 870-881  
DOI: 10.1055/s-0029-1218663
FEATUREARTICLE
© Georg Thieme Verlag Stuttgart ˙ New York

Development of Oxidative Formylation and Ketonylation Reactions

Lisa M. Ambrosini, Tim A. Cernak, Tristan H. Lambert*
Department of Chemistry, Columbia University, New York, NY 10027, USA
Fax: +1(212)9321289; e-Mail: tl2240@columbia.edu;
Further Information

Publication History

Received 2 November 2009
Publication Date:
05 February 2010 (online)

Abstract

The first oxidative formylation and oxidative ketonylation of alkenylamines and alkenyl alcohols is demonstrated. A range of substrates that participate in this process are provided. Oxidative formylation was found to proceed optimally with the use of triphenylsilane as the hydride source. Oxidative ketonylation was feasible with a number of organometallic partners, especially dialkylzinc or organostannanes. An interesting finding regarding the fate of various acylpalladium intermediates is discussed.

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8

Probe experiments using standard co-oxidants including copper(II) salts, benzoquinone, and PhI(OAc)2 have not been productive.