The Origins of Stereoselection in Asymmetric Reductions and Hydrogenations

不对称还原和氢化中立体选择的起源

• 批准号: 1058483
• 负责人: Matthew Meyer
• 金额: $ 42.72万
• 依托单位: University of California - Merced
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2011
• 资助国家: 美国
• 起止时间: 2011-08-15 至 2014-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1058483&HistoricalAwards=false
• 关键词: Origins; Stereoselection; Asymmetric; Reductions; Hydrogenations

The Chemical Structure, Dynamics and Mechanisms Program of the Chemistry Division supports Professor Matthew Meyer at the University of California, Merced for studies into the origins of stereoselection in asymmetric reductions and hydrogenations. Kinetic isotope effects will be used (KIEs) to quantitatively probe physical interactions that govern stereoselection in Corey-Bakshi-Shibata reductions and in Ru(II) catalyzed hydrogenations. The KIEs will be used to develop experimentally-corroborated transition structure models of highly stereoselective hydrogenations. A new method, isotopic perturbation of stereoselection, will be used to study systematic changes in Ru(II) catalyst environment using the series of TunePhos ligands. The transition structures for the reactions studied will be investigated computationally in order to interrogate the interactions that govern stereoselection. Catalytic asymmetric reactions are of great importance to the fine chemicals and pharmaceutical industry. These industries, with their current focus on reducing feedstocks and enabling environmentally friendly technologies, have a critical need for new catalytic asymmetric methodologies. Surprisingly, the detailed mechanisms by which chirality is transferred are poorly understood in most developing methodologies. This project will refine the mechanistic understanding of stereoselection in two broad classes of reactions. Young scientists must be stewarded as they develop into professionals. The project will provide training to a diverse group of students, many from under-represented groups. An important component will involve exposing undergraduates to computational chemistry as well as the experimental aspects of organic chemistry. The PI will also be involved in outreach activities with Merced County 4-H that include the National Science Day 4-H experiment.

化学系的化学结构，动力学和机制计划支持加州大学默塞德的Matthew Meyer教授研究不对称还原和氢化中立体选择的起源。动力学同位素效应（KIE）将被用来定量探测物理相互作用，支配Corey-Bakshi-柴田还原和Ru（II）催化氢化的立体选择性。KIE将用于开发实验证实的高度立体选择性氢化的过渡结构模型。一种新的方法，同位素扰动的立体选择性，将被用来研究系统的变化，钌（II）催化剂环境使用系列TunePhos配体。研究的反应的过渡结构将通过计算进行研究，以询问管理立体选择的相互作用。催化不对称反应在精细化工和医药工业中具有重要的意义。这些工业目前的重点是减少原料和实现环境友好型技术，迫切需要新的催化不对称方法。令人惊讶的是，手性转移的详细机制在大多数发展中的方法中知之甚少。这个项目将完善两大类反应中立体选择的机理理解。年轻科学家在成长为专业人员时必须得到指导。该项目将向各种学生群体提供培训，其中许多人来自代表性不足的群体。一个重要的组成部分将涉及暴露本科生计算化学以及有机化学的实验方面。PI还将参与与默塞德县4-H的外联活动，其中包括国家科学日4-H实验。