烯醇盐稳定的烯醇碳酸酯不对称脱羧烷基化反应的高通量筛选
High-Throughput Screening of the Asymmetric Decarboxylative Alkylation Reaction of Enolate-Stabilized Enol Carbonates.
作者信息
McDougal Nolan T, Virgil Scott C, Stoltz Brian M
机构信息
The Warren and Katharine Schlinger Laboratory of Chemistry and Chemical Engineering, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, USA.
出版信息
Synlett. 2010 Jan 1;11:1712-1716. doi: 10.1055/s-0030-1258094.
Abstract
The use of high-throughput screening allowed for the optimization of reaction conditions for the palladium-catalyzed asymmetric decarboxylative alkylation reaction of enolate-stabilized enol carbonates. Changing to a non-polar reaction solvent and to an electron-deficient PHOX derivative as ligand from our standard reaction conditions improved the enantioselectivity for the alkylation of a ketal-protected,1,3-diketone-derived enol carbonate from 28% ee to 84% ee. Similar improvements in enantioselectivity were seen for a β-keto-ester derived- and an α-phenyl cyclohexanone-derived enol carbonate.
摘要
高通量筛选的应用使得烯醇化物稳定的烯醇碳酸酯的钯催化不对称脱羧烷基化反应的反应条件得以优化。从我们的标准反应条件转变为使用非极性反应溶剂以及缺电子的PHOX衍生物作为配体，使缩酮保护的、由1,3 - 二酮衍生的烯醇碳酸酯的烷基化对映选择性从28% ee提高到了84% ee。对于由β - 酮酯衍生的和由α - 苯基环己酮衍生的烯醇碳酸酯，也观察到了类似的对映选择性提高。
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