Catalytic C-C Bond Forming Hydrogenations.

描述（由申请人提供）：我们正在进行除氢甲酰化外的C-C偶联氢化的首次系统研究。使用阳离子铑和铱催化剂，我们发现了不同的？-不饱和反应物在加氢条件下还原偶联羰基化合物和亚胺，在一系列经典的C=X （X = O， NR）加成过程中提供了一种无副产物的化学计量有机金属替代品。这一概念通过“C-C键形成转移氢化”得到进一步扩展。在这里，使用钌或铱催化剂，醇作为氢供体和醛前体的双重作用，使羰基直接从醇氧化水平加成，没有化学计量副产物。在拟议的资助期内，将开发酒精和胺与丰富的可再生原料的无副产物C-C偶联，包括第一个氢介导的有机卤化物的格氏添加物。其他研究领域包括氧化还原中性偶联？将-烯烃转化为羰基，并初步探索利用铁基催化剂进行转移氢化偶联。

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.