Phosphine-catalyzed asymmetric additions of malonate esters to {gamma}-substituted allenoates and allenamides.

Sinisi, Riccardo; Sun, Jianwei; Fu, Gregory C · Proc Natl Acad Sci U S A · 2010

basic_science · Level V

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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.