Organoboronates as Lewis Acidic Nucleophiles in Enantioselective Catalysis

在化学部合成项目的资助下，休斯顿大学的Jeremy May教授正在设计和合成催化剂，特别是碳基催化剂（即“有机催化剂”），通过对三维结构的必要控制，提高碳-碳键形成反应的效率。这项研究是革命性的，因为这种有机催化剂的使用避免了与含金属催化剂相关的许多问题，包括毒性和贵金属的费用。此外，这项研究为有机催化反应的机制提供了基本的见解。其中一些反应在生物学上是相关的。梅博士的新反应复制并改进了具有抗菌、抗癌、神经学或免疫系统刺激活性的天然产品。此外，梅教授正在与KIPP夏普斯敦初中合作，向学生介绍实验化学和其他物理科学。梅实验室与处境不利和处境危险的学生合作，增强他们对科学的理解和为上大学做准备的愿望。May教授正在设计和合成不对称有机催化剂，这种催化剂可以促进乙烯基和芳基硼酸盐与α、β -不饱和酮的共轭加成，从而有效地合成碳-碳（C-C）键，并具有高水平的立体控制。这个项目将推进有机催化的基础知识，硼酸试剂的反应性，以及C-C键形成中的立体电子效应。所涉及的试剂和中间体对敏感的化学官能团具有高度的耐受性，允许底物范围的多样性和生物活性分子中常见的原子排列。这个项目的目的是合成难以形成的具有空间负担的C-C键。这项研究具有变革性，因为有机催化剂和硼酸盐的使用避免了与过渡金属催化剂相关的许多问题，包括缺乏杂环或杂原子的耐受性。吲哚酰丙二醇类天然产物的靶点和类似物的合成也正在开发中，这些天然产物已被证明具有抗菌、抗转移、阻断乙酰胆碱酯酶和刺激免疫系统的生物活性。所支持的研究工作在各个层次（研究生、本科生和高中）都有广泛的教育影响。梅教授继续支持与KIPP夏普斯敦初中的合作，向学生介绍实验化学和其他物理科学。该奖项反映了美国国家科学基金会的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。

With funding from the Synthesis Program of the Chemistry Division, Professor Jeremy May of the University of Houston is designing and synthesizing catalysts, especially carbon-based catalysts (i.e., "organocatalysts"), that increase the efficiency of carbon-carbon bonds forming reactions with the necessary control of three-dimentional structure. This research is transformative in that the use of such organocatalysts avoids many problems associated with metal-containing catalysts, including toxicity and the expense of precious metals. In addition, this research is providing fundamental insights into the mechanisms of organocatalyzed reactions. Some of these reactions are biologically relevant. Dr. May's new reactions replicate and improve upon natural products that have antibacterial, anticancer, neurological, or immune system-stimulating activity. In addition, the Professor May is partnering with KIPP Sharpstown Junior High to introduce students to experimental chemistry and other physical sciences. The May lab works with disadvantaged and at-risk students to bolster their scientific understanding and desire to prepare for college. Professor May is designing and synthesizing asymmetric organocatalysts that can promote the conjugate addition of vinyl and aryl boronates to alpha, beta-unsaturated ketones for the synthesis of carbon-carbon (C-C) bonds efficiently and with high levels of stereocontrol. This project is advancing fundamental knowledge of organocatalysis, the reactivity of boronate reagents, and stereoelectronic effects in C-C bond formation. The reagents and intermediates involved are highly tolerant of sensitive chemical functional groups, allowing great diversity in the substrate scope and access to atomic arrangements commonly found in bioactive molecules. The synthesis of sterically encumbered C-C bonds that are otherwise difficult to form is an aim of this project. This research is transformative as the use of organocatalysts and boronates avoids many of the problems associated with transition metal catalysts including a lack of tolerance of heterocycles or heteroatoms. The synthesis of targets and analogs of the indolyl propylene glycol class of natural products, which have been shown to exhibit antibacterial, antimetastatic, acetocholinesterase blocking, and immune system stimulating bioactivities is also being developed. The supported research effort has a broad educational impact at all levels (Graduate, Undergraduate, and High School). Professor May continues to support a partnership with KIPP Sharpstown Junior High to introduce the students to experimental chemistry and other physical sciences.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.