Exploring New Chemical Reactivities for Synthetic Efficiency

背景和目的：化学合成在通过转化自然资源来生产药品、农用化学品、塑料、涂料、纺织品和电子材料方面发挥着至关重要的作用。然而，最先进的化学合成往往需要大量的辅助步骤，导致资源效率总体较低，并引发与化学废物有关的环境/健康问题。如何有效利用有限的自然资源是可持续发展的一个关键方面。该项目的总体目标是为更可持续的未来化学合成发现新的化学反应性，并在绿色/可持续合成化学方面建立领先的研究成果、影响和培训计划。*研究计划：探索新的化学反应性：(A)可以在具有无害溶剂的环境中工作；(B)最大限度地提高原子利用率；(C)直接将自然资源(如可再生生物质)从其原生状态转化为有用的化学产品。避免复杂的化学过程和无水有机溶剂一直是我们开发可持续化学合成的方法。在已有研究成果的基础上，本次发现基金将继续我们在以下三个主要方面的研究：(1)研究水中格氏类型的催化烷基化反应和不对称格氏类型的反应；(2)研究以C-H键作为有机金属试剂在水中的催化亲核加成反应的机理和应用；(3)研究甲烷和短链烷烃的不对称交叉脱氢偶联(CDC)和非氧化催化转化为芳烃和二烯。*意义：水中的Barbier-Grignard反应、水中具有C-H键的催化亲核加成反应和催化的直接C-H/C-H交叉脱氢偶联的共同成功将从根本上改变化学教科书中介绍的有机反应的方法和化学家进行有机合成的方式。这些反应将极大地提高化学合成的效率，避免各种官能团的保护-去保护、卤化-脱卤化和官能化-去功能化过程，从而最大限度地减少化学废物。总而言之，这些都将对未来可持续的化学合成产生深远的影响。

Background and Objectives: Chemical synthesis plays a vital role in producing pharmaceuticals, agrochemicals, plastics, coatings, textiles, and electronic materials by converting natural resources. However, state-of-the-art chemical synthesis often requires extensive auxiliary steps that lead to overall low resource efficiency and raise environmental/health concerns related to chemical waste. How to utilize limited natural resources efficiently constitutes a key aspect of sustainability. The overall objective of this project is to discover new chemical reactivities for more sustainable future chemical syntheses and to establish a leading program of excellence in research output, impact, and training in Green/Sustainable Synthetic Chemistry.******Research Plan: To explore new chemical reactivities that: (a) can work under ambient atmosphere with benign solvents; (b) maximize atom-utilization; and (c) directly transform natural resources such as renewable biomass from their native states into useful chemical products. Avoiding the need for elaborate chemical processes and anhydrous organic solvents has been our approach towards developing sustainable chemical syntheses. Building on our previous successes, this Discovery Grant will continue our research in the following three major avenues: (1) study the catalytic Grignard-type alkylation and asymmetric version of Grignard-type reactions in water; (2) study the mechanism and applications of catalytic nucleophilic additions using C-H bonds as surrogates for organometallic reagents in water; and (3) study the asymmetric Cross-Dehydrogenative-Coupling (CDC) and non-oxidative catalytic conversion of methane and short-chain alkanes into aromatics and dienes. ***Significance: The combined success of the Barbier-Grignard reactions in water, the catalytic nucleophilic addition reactions in water with C-H bonds, and the catalytic direct C-H/C-H Cross-Dehydrogenative Coupling will fundamentally change approaches to organic reactions as they are presented in chemistry textbooks and to the way chemists perform organic synthesis. These reactions will drastically increase the efficiency of chemical syntheses and minimize chemical waste by avoiding protection-deprotection of various functional groups, halogenation-dehalogenation, and functionalization-defunctionalization processes. Together, these will have a profound impact on future sustainable chemical syntheses.**