Synthesis of enantiomerically pure (+)- and (−)-protected 5-aminomethyl-1,3-oxazolidin-2-one derivatives from allylamine and carbon dioxide

The stereoselective synthesis of enantiomerically pure (5R)- and (5S)-aminomethyl-oxazolidinones with different protecting groups have been carried out from an allyl amine as the source of the carbon backbone. The key reaction is the high yield iodiocyclization of enantiomerically pure allylphenethyl amine in the presence of carbon dioxide.

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(1′S,5S)-5-Yodomethyl-3-(1′-phenylethyl)-1,3-oxazolidin-2-oneC12H14INO2Ee = 100%[α]D24=-15.7 (c 0.45, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (1′S,5S)

(1′S,5R)-5-Yodomethyl-3-(1′-phenylethyl)-1,3-oxazolidin-2-oneC12H14INO2Ee = 100%[α]D24=-3.3 (c 0.12, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (1′S,5R)

(1′S,5S)-5-Azidomethyl-3-(1′-phenylethyl)-1,3-oxazolidin-2-oneC12H14N4O2Ee = 100%[α]D24=22.6 (c 0.19, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (1′S,5S)

(1′S,5R)-5-Azidomethyl-3-(1′-phenylethyl)-1,3-oxazolidin-2-oneC12H14N4O2Ee = 100%[α]D24=-220.65 (c 0.10, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (1′S,5R)

(1′S,5R)-5-Aminomethyl-3-(1′-phenylethyl)-1,3-oxazolidin-2-oneC12H16N2O2Ee = 100%[α]D23=-39.6 (c 0.12, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (1′S,5R)

(1′S,5S)-5-Aminomethyl-3-(1′-phenylethyl)-1,3-oxazolidin-2-oneC12H16N2O2Ee = 100%[α]D24=-139.2 (c 0.10, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (1′S,5S)

(1′S,5R)-5-tert-Butoxicarbonylaminomethyl-3-(1′-phenylethyl)-1,3-oxazolidin-2-oneC17H24N2O4Ee = 100%[α]D26=-32.7 (c 0.06, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (1′S,5R)

(1′S,5S)-5-tert-Butoxicarbonylaminomethyl-3-(1′-phenylethyl)-1,3-oxazolidin-2-oneC17H24N2O4Ee = 100%[α]D26=-95.85 (c 0.05, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (1′S,5S)

(5S)-5-tert-Butoxicarbonylaminomethyl-1,3-oxazolidin-2-oneC9H16N2O4Ee = 100%[α]D26=+1.4 (c 2.02, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (5S)

(5R)-5-tert-Butoxycarbonylaminomethyl-3-benzyloxycarbonyl-1,3-oxazolidin-2-oneC17H22N2O6Ee = 100%[α]D26=+11.9 (c 0.05, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (5R)