Use of the Trost Ligand in the Ruthenium-Catalyzed Asymmetric Hydrogenation of Ketones,ChemCatChem

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Use of the Trost Ligand in the Ruthenium-Catalyzed Asymmetric Hydrogenation of Ketones
ChemCatChem ( IF 3.8 ) Pub Date : 2017-06-27 07:34:21 , DOI: 10.1002/cctc.201700545
Mattia Cettolin _{1,

2} , Pim Puylaert ₂ , Luca Pignataro ₁ , Sandra Hinze ₂ , Cesare Gennari ₁ , Johannes G. de Vries ₂

Affiliation

The Trost ligand, (1S,2S)-1,2-diaminocyclohexane-N,N′-bis(2′-diphenylphosphinobenzoyl) (L), is reported for the first time as a ligand for the asymmetric hydrogenation (AH) of ketones. Ligand (S,S)-L was screened in the presence of several metal salts and was found to form active catalysts if combined with ruthenium sources in the presence of hydrogen and a base. Reaction optimization was performed by screening different Ru sources, solvents, and bases. Under the optimized conditions, the complex formed by the combination of (S,S)-L with RuCl₃(H₂O)_x in the presence of Na₂CO₃ was able to promote the AH of several ketones at room temperature in good yields with up to 96 % ee. The reaction kinetics measured under the optimized conditions revealed the presence of a long induction period, during which the initially formed Ru species was transformed into the catalytically active complex by reaction with hydrogen. Remarkably, a ketone that is a precursor of the antiemetic drug aprepitant was hydrogenated in excellent yield with a good ee value.

中文翻译：

Trost配体在钌催化的酮的不对称加氢中的应用

Trost配体（1 S，2 S）-1,2-二氨基环己烷-N，N'-双（2'-二苯基膦基苯甲酰基）（L）首次报道为不对称氢化（AH）的配体酮。在几种金属盐的存在下筛选配体（S，S）-L，发现如果在氢和碱的存在下与钌源结合，则可形成活性催化剂。通过筛选不同的Ru来源，溶剂和碱来进行反应优化。在最佳条件下，（S，S）-L与RuCl结合形成络合物Na ₂ CO ₃存在下的₃（H ₂ O）_x能够在室温下以高达96 ee的良好收率促进几种酮的AH 。在最佳条件下测得的反应动力学表明存在较长的诱导期，在此期间，最初形成的Ru物种通过与氢反应转化为催化活性络合物。值得注意的是，作为止吐药制剂的前体的酮以优异的收率和良好的ee值被氢化。

更新日期：2017-06-28

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