ASYMMETRIC SYNTHESIS--STRUCTURE, STEREOCHEMISTRY AND NMR

不对称合成——结构、立体化学和核磁共振

• 批准号: 3917716
• 负责人: H ZIFFER
• 金额: --
• 依托单位: NATIONAL INSTITUTE OF DIABETES AND DIGESTIVE AND KIDNEY DISEASES
• 依托单位国家: 美国
• 资助国家: 美国
• 起止时间: 至
• 项目状态: 未结题
• 来源: https://reporter.nih.gov/project-details/3917716
• 关键词: X ray crystallography; alcohols; antibody; chemical structure; chemical synthesis; cis trans isomerization; conformation; cyclic compound; high performance liquid chromatography; neurotoxins; nuclear magnetic resonance spectroscopy; photochemistry; stereochemistry; stereoisomer

Antibodies were raised against an analogue of one of the photo products (the head-to-head syn dimer) of trans methyl p- nitrocinnamate. When a solution of the monomer was irradiated in the presence of these antibodies, the product formed preferentially was the one against which antibodies had been raised. Photoisomerization of the monomer, the major photochemical reaction in the absence of antibodies, was greatly suppressed. Thus, the antibody combining site serves as a template for promoting selectively one reaction. The structure and absolute stereochemistry of (Z) (+)-2-bromocycloundec-2-enyl camphanate, a compound prepared as part of a study of the relationship between the chiroptical properties of the corresponding p-bromobenzoate esters and the configuration and conformation of medium-ring allylic esters, was determined in an X-ray crystallographic study. In the course of the same study, the structure and absolute stereochemistry of (E) (-)-2-cyclodecenyl camphanate was also determined by X-ray crystallography. As part of our work on asymmetric synthesis we developed a general method of resolving polycyclic aromatic alcohols, metabolites of polycyclic aromatic hydrocarbons. This method was used to prepare (+)-l-acenaphthenol, a substrate used to analyze several dehydrogenases. The absolute stereochemistry of the camphanate ester of the alcohol was elucidated by an X-ray crystallographic study. Chiral samples of beta-methylaminoalanine (BMAA) (a reported neurotoxin) and of an 15N labeled sample were prepared utilizing an enzymic resolution. The metabolism of the reported neurotoxin and as well as its pharmacology are being investigated by Dr. Markey et al. in NIMH (see Z01-MH-00279-05-LCS).

针对其中一张照片的类似物产生了抗体 反式甲基对-的产物（头对头顺二聚体） 硝基肉桂酸盐。 当单体溶液在 这些抗体的存在，优先形成产物 是针对其产生抗体的一种。 单体的光异构化，主要的光化学反应 在没有抗体的情况下，受到极大的抑制。 因此， 抗体结合位点作为促进的模板 选择性地进行一种反应。 结构和绝对 (Z) (+)-2-溴环十一烷-2-烯基莰酸酯的立体化学，a 作为研究之间关系的一部分而制备的化合物 相应的对溴苯甲酸酯的手性光学性质 酯类以及中环的构型和构象 烯丙酯，是通过 X 射线晶体学研究测定的。 在同一研究过程中，结构和绝对 (E) (-)-2-环癸烯基莰酸酯的立体化学也 通过X射线晶体学测定。 作为我们不对称合成工作的一部分，我们开发了一个通用的 拆分多环芳香醇及其代谢物的方法 多环芳烃。 该方法用于制备 (+)-l-苊酚，一种用于分析多种物质的底物 脱氢酶。 莰烷酸酯的绝对立体化学 醇的酯通过X射线晶体学阐明 学习。 β-甲基氨基丙氨酸 (BMAA) 的手性样品（已报道 神经毒素）和 15N 标记样品的制备利用 酶解。 所报道的神经毒素的代谢 及其药理学正在由博士进行研究。 马基等人。在 NIMH 中（参见 Z01-MH-00279-05-LCS）。