Asymmetric Synthesis Using N-O Compounds.

使用 N-O 化合物的不对称合成。

• 批准号: 6945732
• 负责人: HISASHI None YAMAMOTO
• 金额: $ 32.42万
• 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/6945732
• 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(申请人提供)：这项研究计划描述了一种基于N-O化合物的新化学的高效不对称催化的发展。这项研究将朝着三个目标进行。 第一个目标是设计一种金属催化剂，用于烯醇、烯烃、硫化物和膦的真正有用和实用的不对称氧化。该方法在很大程度上依赖于我们之前对钒不对称环氧化催化剂的观察，并为其开发了独特的异羟肟酸库。我们打算合成一些新的异羟肟酸配体文库，并对它们在钒催化的不对称环氧化反应中的对映选择性和反应性进行评价。 第二个主题将集中在选择性合成新的羟氨基和氨氧羰基化合物。在Lewis酸催化剂存在下，以简单的亚硝基为起始原料，可将各种羰基化合物转化为新的羟氨基和氨氧基衍生物。此外，通过这种方法，将获得不对称催化引入氧和氮官能团到羰基化合物，并作为关键的合成反应用于手性天然和非天然产物的合成。 第三项工作将是开发新的不对称质子化反应，在醇类溶剂中使用带有异羟肟酸的金属催化剂和相关的N-O配位体库。外消旋羰基化合物的高效不对称质子化是一种重要的合成转化，但尚未发展到有用的水平。 总体而言，所有这些目标不仅有望导致高效催化不对称合成的发展，而且还将导致新方法和新概念的发展，这些方法和概念将提供许多有用的有机合成努力，以及各种N-O化合物的新进入，这些化合物在生物学上是一类非常重要的分子。