Metal Catalyzed 1,2-Amino-Alcohol & Diamine Synthesis

金属催化 1,2-氨基醇

• 批准号: 6646079
• 负责人: Donald Allen Watson
• 金额: $ 3.97万
• 依托单位: UNIVERSITY OF CALIFORNIA BERKELEY
• 依托单位国家: 美国
• 财政年份: 2004
• 资助国家: 美国
• 起止时间: 2004-05-17 至 2006-05-16
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/6646079
• 关键词: aminoalcohol; aziridines; catalyst; chemical reaction; chemical synthesis; diamines; epoxides; heavy metals; metal complex; method development; organic chemicals; organometallic compounds; postdoctoral investigator; protonation; stereoisomer

DESCRIPTION (provided by applicant): Vicinal amino-alcohols and diamines are an important class of compounds that are difficult to access in rapid and enantioselective fashion. The recently discovered insertion of imidozirconium complexes into epoxides holds promise for the development of a direct and stereo-controlled method to access these compounds. The proposed study examines the scope and mechanism of this novel insertion reaction, with the goal of developing a new catalytic asymmetric synthesis of both vicinal amino-alcohols and vicinal diamines. The proposed reaction involves the formal insertion of group IV imidometal complexes (LxM=NR, M = Ti or Zr) across the C-X bond (X = O or NP) of epoxides and aziridines. Protonation of the resulting metallacycle is anticipated to liberate the desired vicinal amino-alcohol or diamine. The overall conversion of epoxide or aziridine to amino-alcohol or diamine should be possible in a single operation using catalytic imidometal complex when a stoichiometric amine is used as the proton source. When appropriate chiral, non-racemic ligands are employed, this sequence should be capable of asymmetric catalysis via the desymmetrization of meso substrates or the kinetic resolution of racemic substrates. Depending upon the results of the mechanistic investigations, the dynamic kinetic resolution of racemic substrates may be possible. Ultimately, this method is expected to allow rapid and stereocontrolled access to vicinal amino-alcohols and diamines.

描述（由申请人提供）：邻氨基醇和二胺是一类重要的化合物，很难以快速和对映选择性的方式获得。最近发现的将咪唑啉配合物插入到环氧化物中，为开发一种直接和立体控制的方法来获取这些化合物提供了希望。本研究探讨了这种新型插入反应的范围和机制，目的是开发一种新的催化不对称合成邻胺醇和邻胺。所提出的反应涉及在环氧化物和叠氮嘧啶的C-X键（X = O或NP）上正式插入IV族胺金属配合物（LxM=NR， M= Ti或Zr）。预期得到的金属环质子化反应将释放所需的邻氨基醇或二胺。当使用化学计量胺作为质子源时，使用催化亚胺金属配合物在一次操作中将环氧化物或氮吡啶全部转化为氨基醇或二胺应该是可能的。当使用合适的手性非外消旋配体时，该序列应能够通过介观底物的不对称化或外消旋底物的动力学分解进行不对称催化。根据机理研究的结果，外消旋底物的动态动力学分辨是可能的。最终，这种方法有望实现对邻氨基醇和二胺的快速和立体控制。