SusChEM: Direct functionalization of aldehydes enabled by aminocatalysis

NSF化学部的化学合成项目支持新墨西哥州大学化学生物学系王伟教授的研究。 王教授和他的学生基于氨基催化的概念开发了成本效益和环境友好的有机合成技术。 本研究的目的是开发和利用新的有机催化活化模式的有机转化。 新的化学转化为强大的合成方法，从简单和容易获得的化学物质开始，简单和原子经济地合成多功能的结构单元。 合成也在温和的反应条件下进行。 这些用于制造复杂分子结构的“一锅法”级联方法解决了现代有机合成中的关键挑战。这些方法包括提高合成效率，使用可持续和廉价的化学品，避免有毒试剂，减少废物和危险副产品。 由于操作简单，反应条件温和和环境友好，这项研究非常适合各级科学家的教育。 王教授的研究小组有能力为那些在科学领域代表性不足的学生提供教育和培训。该项目继续努力，旨在将氨基催化的范围扩展到烯胺和亚胺催化的成熟活化模式之外。 王教授和他的团队挑战机械论教条，他们证明了亚胺离子亲核加成产生的加合物中的胺部分可以在随后的亲核取代反应中作为离去基团。中间体胺加成产物的原位释放为醛的氨基催化直接官能化创造了新的场景。 本研究表明，通过仔细操纵催化剂和反应物的电子和空间性质，明智的设计和选择胺催化剂，以及优化反应条件，开发新的和强大的催化级联反应。鉴于醛的容易获得性、反应性和广泛的结构多样性，在有效的一锅反应中构建了大量新的合成结构单元和生物学上重要的复杂分子结构。 教育计划延续了一个传统，即在夏季招收本科生，特别是来自代表性不足的少数民族的学生，在王博士的实验室进行研究。 王博士还将他的学术实验室的研究成果和实验融入他的本科生的经验。

The Chemical Synthesis Program of the NSF Chemistry Division supports the research of Professor Wei Wang in the Department of Chemistry & Chemical Biology at the University of New Mexico. Professor Wang and his students develop cost-effective and environmentally friendly technologies for organic synthesis based on the concept of aminocatalysis. The goal of this research is to develop and exploit new organocatalytic activation modes for organic transformations. New chemistries are transformed into powerful synthetic methods for the facile and atom-economic synthesis of versatile building blocks starting from simple and readily available chemicals. The syntheses are also conducted under mild reaction conditions. These "one-pot" cascade methods, used to make complex molecular architectures, address critical challenges in modern organic synthesis. The methods include the improvement of synthetic efficiency, the use of sustainable and inexpensive chemicals, the avoidance of toxic agents, and the reduction of waste and hazardous byproducts. As a consequence of operational simplicity, mild reaction conditions and environmental friendliness, this research is well suited for the education of scientists at all levels. Professor Wang's group is well positioned to provide education and training for students from groups that are underrepresented in science.This project continues efforts aimed at expanding the scope of aminocatalysis beyond the well-established activation modes of enamine and iminium catalysis. Professor Wang and his team challenge mechanistic dogma by showing that amine moieties in adducts which result from nucleophilic additions to iminum ions can serve as leaving groups in ensuing nucleophilic substitution reactions. In situ release of the intermediate amine addition products creates a new scenario for aminocatalytic direct functionalization of aldehydes. This research demonstrates that through careful manipulation of the electronic and steric properties of catalysts and reactants, judicious design and selection of amine catalysts, and optimization of reaction conditions, new and powerful catalytic cascade reactions are developed. Given the ready accessibility, reactivity and broad structural diversity of aldehydes, a wide array of new synthetic building blocks and biologically-important complex molecular architectures are constructed in efficient one-pot reactions. The educational plan continues a tradition to recruit undergraduate students especially from underrepresented minority groups over the summer to conduct research in Dr. Wang's laboratory. Dr. Wang also integrates the research results and experiments from in his academic laboratory into his undergraduate students' experiences.