Bifunctional chiral phosphine-containing Lewis base catalyzed asymmetric Morita–Baylis–Hillman reaction of aldehydes with activated alkenes

A series of novel bifunctional chiral phosphine-containing Lewis bases were synthesized and successfully applied to the asymmetric Morita–Baylis–Hillman reaction of aldehydes with methyl vinyl ketone (MVK) and ethyl vinyl ketone (EVK) to give the corresponding adducts in moderate yields and enantioselectivities under mild reaction conditions.

A series of novel bifunctional chiral phosphine-containing Lewis bases were synthesized and successfully applied to the asymmetric Morita–Baylis–Hillman reaction of aldehydes with methyl vinyl ketone (MVK) and ethyl vinyl ketone (EVK) to give the corresponding adducts in moderate yields and enantioselectivities under mild reaction conditions.Figure optionsDownload as PowerPoint slide

(R)-(+)-3-Bromo-5,6,7,8-tetrahydro-1-(5,6,7,8-tetrahydro-2-hydroxynaphthalen-1-yl)naphthalen-2-olC20H21BrO2Ee = 100%[α]D25=+55.9 (c 1.19, CH2Cl2)Source of chirality: resolutionAbsolute configuration: (R)

(R)-(+)-5,6,7,8-Tetrahydro-1-(5,6,7,8-tetrahydro-2-hydroxynaphthalen-1-yl)-3-phenylnaphthalen-2-olC26H26O2Ee = 100%[α]D25=+83.5 (c 0.76, CH2Cl2)Source of chirality: resolutionAbsolute configuration: (R)

(R)-(−)-2,2′-Bis((trifluoromethanesulfony1)oxy)-3-phenyl-1,1′-H8-binaphthaleneC28H24F6O6S2Ee = 100%[α]D25=-59.2 (c 1.05, CH2Cl2)Source of chirality: resolutionAbsolute configuration: (R)

(1R,2S)-(−)-2-(Ethyl(phenyl)phosphinyl)-2′-[(trifluoromethanesulfonyl)oxy]-1,1′-binaphthaleneC29H22F3O4PSEe = 100%[α]D25=-48.6 (c 0.70, CH2Cl2)Source of chirality: resolutionAbsolute configuration: (1R,2S)

(1R,2R)-(+)-2-(Ethyl(phenyl)phosphinyl)-2′-[(trifluoromethanesulfonyl)oxy]-1,1′-binaphthaleneC29H22F3O4PSEe = 100%[α]D25=+26.1 (c 1.13, CH2Cl2)Source of chirality: resolutionAbsolute configuration: (1R,2R)

(1R,2S)-(−)-2-(Isopropyl(phenyl)phosphinyl)-2′-[trifluoromethanesulfonyl)oxy]-1,1′-binaphthaleneC30H24F3O4PSEe = 100%[α]D25=-75.0 (c 0.92, CH2Cl2)Source of chirality: resolutionAbsolute configuration: (1R,2S)

(1R,2R)-(+)-2-(Isopropyl(phenyl)phosphinyl)-2′-[trifluoromethanesulfonyl)oxy]-1,1′-binaphthaleneC30H24F3O4PSEe = 100%[α]D25=+28.2 (c 1.06, CH2Cl2)Source of chirality: resolutionAbsolute configuration: (1R,2R)

(1R,2S)-(−)-2-(Butyl(phenyl)phosphinyl)-2′-[trifluoromethanesulfonyl)oxy]-1,1′-binaphthaleneC31H26F3O4PSEe = 100%[α]D25=-69.2 (c 0.86, CH2Cl2)Source of chirality: resolutionAbsolute configuration: (1R,2S)

(1R,2R)-(+)-2-(Butyl(phenyl)phosphinyl)-2′-[trifluoromethanesulfonyl)oxy]-1,1′-binaphthaleneC31H26F3O4PSEe = 100%[α]D25=+31.7 (c 1.08, CH2Cl2)Source of chirality: resolutionAbsolute configuration: (1R,2R)