Asymmetric Synthesis Using N-O Compounds

使用 N-O 化合物的不对称合成

• 批准号: 6666571
• 负责人: HISASHI None YAMAMOTO
• 金额: $ 30.58万
• 依托单位: UNIVERSITY OF CHICAGO
• 依托单位国家: 美国
• 财政年份: 2003
• 资助国家: 美国
• 起止时间: 2003-09-01 至 2007-08-31
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/6666571
• 关键词: alkenes; carbonyl compound; catalyst; chemical registry /resource; chemical synthesis; combinatorial chemistry; hydroxylamine; metals; molecular asymmetry; nitric oxide; oxidation; phosphines; protonation; stereochemistry; sulfides; technology /technique development

DESCRIPTION (provided by applicant): This research proposal describes the development of an efficient asymmetric catalysis based on the new chemistry of N-O compounds. The research will be directed towards three goals. The first goal will be to design a metal catalyst for a truly useful and practical asymmetric oxidation of olefinic alcohols, alkenes, sulfides, and phosphines. The method heavily depends on our previous observations of vanadium asymmetric epoxidation catalyst for which unique hydroxamic acid libraries were developed. We intend to synthesize a number of new hydroxamic acid ligand libraries and evaluate them for enantioselectivity and reactivity in vanadium-catalyzed asymmetric epoxidation. The second theme will focus on selective synthesis of new hydroxyamino and aminooxy carbonyl compounds. Using simple nitroso starting materials in the presence of Lewis acid catalysts, various carbonyl compounds could be converted to new hydroxyamino and aminooxy derivatives. Furthermore, with this approach, asymmetric catalytic introduction of oxygen and nitrogen functional groups alpha to carbonyl compounds will be obtained and used as a key synthetic reaction useful for chiral natural and unnatural product synthesis. The third effort will be to develop new asymmetric protonation in alcoholic solvents using metal catalysts with hydroxamic acid and related N-O ligand libraries. Efficient asymmetric protonation of racemic carbonyl compounds is an important synthetic transformation, which has not been developed to a useful level. Overall, all of these goals are expected to result in not only the development of highly efficient catalytic asymmetric synthesis but also the development of new methods and concepts that should provide a number of useful organic synthesis endeavors as well as new entry into various N-O compounds, which biologically are a highly important class of molecules.

描述（由申请人提供）：本研究计划描述了基于N-O化合物新化学的高效不对称催化的发展。这项研究将针对三个目标。