New Strategies for the Synthesis of Carbocyclic and Heterocyclic Compounds

碳环和杂环化合物合成新策略

• 批准号: 8921505
• 负责人: Rick Danheiser
• 金额: $ 43.7万
• 依托单位: Massachusetts Institute of Technology
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1990
• 资助国家: 美国
• 起止时间: 1990-01-15 至 1993-12-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=8921505&HistoricalAwards=false
• 关键词: New; Strategies; Synthesis; Carbocyclic; Heterocyclic

The Organic Synthesis Program is funding the continuation of the research program of Dr. Rick L. Danheiser. Dr. Danheiser will continue his fruitful development of new methods to synthesize carbocyclic and heterocyclic compounds containing five-membered rings. This will provide the new tools required by the increasingly complex requirements of industry and agriculture. One important aim of the project is the continued development of the recently discovered general ı3+2! annulation strategy. In this process an allenylsilane functions as a three-carbon annulation unit combining with an electrophilic pi bond to form a new five-membered ring. The extension of this strategy to the synthesis of several important classes of five-membered ring compounds will be investigated. Specific targets of interest include cyclopentanone derivatives and heterocyclic systems such as pyrroles and carbapenems. Research will also be carried out aimed at the development of a general synthesis of substituted azulenes. The azulenes constitute the best known class of polycyclic nonbenzenoid aromatic compounds, and recently the novel electronic properties and biological activity of certain natural and semi-synthetic azulenes have led to commercially important applications of these compounds in fields such as medicine and electrophotography. However, progress in these areas has been hindered by the availability of very few general methods for the synthesis of azulenes, particularly substituted systems. The development of a general ı3+2! annulation route to substituted azulenes will provide access to compounds with potential applications as drugs, liquid crystal elements, and novel electronic materials. Another important objective of the project is the development of new cyclization methods based on unusually facile pericyclic and anionic ring closure reactions of allenes. Preliminary experiments have been carried out that indicate that certain allene derivatives undergo efficient cyclization under remarkably mild conditions. A principal aim of the project will be the application of this process in a new synthesis of substituted indoles. The indole nucleus is the central structural feature in a large array of natural products including plant growth regulators and clinically important pharmaceuticals. Relatively few general methods for the construction of substituted indoles exist, and the new methodology to be investigated will provide improved access to a variety of important indole derivatives.

有机合成项目资助了Rick L. Danheiser博士的研究项目。Danheiser博士将继续他卓有成效的新方法来合成含五元环的碳环和杂环化合物。这将为日益复杂的工农业需求提供所需的新工具。该项目的一个重要目标是继续发展最近发现的一般ı3+2！环状结构的策略。在这个过程中，烯基硅烷作为一个三碳环单位与一个亲电键结合形成一个新的五元环。将这一策略扩展到几种重要的五元环化合物的合成中。具体的目标包括环戊酮衍生物和杂环系统，如吡咯和碳青霉烯类。还将进行旨在发展取代偶氮烯的一般合成方法的研究。azulenes是最著名的一类多环非苯芳香族化合物，近年来，某些天然和半合成azulenes的新电子特性和生物活性使这些化合物在医学和电子摄影等领域得到了重要的商业应用。然而，在这些领域的进展一直受到阻碍，因为很少有合成偶氮烯的一般方法，特别是取代体系。开发了一个通用的ı3+2！取代偶氮烯的环化途径将为药物、液晶元件和新型电子材料等具有潜在应用价值的化合物提供途径。该项目的另一个重要目标是开发新的环化方法，基于异常容易的烯的周环和阴离子环闭合反应。初步实验表明，某些烯衍生物在非常温和的条件下进行了有效的环化。该项目的一个主要目的是将这一方法应用于取代吲哚的新合成。吲哚核是包括植物生长调节剂和临床重要药物在内的大量天然产物的中心结构特征。相对较少的一般方法来构建取代吲哚存在，和新的方法来研究将提供改进的途径，以获得各种重要的吲哚衍生物。