Chi Yonggui, Scroggins Steven T, Fréchet Jean M J
Division of Materials Sciences, Lawrence Berkeley National Laboratory, and College of Chemistry, University of California, Berkeley, California 94720-1460, USA.
J Am Chem Soc. 2008 May 21;130(20):6322-3. doi: 10.1021/ja8013456. Epub 2008 Apr 24.
Non-interpenetrating star polymer catalysts designed to mimic the site isolation characteristics of enzymes enable the one-pot combination of multiple otherwise incompatible catalysts for asymmetric cascade reactions that involve iminium, enamine, and H-bonding catalysis. Control experiments replacing star polymer catalysts with the corresponding small molecule or linear polymer analogues lead to little or no cascade reaction. Our strategy also allows straightforward access to all possible stereoisomers of the cascade product individually by proper choice of catalyst chirality. To our knowledge, this work represents the most sophisticated study of soluble polymers for site isolation, enzyme-like catalysis that generates cascade products with multiple chiral centers.
设计用于模拟酶的位点隔离特性的非互穿星形聚合物催化剂,能够实现多种原本不相容的催化剂在一锅反应中用于涉及亚胺离子、烯胺和氢键催化的不对称串联反应。用相应的小分子或线性聚合物类似物替代星形聚合物催化剂的对照实验几乎没有或根本没有导致串联反应。我们的策略还允许通过适当选择催化剂的手性,直接单独获得串联产物的所有可能立体异构体。据我们所知,这项工作代表了对用于位点隔离的可溶性聚合物进行的最复杂的研究,这种类似酶的催化作用能够生成具有多个手性中心的串联产物。