CHEMISTRY OF COBALT-DIENE AND ACETYLENE COMPLEXES

钴二烯和乙炔络合物的化学

• 批准号: 3286392
• 负责人: KENNETH NICHOLAS
• 金额: $ 11.92万
• 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 1994-06-30
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/3286392
• 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(丙叉基)CO(CO)6-nLn+BF4-(1)， (丙叉)Co4(CO)10BF4(2)和(二烯)Co(CO)3-nLn(3)，以 用选定的亲核偶联建立它们的反应性模式 合作伙伴，特别是在立体声和区域控制方面，以及 发展该化学在天然产物合成中的应用 和其他生物活性化合物。生殖器功能的研究 由乙炔缩醛和醛衍生的配合物1(L=CO)将是 旨在开发非对映的新方法--和 与亲核试剂的对映选择性偶联反应。利用这些资源 含2-5的手性构筑块合成中的反应 邻近的立体中心(碳水化合物抗生素的前体)和 本课程将考察大环的合成。新型手性化合物的研究 双金属配合物1b，c将被用于研究它们的 结构和评估它们指导立体选择的潜力(和 可能是立体专一性的)与亲核试剂的偶联反应。谦虚的 致力于制备、表征和反应性筛选 未知的簇导数2的计划是为了确定 它们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、更好的机会 一般情况下，基于簇合物的立体选择性反应的未来基础。我们的 第二个主要重点将是综合扩大 二烯类化合物的有用化学3.主要目标包括：1) 深化对区域选择性控制因素的认识 对3(和中间烯丙基络合物)的亲核攻击； 扩大双核亲核加成反应的范围 它们在前列环素和前列环素合成中的应用 3)手性、非手性和手性化合物的制备和应用 对映体选择性合成中的外消旋3，包括碳水化合物 以及4)开发新的反应模式。 有机金属络合物以及有价值的新合成工具 立体选择性合成具有生物活性的复杂物质。