Chiral Relay: A Powerful Strategy for Enantioselective Transformations

本提案概述了一种新的“手性接力”方案，该方案依赖于使用流态基团来影响面选择性，并在各种对映选择性转化中提供反应性增强。两种新的和强大的方法来控制立体化学-模板和添加剂-将利用他们在转化的意义。在建议的工作中发展的关键方法是：(1)外选择性Diels-Alder反应，(2)与烷基酸酯和烯酰亚胺的环加成，(3)对映选择性Friedel-Crafts烷基化，以及(4)高温下的对映选择性反应。所提出的实验将进一步加深我们对静态手性和流动手性之间相互作用的理解。通过这个奖项，有机和大分子化学项目支持北达科他州立大学化学系Mukund Sibi教授的工作。Sibi教授和他的学生们正在开发控制复杂有机分子中原子的精确三维位置的方法，使用新的方法来创建和传递分子的一部分到新形成的结构部分的立体化学信息。使用催化过程制备对映体纯化合物的通用方法的发现和发展将为制备重要的药物制剂和中间体提供工具，从而造福社会。

This proposal outlines a novel program on 'Chiral Relay' which relies on the use of fluxional groups to impact face selectivity as well as provide reactivity enhancements in a variety of enantioselective transformations. Two novel and powerful methods for controlling stereochemistry - templates and additives - will be exploited by employing them in transformations of significance. Key methodologies to be developed in the proposed work are (1) exo selective Diels-Alder reactions, (2) cycloadditions with alkynoates and alleneimides, (3) enantioselective Friedel-Crafts alkylations, and (4) enantioselective reactions at higher temperatures. The proposed experiments will further our understanding of the interplay between static chirality and fluxional chirality. With this award, the Organic and Macromolecular Chemistry Program is supporting the work of Professor Mukund Sibi, of the Department of Chemistry at North Dakota State University. Professor Sibi and his students are developing methods for the control of the precise three-dimensional placement of atoms in complex organic molecules, using novel methods for the creation and communication of stereochemical information from one part of a molecule to a newly forming portion of the structure. The discovery and development of general methods for the preparation of enantiomerically pure compounds using catalytic processes will benefit society by providing tools for the preparation of important pharmaceutical agents and intermediates.