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。

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.