Highly Diastereoselective and Enantioselective Olefin Cyclopropanation Using Engineered Myoglobin‐Based Catalysts

Melanie Bordeaux, Vikas Tyagi, Rudi Fasan

doi:10.1002/anie.201409928

Highly Diastereoselective and Enantioselective Olefin Cyclopropanation Using Engineered Myoglobin‐Based Catalysts

DOI Web Site Web Site 被引用文献17件

書誌事項

公開日: 2014-12-23

権利情報

http://onlinelibrary.wiley.com/termsAndConditions#vor

DOI

10.1002/anie.201409928

公開者: Wiley

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説明

<jats:title>Abstract</jats:title><jats:p>Using rational design, an engineered myoglobin‐based catalyst capable of catalyzing the cyclopropanation of aryl‐substituted olefins with catalytic proficiency (up to 46 800 turnovers) and excellent diastereo‐ and enantioselectivity (98–99.9 %) was developed. This transformation could be carried out in the presence of up to 20 g L<jats:sup>−1</jats:sup> olefin substrate with no loss in diastereo‐ and/or enantioselectivity. Mutagenesis and mechanistic studies support a cyclopropanation mechanism mediated by an electrophilic, heme‐bound carbene species and a model is provided to rationalize the stereopreference of the protein catalyst. This work shows that myoglobin constitutes a promising and robust scaffold for the development of biocatalysts with carbene‐transfer reactivity.</jats:p>