一种用于α-季碳酮、α-酮酯和醛的对映选择性合成的催化方法。
A Catalytic Method for the Enantioselective Synthesis of α-Quaternary Ketones, α-Ketoesters and Aldehydes.
机构信息
Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, NC 27599-3290, USA.
出版信息
Angew Chem Int Ed Engl. 2023 Apr 24;62(18):e202215855. doi: 10.1002/anie.202215855. Epub 2023 Jan 25.
Abstract
A practical method for the efficient and enantioselective preparation of versatile ketones and aldehydes that contain an α-quaternary stereocenter is described. Reactions utilize simple carboxylic acid or ester starting materials, a monodentate chiral phosphine, and afford a variety of aryl, alkenyl, alkynyl, and alkyl-substituted ketone and aldehyde products in 25-94 % yield and 90 : 10 to >99 : 1 enantiomeric ratio. Reactions proceed by acyl substitution with in situ formed chiral allylic nucleophiles, and display selectivity and conversion dependence on a protic additive. The utility of the approach is demonstrated through several product transformations.
摘要
描述了一种用于高效和对映选择性制备含有α-季立体中心的多功能酮和醛的实用方法。该反应利用简单的羧酸或酯起始原料、单齿手性膦，以 25-94%的产率和 90:10 至>99:1 的对映选择性得到各种芳基、烯基、炔基和烷基取代的酮和醛产物。反应通过酰基取代进行，使用原位形成的手性烯丙基亲核试剂，并且显示出对质子添加剂的选择性和转化率依赖性。该方法的实用性通过几种产物转化得到了证明。
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