Published November 30, 2010 | Supplemental Material + Published
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Phosphine-catalyzed asymmetric additions of malonate esters to γ-substituted allenoates and allenamides

Abstract

Because carbonyl groups are ubiquitous in organic chemistry, the ability to synthesize functionalized carbonyl compounds, particularly enantioselectively, is an important objective. We have developed a straightforward and versatile method for catalytic asymmetric carbon–carbon bond formation at the γ-position of carbonyl compounds, specifically, phosphine-catalyzed additions of malonate esters to γ-substituted allenoates and allenamides. Mechanistic studies have provided insight into the reaction pathway.

Additional Information

© 2010 National Academy of Sciences. Edited by David W. C. MacMillan, Princeton University, Princeton, NJ, and accepted by the Editorial Board May 30, 2010 (received for review March 18, 2010). PNAS first published July 12, 2010. We thank Dr. Sean W. Smith for preliminary studies and Dr. Meiliana Tjandra and Shaun D. Fontaine for experimental assistance. Support has been provided by the National Institutes of Health (National Institute of General Medical Sciences, Grant R01-GM57034), the University of Bologna (Marco Polo fellowship for R.S.), Merck Research Laboratories, and Novartis. R.S. and J.S. contributed equally to this work. Author contributions: R.S., J.S., and G.C.F. designed research; R.S. and J.S. performed research; R.S., J.S., and G.C.F. analyzed data; and J.S. and G.C.F. wrote the paper. The authors declare no conflict of interest. This article is a PNAS Direct Submission. D.W.M. is a guest editor invited by the Editorial Board. This article contains supporting information online at www.pnas.org/lookup/suppl/doi:10.1073/pnas.1003597107/-/DCSupplemental.

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