"Organic Synthesis"

描述(申请人提供)：这项研究计划涉及第二类分子内Diels-Alder反应的新合成方法和应用的发展。第二类分子内Diels-Alder反应及其生成的反Bredt烯烃已在有机合成中得到应用。Diels-Alder前体的连接性导致的限制在环加成步骤中造成了强烈的区域和立体化学偏见。这种偏置的最终结果是高取代碳环和杂环的立体选择性合成。该反应作为复杂天然产物全合成的关键步骤，最近在第二类IMDA反应中的应用证明了该反应的实用性。该建议包括三个部分：1)第二类IMDA反应的不对称催化剂的开发；2)第二类分子内酰基亚硝基Diels-Alder环加成反应和相关的杂原子反应的探索；3)桥头烯丙基硅烷的合成和化学。这一研究将产生的合成方法和新颖的多环结构将增强这种转化的实用性，并为合成具有重要生物意义的化合物提供强有力的工具。

DESCRIPTION (provided by applicant): This research proposal is concerned with the development of new synthetic methods and applications of the type 2 intramolecular Diels-Alder reaction. The type 2 intramolecular Diels-Alder reaction and the resulting anti-Bredt olefins have found application in organic synthesis. The constraints resulting from the connectivity in the Diels-Alder precursor creates a strong regio- and stereochemical bias in the cycloaddition step. The end result of this bias is the stereoselective synthesis of highly substituted carbocyclic and heterocyclic rings. The utility of this reaction has been demonstrated in recent applications of the type 2 IMDA reaction as a key step in the total synthesis of complex natural products. The proposal contains three sections; 1) the development of asymmetric catalysts for the type 2 IMDA reaction; 2) an exploration of the type 2 intramolecular acyl nitroso Diels-Alder cycloaddition and related heteroatom reactions, and 3) the synthesis and chemistry of bridgehead allyl silanes. The synthetic methods and novel polycyclic structures that will result from this research will enhance the utility of this transformation and provide powerful tools for the synthesis of biologically important compounds.