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.

本赠款更新申请的主要重点是进一步调查 高度有机反应的反应性和选择性 极地培养基，例如3.0-5.0 m高氯酸锂二乙基乙醚， 应用于生物学兴趣分子。 该提议是 分为三个部分。 该提案的第一部分集中于 离子Diels-Alder反应与全合成的应用 Endiandric Acid A，11-氧化固醇和氨基丁烷。所有提出的研究 该领域将具有基本性质，以定义限制和 这种潜在有用反应的范围。 第二部分重点 阳离子[5+2]的环加成反应，仅收到很少 在过去30年中的关注尽管有潜力 那些从事自然和不自然产品的合成的人。我们有 发现可以通过使用3.0 m来大大提高产量 在三甲基三甲酯存在的情况下，LICLO4-ETOAC。 我们建议 检查许多分子间和分子内阳离子[5+2]环加成 反应以确定我们发现的一般性。我们建议 将上述化学物应用于新型非 - 类固醇雌激素，米罗strol。 此外，我们计划准备一个数字 Bicyclo [5.3.1]与紫杉醇有关的系统。 在最后一部分中，我们 将专注于完成Tabersonine的综合和发展 iboga生物碱的一种新颖方法。