Template Catalysis of the Diels-Alder Reaction

Diels-Alder反应是化学中最强大的碳-碳键形成反应之一，在一个步骤中产生多达四个立体中心。将构建含有2,6-二（酰基氨基）吡啶和羧酸基团的u型模板，以适当的取向同时结合含马来酰亚胺和二烯的垂坠氨基，用于diols - alder反应。通过焓（氢键）和熵（接近）效应，期望该模板在控制立体选择性和区域选择性的同时催化Diels-Alder反应。研究的目标包括控制取代环戊二烯反应的区域选择性、逆转Diels-Alder反应的自然内选择性和实现对映体选择性。重点将放在战略的发展，以克服产品抑制相互作用。该奖项是诺威克博士化学博士后研究奖学金的启动资助增量，以支持他在加州大学欧文分校的研究。诺威克博士的研究重点是开发一种模板催化剂，以结合合适的二烯和亲二烯组分，并催化区域选择性、立体选择性和对映选择性diols - alder反应。

The Diels-Alder reaction is one of the most powerful carbon-carbon bond forming reactions in chemistry, generating as many as four stereocenters in a single step. A U-shaped template will be developed bearing 2,6-di(acylamino)pyridine and carboxylic acid groups to simultaneously bind maleimide and dienes bearing pendant amino groups in an appropriate orientation for Diels-Alder reaction. By means of enthalpic(hydrogen bonding) and entropic(proximity) effects, the template is anticipated to catalyze the Diels-Alder reaction while controlling the stereo- and regioselectivity. The goals of the research include control of the regioselectivity of reaction of substituted cyclopentadienes, inversion of the natural endo-selectivity of the Diels-Alder reaction, and achievement of enantioselectivity. Emphasis will be placed upon the development of strategies to overcome product inhibition interactions. %%% This award is the starter grant increment of Dr. Nowick's Postdoctoral Research Fellowship in Chemistry in support of his research at the University of California at Irvine. The main thrust of Dr. Nowick's research is the development of a template catalyst to bind suitable diene and dienophile components and catalyze regio-, stereo-, and enantioselective Diels-Alder reactions.