Lithiated Nitriles: Solution Structures and Reaction Stereochemistry

锂化腈：溶液结构和反应立体化学

• 批准号: 0213525
• 负责人: Paul Carlier
• 金额: $ 24万
• 依托单位: Virginia Polytechnic Institute and State University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2002
• 资助国家: 美国
• 起止时间: 2002-08-01 至 2005-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0213525&HistoricalAwards=false
• 关键词: Lithiated; Nitriles; Solution; Structures; Reaction

Professor Carlier and his students will first study the structures of lithiated nitriles in solution. They will use a variety of NMR spectroscopic techniques in these studies. Computational studies will be used to compliment and direct experimental work and have led the PI to propose the study of these lithiation reactions in noncoordinating hydrocarbon solvents. Carbon metallated nitriles discovered in these studies will then be used in an enantioselective deprotonation/alkylation reaction sequence which will be applied to enantioselective syntheses of alpha, alpha-disubstituted-alpha-amino acids.With this award, the Organic and Macromolecular Chemistry Program is supporting the research of Dr. Paul R. Carlier of the Department of Chemistry at Virginia Polytechnic Institute and State University. Professor Carlier and his students will study the structures and reaction chemistry of a class of molecules known as lithiated nitriles. The structures will be predicted using computational chemistry and modelling techniques then studied spectroscopically using nuclear magnetic resonance spectroscopy. Nitriles which can be lithiated on the carbon next to the nitrile functional group will then be used in enantioselective carbon-carbon bond forming reactions called alkylation reactions. These alkylation reactions produce molecules which are chiral (have two nonsuperimposable mirror images) and make only one of the two possible forms (a single enantiomer). Development of this family of reactions is one of the most important problems facing the pharmaceutical industry today. Students trained during the course of this work will gain skills in computational chemistry, nuclear magnetic resonance spectroscopy, and organic synthesis. These skills are needed by the pharmaceutical and speciality chemicals industries.

Carlier教授和他的学生将首先研究锂化腈在溶液中的结构。 他们将在这些研究中使用各种NMR光谱技术。 计算研究将用于补充和指导实验工作，并导致PI提出在非配位烃溶剂中研究这些锂化反应。 在这些研究中发现的碳金属化腈将用于对映选择性去质子化/烷基化反应序列，该反应序列将应用于对映选择性合成α，α-二取代-α-氨基酸。弗吉尼亚理工学院和州立大学化学系的Carlier说。 Carlier教授和他的学生将研究一类被称为锂化腈的分子的结构和反应化学。 将使用计算化学和建模技术预测结构，然后使用核磁共振光谱学进行光谱研究。 可以在腈官能团旁边的碳上锂化的腈然后将用于称为烷基化反应的对映选择性碳-碳键形成反应。 这些烷基化反应产生手性分子（具有两个不可重叠的镜像），并且仅产生两种可能形式中的一种（单一对映异构体）。 这类反应的发展是当今制药工业面临的最重要的问题之一。 在这项工作的过程中培训的学生将获得计算化学，核磁共振光谱学和有机合成的技能。 这些技能是制药和特种化学品行业所需要的。