Bower John F, Krische Michael J
Department of Chemistry and Biochemistry, University of Texas at Austin, 1 University Station - A5300, Austin, TX 78712-0165, USA and Chemistry Research Laboratory, University of Oxford, 12 Mansfield Road, Oxford 1 3TA, UK.
Top Organomet Chem. 2011 Jan 1;34(2011):107-138. doi: 10.1007/978-3-642-15334-1_5.
The formation of C-C bonds via catalytic hydrogenation and transfer hydrogenation enables carbonyl and imine addition in the absence of stoichiometric organometallic reagents. In this review, iridium-catalyzed C-C bond-forming hydrogenations and transfer hydrogenations are surveyed. These processes encompass selective, atom-economic methods for the vinylation and allylation of carbonyl compounds and imines. Notably, under transfer hydrogenation conditions, alcohol dehydrogenation drives reductive generation of organoiridium nucleophiles, enabling carbonyl addition from the aldehyde or alcohol oxidation level. In the latter case, hydrogen exchange between alcohols and π-unsaturated reactants generates electrophile-nucleophile pairs en route to products of hydro-hydroxyalkylation, representing a direct method for the functionalization of carbinol C-H bonds.
通过催化氢化和转移氢化形成碳 - 碳键能够在不存在化学计量有机金属试剂的情况下实现羰基和亚胺加成。在本综述中，对铱催化的形成碳 - 碳键的氢化反应和转移氢化反应进行了概述。这些过程包括用于羰基化合物和亚胺的乙烯基化和烯丙基化的选择性、原子经济性方法。值得注意的是，在转移氢化条件下，醇脱氢驱动有机铱亲核试剂的还原生成，从而能够从醛或醇氧化水平进行羰基加成。在后一种情况下，醇与π-不饱和反应物之间的氢交换在通往氢 - 羟基烷基化产物的过程中产生亲电 - 亲核对，这代表了一种直接使甲醇C - H键官能化的方法。
