Exploring New Chemical Reactivities for Synthetic Efficiency

背景与目的：化学合成通过转化自然资源，在生产药品、农用化学品、塑料、涂料、纺织品和电子材料方面起着至关重要的作用。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，并引起与化学废物有关的环境/健康问题。如何有效地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发现新的化学反应，以实现更可持续的未来化学合成，并在绿色/可持续合成化学的研究成果、影响和培训方面建立一个领先的卓越计划。******研究计划：探索新的化学反应：(a)可以在环境气氛下与良性溶剂一起工作；(b)最大限度地利用原子；(c)直接将可再生生物质等自然资源从其原生状态转化为有用的化学产品。避免需要复杂的化学过程和无水有机溶剂是我们开发可持续化学合成的方法。在我们之前成功的基础上，这项发现基金将继续我们在以下三个主要方面的研究：(1)研究水中催化格氏型烷基化和不对称格氏型反应；(2)研究了在水中用C-H键代替有机金属试剂催化亲核加成的机理及应用；(3)研究了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Barbier-Grignard反应、水中具有C-H键的催化亲核加成反应和催化直接C-H/C-H交叉脱氢偶联反应的联合成功，将从根本上改变化学教科书中描述的有机反应的方法和化学家进行有机合成的方式。这些反应将大大提高化学合成的效率，并通过避免各种官能团的保护-去保护、卤化-去卤化和功能化-去功能化过程，最大限度地减少化学废物。总之，这些将对未来的可持续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.**