Dendritic MonoPhos: synthesis and application in Rh-catalyzed asymmetric hydrogenation

A new class of dendritic monodentate phosphoramidite ligands were synthesized through substitution of the dimethylamino moiety in MonoPhos by the Fréchet-type dendritic wedge and applied in the asymmetric hydrogenation of α-dehydroamino acid esters and dimethyl itaconate. High enantioselectivities (up to 97.9% ee) and catalytic activities (up to 4850 h−1 TOF) were achieved, which are better or comparable to those obtained from MonoPhos. The third generation dendrimer catalyst gave the slightly lower catalytic activity relative to the lower generation ones. The steric shielding by the dendrimer could stabilize the rhodium complex against decomposition caused by hydrolysis in a protic solvent. The inactive catalysts (RhL3 and RhL4) were activated by addition of a free metal precursor Rh(COD)2BF4, and showed high enantioselectivities and catalytic activities.

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O,O′-(R)-(1,1′-Dinaphth-2,2′-diyl)-N-ethyl-N-benzyl-phosphoramiditeC29H24NO2PEe = 100%[α]D16=+315.2 (c 0.33, CH2Cl2)Source of chirality: (R)-BINOLAbsolute configuration: R

O,O′-(R)-(1,1′-Dinaphth-2,2′-diyl)-N-ethyl-N-(3,5-dibenzyloxy)benzyl-phosphoramiditeC43H36NO4PEe = 100%[α]D16=+254.5 (c 0.33, CH2Cl2)Source of chirality: (R)-BINOLAbsolute configuration: R

O,O′-(R)-(1,1′-Dinaphth-2,2′-diyl)-N-ethyl-N-(3,5-bis(3′,5′-dibenzyloxy)benzyloxy)benzyl-phosphoramiditeC71H60NO8PEe = 100%[α]D16=+151.5 (c 0.33, CH2Cl2)Source of chirality: (R)-BINOLAbsolute configuration: R

O,O′-(R)-(1,1′-Dinaphth-2,2′-diyl)-N-ethyl-N-(3,5-bis(3′,5′-bis(3″,5″-dibenzyloxy)benzyloxy)benzyloxy)benzyl-phosphoramiditeC127H108NO16PEe = 100%[α]D16=+72.7 (c 0.33, CH2Cl2)Source of chirality: (R)-BINOLAbsolute configuration: R