Asymmetric synthesis of (4S,5S)-2-oxo-4-phenyloxazolidine-5-carboxylic acid using a 1,2-addition of PhMgBr to an N-sulfinimine derived from (R)-glyceraldehyde acetonide and (S)-t-BSA

We report an asymmetric synthesis of (4S,5S)-2-oxo-4-phenyloxazolidine-5-carboxylic acid via stereoselective addition of phenylmagnesium bromide (PhMgBr) to an N-sulfinimine derived from (R)-glyceraldehyde acetonide. (S)- and (R)-Glyceraldehyde acetonides, important chiral synthons in synthetic organic chemistry, are prepared from the corresponding epichlorohydrin using an identical synthetic methodology.

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(R)-4-(Chloromethyl)-2,2-dimethyl-1,3-dioxolaneC6H11ClO2[α]D25=+35.9 (c 5.3, Bz)Source of chirality: (R)-epichlorohydrinAbsolute configuration: (R)

((R)-2,2-Dimethyl-1,3-dioxolan-4-yl)methyl benzoateC13H16O4[α]D25=+7.3 (c 1.0, CHCl3)Source of chirality: (R)-epichlorohydrinAbsolute configuration: (R)

((S)-2,2-Dimethyl-1,3-dioxolan-4-yl)methanolC6H12O3[α]D25=+14.4 (neat)Source of chirality: (R)-epichlorohydrinAbsolute configuration: (S)

(R)-2,2-Dimethyl-1,3-dioxolane-4-carbaldehydeC6H10O3[α]D25=+53.8 (c 2.0, CHCl3)Source of chirality: (R)-epichlorohydrinAbsolute configuration: (R)

(S,E)-N-(((S)-2,2-Dimethyl-1,3-dioxolan-4-yl)methylene)-2-methylpropane-2-sulfinamideC10H19NO3S[α]D25=+63.8 (c 1.0, EtOH)Source of chirality: (R)-glyceraldehyde acetonide and (S)-t-BSAAbsolute configuration: (S,S)

(S)-N-((S)-((S)-2,2-Dimethyl-1,3-dioxolan-4-yl)(phenyl)methyl)-2-methylpropane-2-sulfinamideC16H25NO3S[α]D25=+77.2 (c 1.0, EtOH)Source of chirality: (R)-glyceraldehyde acetonide and (S)-t-BSAAbsolute configuration: (S,S)

(2S,3S)-3-Amino-3-phenylpropane-1,2-diol hydrochlorideC9H14ClNO2[α]D25=+3.7 (c 1.05, MeOH)Source of chirality: (R)-glyceraldehyde acetonide and (S)-t-BSAAbsolute configuration: (S,S)

tert-Butyl (1S,2S)-2,3-dihydroxy-1-phenylpropylcarbamateC14H24NO4[α]D25=+51.0 (c 0.65, CHCl3)Source of chirality: (R)-glyceraldehyde acetonide and (S)-t-BSAAbsolute configuration: (S,S)

(4S,5S)-5-(Hydroxymethyl)-4-phenyloxazolidin-2-oneC10H11NO3[α]D25=+71.8 (c 1.0, EtOH)Source of chirality: (R)-glyceraldehyde acetonide and (S)-t-BSAAbsolute configuration: (S,S)

(4S,5S)-2-Oxo-4-phenyloxazolidine-5-carboxylic acidC10H9NO4[α]D25=+63.3 (c 1.20, DMF)Source of chirality: (R)-glyceraldehyde acetonide and (S)-t-BSAAbsolute configuration: (S,S)