Point-to-Axial Chirality Transfer: Enabling Stereochemica Determinations and Enantioselective Reactions

在这个项目中，由化学部的化学结构，动力学机制-B计划资助，密歇根州立大学（MSU）化学系的Babak Borhan教授正在开发新的方法来快速识别有机分子的手性。许多分子都具有“手性中心”，其身份对其物理特性和生物功能至关重要。互为镜像的两个分子称为对映体。对映异构体可以具有显著不同的生物活性;例如，（+）-香芹酮是类萜天然产物，是葛缕子的精华，而其镜像，（-）-香芹酮是留兰香的精华。 这些完全不同的风味来自与味觉相关的手性蛋白质的非对映体相互作用。 这和许多其他重要的例子表明，需要准确和可靠的方法来识别分子的手性。这是获得资助的建议的中心主题。教授Borhan的小组也一直在密歇根州立大学在组织和领导项目种子，8- 10周的暑期课程部分通过资助美国化学学会和密歇根州立大学的各种组织在过去24年的领导者，以支持来自经济困难家庭的高中生的研究。这项工作将在下一个资助期间继续进行，该项目需要设计和合成超分子组装体，作为检测分子结构不对称性的传感器。本研究的主要目的是发展直接、快速、有效和明确的方法来确定手性有机分子的绝对立体化学。这些分子中的许多在生物活性化合物的合成中充当中间体或者是新发现的生物活性代谢物。圆二色谱（CD）将作为观察手性化合物与受体之间相互作用的主要工具。该项目侧重于各种官能团，包括手性环氧化物，醇，硅烷醇，硼烷，烯烃，联烯，炔和烷基芳烃。此外，引入“分子夹”作为一种新的主机系统将进行探索和分析。此外，MSU团队计划利用这些超分子复合物的内在螺旋性，这是由它们与结合的不对称客体分子的相互作用引起的，用于不对称催化，例如，该奖项反映了NSF的法定使命，并通过使用基金会的智力价值和更广泛的评估被认为值得支持。影响审查标准。

In this project, funded by the Chemical Structure, Dynamics & Mechanisms-B Program of the Chemistry Division, Professor Babak Borhan of the Chemistry Department at Michigan State University (MSU) is developing new methodologies to rapidly identify the chirality of organic molecules. Many molecules have ‘chiral centers’, the identity of which is critical to their physical characteristics and biological function. Two molecules that are mirror images of each other are referred to as enantiomers. Enantiomers can have dramatically different biological activities; for example, (+)-carvone is terpenoid natural product that is the essence of caraway, whereas its mirror image, (-)-carvone is the essence of spearmint. These completely different flavors arise from diastereomeric interactions with the chiral proteins associated with the sensing of taste. This, and many other important examples, show the need for accurate and reliable methods to identify chiralities of molecules. This is the central theme of the funded proposal. Professor Borhan's group has also been the leader at MSU for the past 24 years in organizing and leading Project SEED, an 8– 10-week summer program funded in part through the American Chemical Society and various organizations at MSU, to support research of high school students from financially disadvantaged families. This effort will continue during the next funding period.The project entails designing and synthesizing supramolecular assemblies to function as sensors for detecting molecular structural asymmetry. The principal objectives of this research are to develop straightforward, rapid, efficient, and unambiguous methods for determining the absolute stereochemistry of chiral organic molecules. Many of these molecules serve as intermediates in the synthesis of bioactive compounds or are newly discovered pharmacologically active metabolites. Circular dichroism (CD) will serve as the primary tool for observing the interactions between the chiral compounds and receptors in host-guest interactions. The project focuses on various functional groups, including chiral epoxides, alcohols, silanols, boranes, alkenes, allenes, alkynes, and alkyl arenes. Moreover, the introduction of 'molecular clips' as a novel host system will be explored and analyzed. Additionally, the MSU team plans to exploit the intrinsic helicity of these supramolecular complexes, induced by their interactions with bound asymmetric guest molecules, for applications in asymmetric catalysis, for example, in asymmetric transfer hydrogenation and in asymmetric excited state proton transfer.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.