U.S.-Croatia Chemistry Research on Biomimetic Rearrangements in Carbocations

美国-克罗地亚碳阳离子仿生重排化学研究

• 批准号: 0120505
• 负责人: Martin Saunders
• 金额: $ 4.94万
• 依托单位: Yale University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2001
• 资助国家: 美国
• 起止时间: 2001-12-01 至 2007-11-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0120505&HistoricalAwards=false
• 关键词: U.S.; Croatia; Chemistry; Research; Biomimetic

This U.S.-Croatian research project between Martin Saunders of Yale University and his partner, Olga Kronja of the University of Zagreb, examines the biological pathways important in the formation of steroids and triterpenoids. The researchers seek new fundamental knowledge about the physical organic chemistry of carbocations, including protosteryl cation in animals and dammarenyl cation in plants. These are to be investigated using both experimental techniques and quantum chemical calculations.The US-Croatian team intends to determine the structural features specific for rearrangement of naturally occurring carbocation in biosynthesis. To do so the researchers will investigate the following groups of model carbocations and their parent alcohols or chlorides: 1) the tert-amyl cation, 2) the methylated and deuterated derivatives of 2-cyclopenyl-e-propyl cation and 3) the carbocation derivatives of bicyclo[3.2.0]noname with various alkyl groups at C-1 and C-8. The research plan includes: (a) NMR spectroscopic studies on stable solutions of model carbocations and their isotopically labeled analogues in non-nucleophillic solution, (b) quantum chemical calculations with the model cation and natural cations themselves, and (c) analysis of the rearrangement processes of the model compound in aqueous or nonpolar solvents. Results should yield new insight into details of structure and rearrangements related to chemical behavior of the carbocations involved in biosynthesis of steroids. If successful, this may have implications for future medical research designed to synthesize artificial hormones.This project in organic dynamics of chemistry fulfills the program objective of advancing scientific knowledge by enabling leading experts in the United States and Central Europe to combine complementary talents and pool resources in areas of strong mutual interest and competence.

耶鲁大学的Martin Saunders和他的搭档，萨格勒布大学的Olga Kronja共同进行了一个美国和克罗地亚的研究项目，研究了类固醇和三萜形成过程中重要的生物途径。研究人员寻求关于碳正离子的物理有机化学的新基础知识，包括动物中的原甾基阳离子和植物中的达马酚基阳离子。这些都将使用实验技术和量子化学计算进行研究。美国-克罗地亚团队打算确定生物合成中自然发生的碳正离子重排的结构特征。为此，研究人员将研究以下几种模式碳正离子及其母体醇或氯化物：1)叔戊基阳离子，2)2-环戊基-e-丙基阳离子的甲基化和氘化衍生物，以及3)在C-1和C-8上具有不同烷基的双环[3.2.0]名称的碳正离子衍生物。研究计划包括：(a)模型碳阳离子及其同位素标记类似物在非亲核溶液中稳定溶液的核磁共振波谱研究；(b)模型阳离子和天然阳离子本身的量子化学计算；(c)模型化合物在水或非极性溶剂中的重排过程分析。研究结果将对类固醇生物合成中涉及的碳正离子的化学行为的结构和重排细节产生新的见解。如果成功，这可能会对未来合成人工激素的医学研究产生影响。该有机化学动力学项目通过使美国和中欧的领先专家在共同感兴趣和能力强的领域结合互补的人才和汇集资源，实现了推进科学知识的计划目标。