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. 2015 Jan 14;137(1):122-5.
doi: 10.1021/ja511701j. Epub 2014 Dec 23.

Enantioconvergent synthesis of functionalized γ-butyrolactones via (3 + 2)-annulation

C Guy Goodman  1 , Morgan M Walker, Jeffrey S Johnson
Affiliations

Enantioconvergent synthesis of functionalized γ-butyrolactones via (3 + 2)-annulation

C Guy Goodman et al. J Am Chem Soc. .

Erratum in

Abstract

A dynamic kinetic resolution of β-halo α-keto esters in an asymmetric homoenolate reaction is described. A chiral N-hetereocyclic carbene catalyzes the a(3) → d(3)-umpolung addition of α,β-enals to racemic α-keto esters, forming γ-butyrolactones with three contiguous stereocenters. The addition occurs with high regio-, diastereo-, and enantiocontrol. This methodology constitutes an intermolecular DKR process to set three stereocenters during the key bond forming event.

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Figures

Scheme 1
Scheme 1. Degrees of Stereocomplexity in Dynamic Kinetic Transformations
Scheme 2
Scheme 2. Chemoselectivity Challenges for the Carbene Catalyzed Coupling of α,β-Enals (Blue) and Enolizable α-Keto Esters (Red)
Scheme 3
Scheme 3. Gram Scale Reaction of 1i and Cinnamaldehyde
See this image and copyright information in PMC

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