LITHIUM PERCHLORATE DIETHYL ETHER MEDIATED REACTIONS

高氯酸锂二乙醚介导的反应

• 批准号: 2177071
• 负责人: PAUL A GRIECO
• 金额: $ 23.98万
• 依托单位: TRUSTEES OF INDIANA UNIVERSITY
• 依托单位国家: 美国
• 财政年份: 1980
• 资助国家: 美国
• 起止时间: 1980-07-01 至 1998-06-30
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/2177071
• 关键词: Diels Alder reaction; chemical addition; chemical synthesis; ibogaine; lithium; molecular polarity; paclitaxel; sex hormone analog; stereochemistry; steroid analog

The major focus of this grant renewal application is to probe further the reactivity and selectivity of a number of organic reactions in highly polar media such as 3.0-5.0 M lithium perchlorate-diethyl ether with applications to molecules of biological interest. This proposal is divided into three parts. The first part of this proposal concentrates on ionic Diels-Alder reactions with applications to the total synthesis of endiandric acid A, 11-oxosteroids, and lycopodine. All studies proposed in this area will be of a fundamental nature in order to define limits and scope of this potentially useful reaction. The second part focuses on cationic [5+2] cycloaddition reactions which have received only scant attention during the past 30 years despite the potential it holds for those engaged in the synthesis of natural and unnatural products. We have found that the yields can be dramatically improved by employing 3.0 M LiClO4-EtOAc in the presence of trimethylsilyl triflate. We propose to examine a number of inter- and intramolecular cationic [5+2] cycloaddition reactions in order to determine the generality of our findings. We propose to apply the above chemistry to the total synthesis of the novel non- steroidal estrogen, miroestrol. In addition we plan to prepare a number of bicyclo [5.3.1] systems related to taxol. In the final section, we will focus on completion of a synthesis of tabersonine and development of a novel approach to iboga alkaloids.

是次拨款续期申请的重点是进一步探讨