Optically active P-chiral phosphinoselenoic amides: stereochemical outcome at the P-stereogenic center in the synthesis of these substances and their characterization

A variety of optically active P-chiral phosphinoselenoic amides were synthesized with high efficiency by reacting racemic P-chiral phosphinoselenoic chlorides with optically active lithium amides. Some of the diastereomers of the amides were separated by column chromatography on silica gel. The absolute configurations of the phosphinoselenoic amides were determined by X-ray molecular structure analyses. Optically active P-chiral phosphinoselenoic chlorides were also reacted with optically active lithium amide. The reaction proceeded predominantly with inversion of configuration, but also involved retention of stereochemistry at the phosphorus atom during the substitution reaction.

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(RP,S)-P-(1-Methylethyl)-P-phenyl-N-(1-phenylethyl)phosphinoselenoic amideC17H22NPSeDe >99%[α]D20=-44 (c 1.0, CH2Cl2)Source of chirality: starting reactantAbsolute configuration: RP,S

(SP,S)-P-(1-Methylethyl)-P-phenyl-N-(1-phenylethyl)phosphinoselenoic amideC17H22NPSeDe >99%[α]D20=-55 (c 1.0, CH2Cl2)Source of chirality: starting reactantAbsolute configuration: SP,S

(SP,R)-P-(1-Methylethyl)-P-phenyl-N-(1-phenylethyl)phosphinoselenoic amideC17H22NPSeDe >99%[α]D20=+44 (c 1.0, CH2Cl2)Source of chirality: starting reactantAbsolute configuration: SP,R

(RP,R)-P-(1-Methylethyl)-P-phenyl-N-(1-phenylethyl)phosphinoselenoic amideC17H22NPSeDe >99%[α]D20=+53 (c 1.0, CH2Cl2)Source of chirality: starting reactantAbsolute configuration: RP,S

(RP,S)-P-Cyclohexyl-P-phenyl-N-(1-phenylethyl)phosphinoselenoic amideC20H26NPSeDe >99%[α]D20=-40 (c 1.0, CH2Cl2)Source of chirality: starting reactantAbsolute configuration: RP,S

(SP,S)-P-Cyclohexyl-P-phenyl-N-(1-phenylethyl)phosphinoselenoic amideC20H26NPSeDe >99%[α]D20=-37 (c 1.0, CH2Cl2)Source of chirality: starting reactantAbsolute configuration: SP,S

(SP,R)-P-Cyclohexyl-P-phenyl-N-(1-phenylethyl)phosphinoselenoic amideC20H26NPSeDe >99%[α]D20=+39 (c 1.0, CH2Cl2)Source of chirality: starting reactantAbsolute configuration: SP,R

(RP,R)-P-Cyclohexyl-P-phenyl-N-(1-phenylethyl)phosphinoselenoic amideC20H26NPSeDe >99%[α]D20=+35 (c 1.0, CH2Cl2)Source of chirality: starting reactantAbsolute configuration: RP,R

(RP,S)-P-(1,1-Dimethylethyl)-P-phenyl-N-(1-phenylethyl)phosphinoselenoic amideC18H24NPSeDe >99%[α]D20=-40 (c 1.0, CH2Cl2)Source of chirality: starting reactantAbsolute configuration: RP,S

(SP,S)-P-(1,1-Dimethylethyl)-P-phenyl-N-(1-phenylethyl)phosphinoselenoic amideC18H24NPSeDe >99%[α]D20=-62 (c 1.0, CH2Cl2)Source of chirality: starting reactantAbsolute configuration: SP,S

(SP,R)-P-(1,1-Dimethylethyl)-P-phenyl-N-(1- phenylethyl)phosphinoselenoic amideC18H24NPSeDe >99%[α]D20=+40 (c 1.0, CH2Cl2)Source of chirality: starting reactantAbsolute configuration: SP,R

(RP,R)-P-(1,1-Dimethylethyl)-P-phenyl-N-(1-phenylethyl)phosphinoselenoic amideC18H24NPSeDe >99%[α]D20=+60 (c 1.0, CH2Cl2)Source of chirality: starting reactantAbsolute configuration: RP,R

(RP,S)-P-(1-Methylethyl)-N-[1-(1-naphthyl)ethyl]-P-phenylphosphinoselenoic amideC21H24NPSeDe >99%[α]D20=-28 (c 1.0, CH2Cl2)Source of chirality: starting reactantAbsolute configuration: RP,S

(SP,S)-P-(1-Methylethyl)-N-[1-(1-naphthyl)ethyl]-P-phenylphosphinoselenoic amideC21H24NPSeDe >99%[α]D20=+15 (c 1.0, CH2Cl2)Source of chirality: starting reactantAbsolute configuration: SP,S

(SP,R)-P-(1-Methylethyl)-N-[1-(1-naphthyl)ethyl]-P-phenylphosphinoselenoic amideC21H24NPSeDe >99%[α]D20=+26 (c 1.0, CH2Cl2)Source of chirality: starting reactantAbsolute configuration: SP,R

(RP,R)-P-(1- Methylethyl)-N-[1-(1-naphthyl)ethyl]-P-phenylphosphinoselenoic amideC21H24NPSeDe >99%[α]D20=-14 (c 1.0, CH2Cl2)Source of chirality: starting reactantAbsolute configuration: RP,R

(RP,S)-P-Cyclohexyl-N-[1-(1-naphthyl)ethyl]-P-phenylphosphinoselenoic amideC24H28NPSeDe >99%[α]D20=-13 (c 1.0, CH2Cl2)Source of chirality: starting reactantAbsolute configuration: RP,S

(SP,S)-P-Cyclohexyl-N-[1-(1-naphthyl)ethyl]-P-phenylphosphinoselenoic amideC24H28NPSeDe >99%[α]D20=+27 (c 1.0, CH2Cl2)Source of chirality: starting reactantAbsolute configuration: SP,S

(SP,R)-P-Cyclohexyl-N-[1-(1-naphthyl)ethyl]-P-phenylphosphinoselenoic amideC24H28NPSeDe >99%[α]D20=+13 (c 1.0, CH2Cl2)Source of chirality: starting reactantAbsolute configuration: SP,R

(RP,R)-P-Cyclohexyl-N-[1-(1-naphthyl)ethyl]-P-phenylphosphinoselenoic amideC24H28NPSeDe >99%[α]D20=-27 (c 1.0, CH2Cl2)Source of chirality: starting reactantAbsolute configuration: RP,R

(RP,S)-P-(1,1-Dimethylethyl)-N-[1-(1-naphthyl)ethyl]-P-phenylphosphinoselenoic amideC22H28NPSeDe >99%[α]D20=-13 (c 1.0, CH2Cl2)Source of chirality: starting reactantAbsolute configuration: RP,S

(SP,S)-P-(1,1-Dimethylethyl)-N-[1-(1-naphthyl)ethyl]-P-phenylphosphinoselenoic amideC22H28NPSeDe >99%[α]D20=-18 (c 1.0, CH2Cl2)Source of chirality: starting reactantAbsolute configuration: SP,S

(SP,R)-P-(1,1-Dimethylethyl)-N-[1-(1-naphthyl)ethyl]-P-phenylphosphinoselenoic amideC22H28NPSeDe >99%[α]D20=+12 (c 1.0, CH2Cl2)Source of chirality: starting reactantAbsolute configuration: SP,R

(RP,R)-P-(1,1-Dimethylethyl)-N-[1-(1-naphthyl)ethyl]-P-phenylphosphinoselenoic amideC22H28NPSeDe >99%[α]D20=+16 (c 1.0, CH2Cl2)Source of chirality: starting reactantAbsolute configuration: RP,R

(RP,S)-N-(1-Cyclohexylethyl)-P-(1-methylethyl)-P-phenylphosphinoselenoic amideC17H28NPSeDe >99%[α]D20=-33 (c 1.0, CH2Cl2)Source of chirality: starting reactantAbsolute configuration: RP,S

(SP,S)-N-(1-Cyclohexylethyl)-P-(1-methylethyl)-P-phenylphosphinoselenoic amideC17H28NPSeDe >99%[α]D20=+25 (c 1.0, CH2Cl2)Source of chirality: starting reactantAbsolute configuration: SP,S

(SP,R)-N-(1-Cyclohexylethyl)-P-(1-methylethyl)-P-phosphinoselenoic amideC17H28NPSeDe >99%[α]D20=+33 (c 1.0, CH2Cl2)Source of chirality: starting reactantAbsolute configuration: SP,R

(RP,R)-N-(1-Cyclohexylethyl)-P-(1-methylethyl)-P-phenylphosphinoselenoic amideC17H28NPSeDe >99%[α]D20=-25 (c 1.0, CH2Cl2)Source of chirality: starting reactantAbsolute configuration: RP,R

(RP,S)-P-Cyclohexyl-N-(1-cyclohexylethyl)-P-phenylphosphinoselenoic amideC20H32NPSeDe >99%[α]D20=-33 (c 1.0, CH2Cl2)Source of chirality: starting reactantAbsolute configuration: RP,S

(SP,S)-P-Cyclohexyl-N-(1-cyclohexylethyl)-P-phenylphosphinoselenoic amideC20H32NPSeDe >99%[α]D20=+31 (c 1.0, CH2Cl2)Source of chirality: starting reactantAbsolute configuration: SP,S

(SP,R)-P-Cyclohexyl-N-(1-cyclohexylethyl)-P-phenylphosphinoselenoic amideC20H32NPSeDe >99%[α]D20=+33 (c 1.0, CH2Cl2)Source of chirality: starting reactantAbsolute configuration: SP,R

(RP,R)-P-Cyclohexyl-N-(1-cyclohexylethyl)-P-phenylphosphinoselenoic amideC20H32NPSeDe >99%[α]D20=-31 (c 1.0, CH2Cl2)Source of chirality: starting reactantAbsolute configuration: RP,R

(RP,S)-P-Cyclohexyl-N-(1,1-dimethylethyl)-P-phenylphosphinoselenoic amideC18H30NPSeDe >99%[α]D20=-32 (c 1.0, CH2Cl2)Source of chirality: starting reactantAbsolute configuration: RP,S

(SP,S)-N-(1-Cyclohexylethyl)-P-(1,1-dimethylethyl)-P-phenylphosphinoselenoic amideC18H30NPSeDe >99%[α]D20=+18 (c 1.0, CH2Cl2)Source of chirality: starting reactantAbsolute configuration: SP,S

(SP,R)-N-(1-Cyclohexylethyl)-P-(1,1-dimethylethyl)-P-phenylphosphinoselenoic amideC18H30NPSeDe >99%[α]D20=+32 (c 1.0, CH2Cl2)Source of chirality: starting reactantAbsolute configuration: SP,R

(RP,R)-N-(1-Cyclohexylethyl)-P-(1,1-dimethylethyl)-P-phenylphosphinoselenoic amideC18H30NPSeDe >99%[α]D20=-18 (c 1.0, CH2Cl2)Source of chirality: starting reactantAbsolute configuration: RP,R