Salomó Ernest, Gallen Albert, Sciortino Giuseppe, Ujaque Gregori, Grabulosa Arnald, Lledós Agustí, Riera Antoni, Verdaguer Xavier
Institute for Research in Biomedicine (IRB Barcelona), Barcelona Institute of Science and Technology , Baldiri Reixac 10 , 08028 Barcelona , Spain.
Dept. Química Inorgànica i Orgànica , Universitat de Barcelona , Martí i Franquès 1 , 08028 Barcelona , Spain.
J Am Chem Soc. 2018 Dec 12;140(49):16967-16970. doi: 10.1021/jacs.8b11547. Epub 2018 Nov 29.
A novel cationic [IrH(THF)(P,N)(imine)] [BAr] catalyst containing a P-stereogenic MaxPHOX ligand is described for the direct asymmetric hydrogenation of N-methyl and N-alkyl imines. This is the first catalytic system to attain high enantioselectivity (up to 94% ee) in this type of transformation. The labile tetrahydrofuran ligand allows for effective activation and reactivity, even at low temperatures. Density functional theory calculations allowed the rationalization of the stereochemical course of the reaction.
描述了一种新型阳离子[IrH(THF)(P,N)(亚胺)][BAr]催化剂，其含有P-立体异构的MaxPHOX配体，用于N-甲基和N-烷基亚胺的直接不对称氢化反应。这是在这类转化反应中首个获得高对映选择性（高达94% ee）的催化体系。不稳定的四氢呋喃配体即使在低温下也能实现有效的活化和反应活性。密度泛函理论计算使得该反应的立体化学过程得以合理化。
