Catalytic C-C Bond Forming Hydrogenations.

描述(由申请人提供)：我们正在进行第一个系统的努力，以利用氢甲酰化以外的C-C偶联中的氢化。使用阳离子Rh和Ir催化剂，我们发现各种不饱和反应物在加氢条件下还原偶联为羰基化合物和亚胺，在一系列经典的C=X(X=O，NR)加成过程中提供了一种化学计量有机金属的无副产物替代。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Ru或Ir催化剂，醇同时充当氢给体和醛的前体，在没有化学计量比副产物的情况下，可以直接在醇的氧化水平上进行羰基加成。在拟议的供资期间，将开发无副产物的醇和胺与丰富的可再生原料的C-C偶联反应，包括有机卤化物的第一次氢中介格氏加成反应。其他研究领域包括α-烯烃与羰基伙伴的氧化还原中性偶联，以及使用铁基催化剂进行转移氢化偶联的初步探索。

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.