Substituted Piperidine Formation via C-C Bond Forming Transfer Hydrogenation

通过 C-C 键形成转移氢化形成取代哌啶

• 批准号: 8748599
• 负责人: MICHAEL J KRISCHE
• 金额: $ 1.51万
• 依托单位: UNIVERSITY OF TEXAS AT AUSTIN
• 依托单位国家: 美国
• 财政年份: 2005
• 资助国家: 美国
• 起止时间: 2005-03-15 至 2017-03-31
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/8748599
• 关键词: Accounting; Alcohols; Aldehydes; Alkenes; Amines; Area; Biological Assay; Butadiene; Bypass; Carbon Monoxide; Coupling; Development; Ethylenes; Felis catus; Funding; Generations; Hydrogen; Hydrogenation; Imines; Investigation; Iridium; Iron; Marketing; Mediating; Methylation; Oxidation-Reduction; Parents; Pharmaceutical Preparations; Process; Production; Reaction; Reagent; Resolution; Rhodium; Ruthenium; Sales; Salts; adduct; base; carbonyl compound; catalyst; drug market; enantiomer; oxidation; piperidine; propylene; public health relevance

DESCRIPTION (provided by applicant): We are engaged in the first systematic efforts to exploit hydrogenation in C-C couplings beyond hydroformylation. Using cationic rhodium and iridium catalysts, we have found that diverse ?-unsaturated reactants reductively couple to carbonyl compounds and imines under hydrogenation conditions, offering a byproduct-free alternative to stoichiometric organometallics in a range of classical C=X (X = O, NR) addition processes. This concept is extended further via "C-C bond forming transfer hydrogenation". Here, using ruthenium or iridium catalysts, alcohols serve dually as hydrogen donors and aldehyde precursors, enabling carbonyl addition directly from the alcohol oxidation level in the absence of stoichiometric byproducts. In the proposed funding period, byproduct-free C-C couplings of alcohol and amines with abundant, renewable feedstocks will be developed, including the first hydrogen-mediated Grignard additions of organic halides. Other areas of investigation include redox neutral couplings of ?-olefins to carbonyl partners, and initial explorations into the use of iron-based catalysts for transfer hydrogenative coupling.

描述（由申请人提供）：我们正在进行第一次系统性的努力，以开发除加氢外的C-C偶联中的加氢。使用阳离子铑和铱催化剂，我们发现不同的？不饱和反应物在氢化条件下还原偶联到羰基化合物和亚胺，在一系列经典的C=X（X = O，NR）加成过程中为化学计量的有机金属化合物提供了无副产物的替代方案。该概念通过“C-C键形成转移氢化”进一步扩展。在此，使用钌或铱催化剂，醇双重用作氢供体和醛前体，使得能够在不存在化学计量副产物的情况下直接从醇氧化水平进行羰基加成。在拟议的资助期内，将开发无副产物的醇和胺与丰富的可再生原料的C-C偶联，包括第一个氢介导的有机卤化物的格氏加成。其他领域的研究包括氧化还原中性耦合？-烯烃羰基合作伙伴，并初步探索使用铁基催化剂转移加氢偶联。