CHEMISTRY OF COBALT-DIENE AND ACETYLENE COMPLEXES

钴二烯和乙炔络合物的化学

• 批准号: 3286391
• 负责人: KENNETH NICHOLAS
• 金额: $ 11.52万
• 依托单位: UNIVERSITY OF OKLAHOMA
• 依托单位国家: 美国
• 财政年份: 1984
• 资助国家: 美国
• 起止时间: 1984-09-01 至 1993-06-30
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/3286391
• 关键词: alkynes; allyl compound; chemical structure function; cobalt; diene; drug design /synthesis /production; heterocyclic compounds; metal complex; organometallic compounds; prostacyclins; stereoisomer

Our broad objectives are to explore new reaction chemistry of three classes of cobalt complexes (propargylium)Co2(CO)6-nLn+BF4-(1), (propargylium)Co4(CO)10BF4(2), and (diene)Co(CO)3-nLn(3) in order to establish their patterns of reactivity with selected nucleophilic coupling partners, especially with respect to stereo- and regiocontrol, and to develop applications of this chemistry in the synthesis of natural products and other biologically active compounds. Studies of the propargylium complexes 1 (L=CO) derived from acetylenic acetals and aldehydes will be directed towards developing new approaches to diastero- and enantioselective coupling reactions with nucleophiles. Utilization of such reactions in the synthesis of chiral building blocks containing 2-5 adjacent stereocenters (precursors to carbohydrate antibiotics) and for the synthesis of macrocycles will be examined. Studies of the novel chiral bimetallic complexes 1b,c will be directed towards examining their structures and assessing their potential for directing stereoselective (and possibly stereospecific) coupling reactions with nucleophiles. A modest effort aimed at the preparation, characterization, and reactivity screening of the unknown cluster derivatives 2 is planned in order to determine if their anticipated unique structural and electronic features will provide new, improved opportunities for stereocontrolled coupling reactions an d a future basis for cluster-based stereoselective reactions in general. Our second major emphasis will be directed towards expanding the synthetically useful chemistry of the diene complexes 3. Primary objectives include: 1) deepening our understanding of the factors controlling the regioselectivity of nucleophilic attack on 3 (and the intermediate allyl-complexes); 2) expansion of the scope of annelative bisnucleophilic additions and illustration of their application in the synthesis of prostacyclin and heterocyclic derivatives; 3) preparation and utilization of chiral, non- racemic 3 in enantioselective syntheses, including carbohydrate derivatives; and 4) development of new reactivity patterns of organometallic complexes as well as valuable new synthetic tools for the stereoselective synthesis of complex and biologically active substances.

我们的主要目标是探索三类新的反应化学 钴配合物（炔丙基）Co 2（CO）6-nLn+ BF 4-（1）， （炔丙基）Co 4（CO）10 BF 4（2）和（二烯）Co（CO）3-nLn（3），以便 建立它们与所选亲核偶联反应性模式 合作伙伴，特别是关于立体声和区域控制，并 开发这种化学在天然产物合成中的应用 和其他生物活性化合物。 炔丙基的研究 由炔属缩醛和醛衍生的络合物1（L=CO）将是 旨在制定新的移民办法， 与亲核试剂的对映选择性偶联反应。 利用此等 在合成含有2-5个 相邻的立体中心（碳水化合物抗生素的前体）， 将研究大环化合物的合成。 新型手性化合物的研究 复合物1b，c将被引导到检查它们的 结构和评估其定向立体选择性（和 可能立体定向）与亲核试剂的偶联反应。 适度 旨在制备、表征和反应性筛选的努力 计划未知的聚类导数2，以确定是否 其预期的独特结构和电子特征将提供 立体控制偶联反应的新的、改进的机会 未来的基础上，集群为基础的立体选择性反应一般。 我们 第二个主要重点将是扩大综合 二烯配合物的有用化学3. 主要目标包括：1） 加深了对区域选择性控制因素的认识 对3（和中间体烯丙基络合物）的亲核攻击; 2） 扩大了亲核加成反应的范围， 说明它们在合成前列环素和 杂环衍生物; 3）手性，非- 在对映选择性合成中的外消旋3，包括碳水化合物 衍生物;和4）开发新的反应模式， 有机金属配合物以及有价值的新的合成工具， 复杂和生物活性物质的立体选择性合成。