MECHANISMS OF BIOORGANIC AND ORGANOMETALLIC CYCLIZATION REACTIONS

生物有机和有机金属环化反应的机制

• 批准号: 8364197
• 负责人: Dean Tantillo
• 金额: $ 0.11万
• 依托单位: CARNEGIE-MELLON UNIVERSITY
• 依托单位国家: 美国
• 财政年份: 2011
• 资助国家: 美国
• 起止时间: 2011-09-15 至 2013-07-31
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/8364197
• 关键词: Anabolism; Award; Biological Factors; Biomedical Research; Cations; Chemicals; Complex; Cyclization; Electrostatics; Funding; Goals; Grant; High Performance Computing; Hydrogen Bonding; Intervention; Investigation; Methods; Molecular; National Center for Research Resources; Organic Chemicals; Principal Investigator; Reaction; Relative (related person); Research; Research Infrastructure; Resources; Source; Terpenes; Transition Elements; United States National Institutes of Health; chemical reaction; cost; design; insight; quantum

This subproject is one of many research subprojects utilizing the resources provided by a Center grant funded by NIH/NCRR. Primary support for the subproject and the subproject's principal investigator may have been provided by other sources, including other NIH sources. The Total Cost listed for the subproject likely represents the estimated amount of Center infrastructure utilized by the subproject, not direct funding provided by the NCRR grant to the subproject or subproject staff. The focus of the research proposed herein, a renewal of CHE030089N, is to apply modern quantum chemical methods to the elucidation of molecular mechanisms of organic chemical reactions that are used in the synthesis and biosynthesis of polycyclic organic molecules. During this award period, we will concentrate on two subprojects: project 1 (continued from the previous grant period) cation-promoted polycyclization reactions involved in biosyntheses of terpene natural products; project 2 (continued from the previous grant period) pericyclic reactions used in the synthesis of complex cyclic molecules. These investigations should allow us to answer many long-standing questions about the relative importance of preorganization and encapsulation, conjugation, hyperconjugation and homoconjugation, transition metal intervention, electrostatic interactions, hydrogen bonds, and hydrophobic forces in controlling cyclization rates and regio- and stereoselectivities, thus providing important insights into the mechanisms of biosynthetic and synthetic cyclization reactions. Our ultimate goal is to define the specific factors responsible for the efficiency of these transformations, thereby compiling sets of design principles for use in creating new synthetic reactions.

该子项目是利用资源的众多研究子项目之一 由 NIH/NCRR 资助的中心拨款提供。子项目的主要支持 并且子项目的主要研究者可能是由其他来源提供的， 包括其他 NIH 来源。 子项目可能列出的总成本 代表子项目使用的中心基础设施的估计数量， NCRR 赠款不直接向子项目或子项目工作人员提供资金。 本文提出的研究重点是CHE030089N的更新，是将现代量子化学方法应用于阐明用于多环有机分子的合成和生物合成的有机化学反应的分子机制。在本资助期内，我们将重点开展两个子项目：项目1（上一资助期的延续）涉及萜类天然产物生物合成的阳离子促进的多环化反应；项目2（上一个资助期的延续）用于合成复杂环状分子的周环反应。这些研究应该使我们能够回答许多长期存在的问题，即预组织和封装、共轭、超共轭和同共轭、过渡金属干预、静电相互作用、氢键和疏水力在控制环化速率以及区域和立体选择性方面的相对重要性，从而为生物合成和合成环化反应的机制提供重要的见解。我们的最终目标是定义影响这些转化效率的具体因素，从而编制用于创建新合成反应的设计原则集。