Stereoselective synthesis of both enantiomers of α-(hydroxymethyl)glutamic acid

An efficient stereoselective synthesis of both enantiomers of 2-(hydroxymethyl)glutamic (HMG) acid starting from highly functionalized (2R)-2-(tert-butyldimethylsilyloxymethyl)-2-(methoxycarbonylamino)but-3-enal 11 as a suitable synthon is reported.

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5-O-Acetyl-3-deoxy-1,2-O-isopropylidene-3-(methoxycarbonylamino)-3-C-vinyl-α-d-xylofuranoseC14H21NO7[α]D20=+56.1 (c 0.30, CHCl3)Source of chirality: d-xyloseAbsolute configuration: (2R,3R,4S,5S)

(2R,3S)-4-O-Acetyl-2-(methoxycarbonylamino)-2-vinylbutane-1,3-diolC10H17NO6[α]D20=+10.3 (c 0.34, CHCl3)Source of chirality: d-xyloseAbsolute configuration: (2R,3S)

(2R,3S)-1-O-(tert-Butyldimethylsilyl)-2-(methoxycarbonylamino)-2-vinylbutane-3,4-diolC14H29NO5Si[α]D20=+16.9 (c 0.32, CHCl3)Source of chirality: d-xyloseAbsolute configuration: (2R,3S)

(2R,3S)-4-O-Acetyl-1-O-(tert-butyldimethylsilyl)-2-(methoxycarbonylamino)-2-vinylbutane-3-olC16H31NO6Si[α]D20=+10.3 (c 0.34, CHCl3)Source of chirality: d-xyloseAbsolute configuration: (2R,3S)

Methyl (2R)-2-(tert-butyldimethylsilyloxymethyl)-2-(methoxycarbonylamino)but-3-enoateC14H27NO5Si[α]D20=-63.7 (c 0.27, CHCl3)Source of chirality: d-xyloseAbsolute configuration: (2R)

Dimethyl (E,2R)-2-(tert-butyldimethylsilyloxymethyl)-2-(methoxycarbonylamino)pent-3-endioateC16H29NO7Si[α]D20=-111.1 (c 0.27, CHCl3)Source of chirality: d-xyloseAbsolute configuration: (2R)

(2S)-1-O-(tert-Butyldimethylsilyl)-2-(methoxycarbonylamino)-2-vinylpropane-3-olC13H27NO4Si[α]D20=+13.4 (c 0.42, CHCl3)Source of chirality: d-xyloseAbsolute configuration: (2S)

(4S)-4-(tert-Butyldimethylsilyloxymethyl)-4-vinyloxazolidine-2-oneC12H23NO3Si[α]D20=+66.6 (c 0.36, CHCl3)Source of chirality: d-xyloseAbsolute configuration: (4S)

Methyl (E,4S)-3-[4-(tert-butyldimethylsilyloxymethyl)-2-oxooxazolidin-4-yl]prop-2-enoateC14H25NO5Si[α]D20=+66.7 (c 0.33, CHCl3)Source of chirality: d-xyloseAbsolute configuration: (4S)

(4S)-4-[2-(Methoxycarbonylethyl)]-2-oxooxazolidine-4-carboxylic acidC8H11NO6[α]D20=-31.0 (c 0.49, CHCl3)Source of chirality: d-xyloseAbsolute configuration: (4S)

(2R)-α-(Hydroxymethyl)glutamic acidC6H11NO5·HCl·0.5H2O[α]D20=-1.4 (c 0.45, H2O)Source of chirality: d-xyloseAbsolute configuration: (2R)