"Organic Synthesis"

描述（由申请人提供）：本研究计划涉及2型分子内Diels-Alder反应的新合成方法和应用的开发。第二类分子内Diels-Alder反应及其生成的反Bredt烯烃在有机合成中有着广泛的应用。由Diels-Alder前体中的连接性产生的约束在环加成步骤中产生强烈的区域和立体化学偏差。这种偏向的最终结果是高度取代的碳环和杂环的立体选择性合成。该反应的实用性已被证明在最近的应用中的2型IMDA反应作为一个关键步骤，在复杂的天然产物的全合成。该提案包含三个部分：1）2型IMDA反应的不对称催化剂的开发; 2）2型分子内酰基亚硝基Diels-Alder环加成和相关杂原子反应的探索;以及3）桥头烯丙基硅烷的合成和化学。本研究所得到的合成方法和新的多环结构将提高这种转化的实用性，并为合成具有生物学意义的化合物提供有力的工具。

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.