肌红蛋白催化的醛的烯化反应。
Myoglobin-Catalyzed Olefination of Aldehydes.
作者信息
Tyagi Vikas, Fasan Rudi
机构信息
Department of Chemistry, University of Rochester, 120 Trustee Road, Rochester, NY, 14627, USA.
出版信息
Angew Chem Int Ed Engl. 2016 Feb 12;55(7):2512-6. doi: 10.1002/anie.201508817. Epub 2016 Jan 14.
Abstract
The olefination of aldehydes constitutes a most valuable and widely adopted strategy for constructing carbon-carbon double bonds in organic chemistry. While various synthetic methods have been made available for this purpose, no biocatalysts are known to mediate this transformation. Reported herein is that engineered myoglobin variants can catalyze the olefination of aldehydes in the presence of α-diazoesters with high catalytic efficiency (up to 4,900 turnovers) and excellent E diastereoselectivity (92-99.9 % de). This transformation could be applied to the olefination of a variety of substituted benzaldehydes and heteroaromatic aldehydes, also in combination with different alkyl α-diazoacetate reagents. This work provides a first example of biocatalytic aldehyde olefination and extends the spectrum of synthetically valuable chemical transformations accessible using metalloprotein-based catalysts.
摘要
醛的烯化反应是有机化学中构建碳-碳双键最有价值且广泛采用的策略。尽管为此已有多种合成方法，但尚无已知的生物催化剂介导这种转化。本文报道了工程改造的肌红蛋白变体能够在α-重氮酯存在下高效催化醛的烯化反应（高达4900次周转），并具有出色的E-非对映选择性（92-99.9%的非对映体过量）。这种转化可应用于多种取代苯甲醛和杂芳族醛的烯化反应，也可与不同的烷基α-重氮乙酸酯试剂联合使用。这项工作提供了生物催化醛烯化反应的首个实例，并扩展了使用基于金属蛋白的催化剂可实现的具有合成价值的化学转化范围。
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