Heterocumulenes in Asymmetric Catalysis

不对称催化中的杂积烯

• 批准号: 7342395
• 负责人: THOMAS C. LECTKA
• 金额: $ 26.15万
• 依托单位: JOHNS HOPKINS UNIVERSITY
• 依托单位国家: 美国
• 财政年份: 2002
• 资助国家: 美国
• 起止时间: 2002-01-01 至 2009-12-31
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/7342395
• 关键词: 6-bromo-3-(bromomethyl)-7-methyl-2,3,7-trichloro-1-octene; Acids; Aldehydes; Amino Acids; Benzoquinones; Biological; Biological Factors; Catalysis; Chemistry; Class; Collaborations; Complement; Development; Diagnosis; Disease; Doctor of Medicine; Equilibrium; Funding; Generations; Goals; Grant; Imides; Iodination reaction; Lactams; Letters; Link; Malignant neoplasm of prostate; Measurement; Medicine; Metals; Methodology; Methods; Mono-S; Nitrates; Numbers; Organic Chemistry; Physical condensation; Prostate-Specific Antigen; Public Health; Publishing; Quinones; Rate; Reaction; Research Project Grants; Route; Scheme; Testing; Work; base; benzoquinone; catalyst; chlorination; cycloaddition; halogenation; inhibitor/antagonist; interest; ketene; nitrate; nitration; novel strategies; professor; quinone methide

The specific aims and long-term objectives of this proposal are to use heterocumulenes (ketenes, ketenimines, and their synthetic equivalents) for new applications in asymmetric catalysis, namely the asymmetric synthesis of p-lactams (especially the trans diastereomers), catalytic asymmetric halogenation (chlorination, bromination and iodination), and catalytic asymmetric a-nitration. We also propose the development of new bifunctionally (Lewis acid-chiral nucleophile) catalyzed asymmetric reactions, including [2+2] as well as [4+2]cycloadditions of ketene enolates. All the chiral, optically enriched products of our reactions are meant to be either pharmacologically active, or to represent key intermediates and branch points in the synthesis of medicinally or academically interesting target molecules. In order to benefit public health, we have established a collaboration with Dr. Samuel Deanmeade, M.D. (JHU Med.) to synthesize p- lactams to develop a new, sensitive test for prostate specific antigen (PSA). PSA is a marker for prostate cancer, and its measurement may be useful to facilitate diagnosis of the disease.

该提案的具体目标和长期目标是使用杂累积烯（烯酮， 烯酮亚胺及其合成等价物）在不对称催化中的新应用，即 β-内酰胺（特别是反式非对映异构体）的不对称合成，催化不对称卤化 （氯化、溴化和碘化）和催化不对称α-硝化。我们亦建议 开发新的双功能（刘易斯酸-手性亲核试剂）催化的不对称反应，包括 [2+2]和[4+2]环加成反应。我们的所有手性、光学富集产品 反应是指要么是双活性的，要么代表关键中间体和分支 在医学或学术上感兴趣的目标分子的合成点。为了造福大众 我们与Samuel Deanmeade博士（医学博士）建立了合作关系。(JHU Med.）合成p- 内酰胺开发一种新的，敏感的前列腺特异性抗原（PSA）测试。PSA是前列腺的标志物 癌症，并且其测量可用于促进疾病的诊断。