Synthetic Reactions Catalyzed by Transition Metals

过渡金属催化的合成反应

• 批准号: 6688969
• 负责人: EI-ICHI NEGISHI
• 金额: $ 33.75万
• 依托单位: PURDUE UNIVERSITY
• 依托单位国家: 美国
• 财政年份: 1986
• 资助国家: 美国
• 起止时间: 1986-07-01 至 2006-11-30
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/6688969
• 关键词: Synthetic; Reactions; Catalyzed; Transition; Metals

DESCRIPTION (provided by applicant): The main objective of the proposed research is to provide new and innovative synthetic methods that are applicable to efficient and selective syntheses of a wide variety or complex natural products and related organic compounds including those of medicinal and biological interest through development of organotransition metal chemistry, especially of palladium and zirconium. Methodological development during the proposed research period will be focused on (1) cross-coupling, (2) carbometallation and hydrometallation, (3) carbonylation and other migratory insertion reactions and (4) oxy- and aminometallation. Special emphasis will be placed on the development of synthetic protocols involving combined uses of (1) - (4), especially (1) and (2), In the proposed research, it is essential to have a research program and system in which methodological developments reciprocally interact with applications to the synthesis of natural products and related target molecules. Most of the target molecules in the proposed research are selected from this viewpoint, and execution of their synthesis primarily from this viewpoint constitutes the second main objective. In some select cases, however, efforts will be made to synthesize compounds of medicinal interest and provide their samples. This then is the third main objective of the proposed research. Both methodological developments and target syntheses will be performed in the following five areas: (1) conjugated oligoenes of defined stereo- and regiechemistry including carotenoids, oligoene macrolide antibiotics, and others, e.g., stipiamide and amphotericin B, (2) oligoenes containing 1,5- and 1,4-diene units including coenzymes Qn, where n is an integer, such as 3, 4, 9, 10, and so on, and other isoprenoids, e.g., mycolactones A and B, (3) chiral aliphatic chain-containing natural products and related compounds, e.g., scyphostatin and fluvircinine A, (4) bi- and oligocarbocycles obtainable via cyclic carbopalladation and acylpalladation, e.g., nagilactone F, and (5) heterocycles preparable via cross-coupling, carbonylation, and oxymetallation or aminometallation. As new and attractive targets become known in the literature, some such targets will also be selected and synthesized. This would necessitate omission of some of the proposed targets and/or deferment of their synthesis as well as deletion, addition, and/or modification of research topics to maximize PI's research contributions within the general areas of the proposed research.

描述（由申请人提供）：拟议研究的主要目标是提供新的和创新的合成方法，适用于通过以下方式有效和选择性地合成多种或复杂的天然产物和相关有机化合物，包括那些具有医学和生物学意义的化合物有机过渡金属化学的发展，特别是钯和锆的化学。拟议研究期间的方法学开发将侧重于（1）交叉偶联，（2）碳金属化和加氢金属化，（3）羰基化和其他迁移插入反应以及（4）氧金属化和氨基金属化。将特别强调开发涉及（1）-（4），特别是（1）和（2）联合使用的合成方案。在拟议的研究中，必须有一个研究计划和系统，其中方法论发展与天然产物和相关目标分子合成的应用相互作用。所提出的研究中的大多数目标分子都是从这个角度来选择的，并且主要从这个角度进行它们的合成构成了第二个主要目标。然而，在某些特定情况下，我们将努力合成具有药用价值的化合物并提供其样品。这是拟议研究的第三个主要目标。方法学开发和目标合成将在以下五个领域进行：(1) 具有明确立体和区域化学的共轭寡烯，包括类胡萝卜素、寡烯大环内酯类抗生素等，例如斯蒂吡酰胺和两性霉素 B，(2) 含有 1、 5-和1，4-二烯单元，包括辅酶Qn，其中n是整数，例如3、4、9， 10等，以及其他类异戊二烯，例如分枝菌内酯A和B，(3)含手性脂肪链的天然产物和相关化合物，例如scyphosstatin和fluvircinine A，(4)可通过环状碳钯化获得的双碳环和寡碳环以及酰基钯化，例如，nagilactone F，和(5)杂环可通过制备交叉偶联、羰基化和氧金属化或氨基金属化。随着新的和有吸引力的目标在文献中变得已知，一些这样的目标也将被选择和合成。这将需要省略一些拟议的目标和/或推迟其综合，以及删除、添加和/或修改研究主题，以最大限度地提高 PI 在拟议研究的一般领域内的研究贡献。