The Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, United States.
Alterome Therapeutics, San Diego, California 92127, United States.
J Am Chem Soc. 2023 May 24;145(20):11301-11310. doi: 10.1021/jacs.3c02104. Epub 2023 May 15.
An asymmetric decarboxylative [4+2] cycloaddition from a catalytically generated chiral Pd enolate was developed, forging four contiguous stereocenters in a single transformation. This was achieved through a strategy termed divergent catalysis, wherein departure from a known catalytic cycle enables novel reactivity of a targeted intermediate prior to re-entry into the original cycle. Mechanistic studies including quantum mechanics calculations, Eyring analysis, and KIE studies offer insight into the reaction mechanism.
发展了一种不对称脱羧[4+2]环加成反应，由催化生成的手性 Pd 烯醇盐引发，在单一转化中构建了四个连续的立体中心。这是通过一种称为发散催化的策略实现的，其中，在重新进入原始循环之前，从已知的催化循环中脱离可以使目标中间体表现出新颖的反应性。包括量子力学计算、艾林分析和 KIE 研究在内的机理研究为反应机理提供了深入了解。
