Enantioselective hydrogenation of olefins with planar chiral iridium ferrocenyloxazolinylphosphine complexes

Chiral iridium Fc-PHOX complexes were readily prepared from Fc-PHOX, [Ir(cod)Cl]2 and NaBArF (or NaPF6) in high yields. They were applied as catalysts in the enantioselective hydrogenation of olefins to afford the corresponding products with high conversions and good enantioselectivities (up to 99% ee).

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(η4-1,5-Cyclooctadiene) [(S,S)-(4,5-dihydro-4-methyl-2-oxazolyl)-2-diphenylphosphinoferrocene] iridium(I) tetrakis[3,5-bis(trifluoromethyl)phenyl]borateC66H48BF24IrFeNOPEe = 100%[α]D20=-336.7 (c 0.28, CH2Cl2)Source of chirality: asymmetric synthesisAbsolute configuration: (S,S)

(η4-1,5-Cyclooctadiene) [(S,S)-(4,5-dihydro-4-isopropyl-2-oxazolyl)-2-diphenylphosphinoferrocene] iridium(I) tetrakis[3,5-bis(trifluoromethyl)phenyl]borateC68H52BF24FeIrNOPEe = 100%[α]D20=-471.2 (c 0.29, CH2Cl2)Source of chirality: asymmetric synthesisAbsolute configuration: (S,S)

(η4-1,5-Cyclooctadiene) [(S,S)-(4,5-dihydro-4-tert-butyl-2-oxazolyl)-2-diphenylphosphinoferrocene] iridium(I) tetrakis[3,5-bis(trifluoromethyl)phenyl]borateC69H54BF24FeIrNOPEe = 100%[α]D20=-641.1 (c 0.18, CH2Cl2)Source of chirality: asymmetric synthesisAbsolute configuration: (S,S)

(η4-1,5-Cyclooctadiene) [(S,S)-(4,5-dihydro-4-phenyl-2-oxazolyl)-2-diphenylphosphinoferrocene] iridium(I) tetrakis[3,5-bis(trifluoromethyl)phenyl]borateC71H50BF24FeIrNOPEe = 100%[α]D20=-578.0 (c 0.20, CH2Cl2)Source of chirality: asymmetric synthesisAbsolute configuration: (S,S)

(η4-1,5-Cyclooctadiene) [(S,S)-(4,5-dihydro-4-benzyl-2-oxazolyl)-2-diphenylphosphinoferrocene] iridium(I) tetrakis[3,5-bis(trifluoromethyl)phenyl]borateC72H52BF24FeIrNOPEe = 100%[α]D20=-397.4 (c 0.20, CH2Cl2)Source of chirality: asymmetric synthesisAbsolute configuration: (S,S)

(η4-1,5-Cyclooctadiene) [(S,R)-(4,5-dihydro-4-tert-buty-2-oxazolyl)-2-diphenylphosphinoferrocene] iridium(I) tetrakis[3,5-bis(trifluoromethyl)phenyl]borateC69H54BF24FeIrNOPEe = 100%[α]D20=+217.2 (c 0.14, CH2Cl2)Source of chirality: asymmetric synthesisAbsolute configuration: (S,R)

(η4-1,5-Cyclooctadiene) [(S,S)-(4,5-dihydro-4-methyl-2-oxazolyl)-2-diphenylphosphinoferrocene] iridium(I) hexafluorophosphateC34H36F6FeIrNOP2Ee = 100%[α]D20=-160.1 (c 0.1, CH2Cl2)Source of chirality: asymmetric synthesisAbsolute configuration: (S,S)