Chiral N-thiophosphoryl imine-induced diastereoselective aza-Morita–Baylis–Hillman reaction

In the presence of an effective air-stable nucleophilic trialkylphosphine organocatalyst, 1,3,5-triaza-7-phosphaadamantane, a chiral N-thiophosphoryl imine bearing a (S)-binaphthalene skeleton induced a diastereoselective aza-MBH reaction with fair chemical yields and moderate to excellent diastereoselectivities (up to >99% de).

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(S)-O-Ethyl N-benzeliydene phenylphosphonamidothioateC15H16NOPS[α]D20=-102.2 (c 1.0, CHCl3)Source of chirality: chiral poolAbsolute configuration: (S)

(S)-N-Benzeliydene 1,1′-binaphthyl 2,2′-cyclic phosphoramidothioateC27H18O2PS[α]D20=+288.5 (c 1.0, CHCl3)Source of chirality: (S)-1,1′-binaphtholAbsolute configuration: (S)

(S)-N-p-Methylbenzeliydene 1,1′-binaphthyl 2,2′-cyclic phosphoramidothioateC28H18NO2PS[α]D20=+153.9 (c 1.0, CHCl3)Source of chirality: (S)-1,1′-binaphtholAbsolute configuration: (S)

(S)-N-p-Methoxybenzeliydene 1,1′-binaphthyl 2,2′-cyclic phosphoramidothioateC28H20NO3PS[α]D20=+103.5 (c 1.0, CHCl3)Source of chirality: (S)-1,1′-binaphtholAbsolute configuration: (S)

(S)-N-o-Chlorobenzeliydene 1,1′-binaphthyl 2,2′-cyclic phosphoramidothioateC27H17ClNO2PS[α]D20=+228.5 (c 1.0, CHCl3)Source of chirality: (S)-1,1′-binaphtholAbsolute configuration: (S)

(S)-N-p-Bromobenzeliydene 1,1′-binaphthyl 2,2′-cyclic phosphoramidothioateC27H17BrNO2PS[α]D20=+99.5 (c 1.0, CHCl3)Source of chirality: (S)-1,1′-binaphtholAbsolute configuration: (S)

(S)-N-p-Trifluoromethylbenzeliydene 1,1′-binaphthyl 2,2′-cyclic phosphoramidothioateC28H17F3NO2PS[α]D20=+254.4 (c 1.0, CHCl3)Source of chirality: (S)-1,1′-binaphtholAbsolute configuration: (S)