Work

Stereodivergent synthesis of 1,4-dicarbonyls by traceless charge–accelerated sulfonium rearrangement

Year: 2018

Type: article

Abstract: The chemistry of the carbonyl group is essential to modern organic synthesis. The preparation of substituted, enantioenriched 1,3- or 1,5-dicarbonyls is well developed, as their disconnection naturally follows from the intrinsic polarity of the carbonyl group. By contrast, a general enantioselective access to quaternary stereocenters in acyclic 1,4-dicarbonyl systems remains an unresolved problem, despite the tremendous importance of 2,3-substituted 1,4-dicarbonyl motifs in natural products and drug scaffolds. Here we present a broad enantioselective and stereodivergent strategy to access acyclic, polysubstituted 1,4-dicarbonyls via acid-catalyzed [3,3]-sulfonium rearrangement starting from vinyl sulfoxides and ynamides. The stereochemistry at sulfur governs the absolute sense of chiral induction, whereas the double bond geometry dictates the relative configuration of the final products.

Source: Science

DOI: 10.1126/science.aat5883

Authors: Dainis Kaldre, Immo Klose, Nuno Maulide

Institution: University of Vienna

Language: English

Topic: Asymmetric Synthesis and Catalysis

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: green

Funders: Deutsche Forschungsgemeinschaft, Österreichischen Akademie der Wissenschaften, Austrian Science Fund, H2020 European Research Council

Awards: Reversing polarity: a family of chemoselective oxidations, G3557203286, A Unified Approach to Redox-Neutral C-C Couplings: Exploiting Vinyl Cation Rearrangements