02588nas a2200217   4500008004100000022001400041245013100055210006900186260011000255300001600365490000600381520166900387100002902056700002502085700002502110700003102135700002602166700002902192700002502221856012402246       2015                        eng d  a2046-206900aRhodium complex with unsymmetrical vicinal diamine ligand: excellent catalyst for asymmetric transfer hydrogenation of ketones0 aRhodium complex with unsymmetrical vicinal diamine ligand excell  aTHOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLANDbROYAL SOC CHEMISTRYcJUN  a51722-517290 v53 a<p>New unsymmetrical vicinal diamine ligands with systematic variation in the regio and stereo positions in the amine and sulphonamide groups were synthesized from cheap starting material such as norephedrine. Catalytic Asymmetric Transfer Hydrogenation (ATH) of aromatic alkyl ketones has been investigated using transition metal complexes and new derivatives of monotosylated unsymmetrical vicinal diamine ligands using sodium formate as the hydrogen source, in water and methanol. Chiral secondary alcohols were obtained with excellent enantioselectivity (&gt;95% ee) and conversion of ketones (&gt;95%) with [Rh(Cp*)Cl-2](2) and ligand 4 as a catalyst. Enantioselectivity was found to be slightly higher with the use of methanol as a solvent for ATH of ketones with sodium formate as the hydrogen source compared to water as a solvent and was found to be consistent with all the ketones investigated. The reaction mixture is homogeneous in methanol unlike in water, where substrate and product are insoluble in water and form separate phase, sodium formate being soluble in water. The activity and enantioselectivity obtained for ATH of ketones using [Rh(Cp*)Cl-2](2) and unsymmetrical vicinal diamine ligand as catalyst was comparable with the C2 symmetric benchmark ligands like TsDPEN ((1R, 2R)-N-(p-tolylsulfonyl)-1,2-diphenylethylene- diamine), and TsCYDN ((1R, 2R)-N-(p-tolylsulfonyl)-1,2-cyclohexyl, diamine) under similar reaction conditions. To the best of our knowledge, this is first example of the ATH of ketones with good activity and high enantioselectivity with [Rh(Cp*)Cl-2](2) and unsymmetrical vicinal diamine ligands as catalyst systems.</p>1 aDeshpande, Sudhindra, H.1 aShende, Vaishali, S.1 aShingote, Savita, K.1 aChakravarty, Debamitra, K.1 aPuranik, Vedavati, G.1 aChaudhari, Raghunath, V.1 aKelkar, Ashutosh, A.  uhttps://library.ncl.res.in/content/rhodium-complex-unsymmetrical-vicinal-diamine-ligand-excellent-catalyst-asymmetric-0