"Organic Synthesis"

描述（由申请人提供）：本研究计划涉及2型分子内Diels-Alder反应的新合成方法的开发和应用。2型分子内Diels-Alder反应及其生成的抗bredt烯烃已在有机合成中得到应用。Diels-Alder前驱体的连性限制在环加成步骤中产生了强烈的区域和立体化学偏倚。这种偏置的最终结果是立体选择性合成高取代的碳环和杂环。该反应的效用已在最近的应用中得到证明，2型IMDA反应是复杂天然产物全合成的关键步骤。该建议包括三个部分；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diols - alder环加成及相关杂原子反应的研究；3)桥头堡烯丙基硅烷的合成与化学研究。本研究将产生的合成方法和新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.