Stereoselective synthesis of a novel natural carbasugar and analogues from hydroxymethylated cycloalkenone scaffolds

Novel carbasugars from Streptomyces lincolnensis have been synthesized from an enantiomerically pure 5-hydroxymethyl-cyclohex-2-enone scaffold via a stereoselective approach. Several structural analogues of those carbasugars have also been synthesized in a stereoselective manner from hydroxymethylated cycloalkenone derivatives.

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(1R,5R)-5-(tert-Butyl-diphenylsilyloxymethyl)-cyclohex-2-enolC23H30O2Si[α]D28=-19.5 (c 0.6, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (1R,5R)

(1R,2R,3R,5R)-5-(Hydroxymethyl)cyclohexane-1,2,3-triolC7H14O4[α]D28=+17.0 (c 1.0, H2O)Source of chirality: asymmetric synthesisAbsolute configuration: (1R,2R,3R,5R)

(1R,2R,4S,6S)-4-(tert-Butyl-diphenylsilyloxymethyl)-7-oxa-bicyclo[4.1.0]heptan-2-olC23H30O3Si[α]D28=-4.4 (c 0.5, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (1R,2R,4S,6S)

(1R,2S,3R,5S)-5-(Hydroxymethyl)cyclohexane-1,2,3-triolC7H14O4[α]D28=-8.8 (c 1.0, H2O)Source of chirality: asymmetric synthesisAbsolute configuration: (1R,2S,3R,5S)

(1S,2R,4R,6R)-4-(tert-Butyldiphenylsilyloxymethyl)bicyclo[4.1.0]heptan-2-olC24H32O2Si[α]D28=-22.1 (c 0.6, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (1S,2R,4R,6R)

(1S,2R,4R,6R)-4-(Hydroxymethyl)bicyclo[4.1.0]heptan-2-olC8H14O2[α]D28=-12.5 (c 1.0, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (1S,2R,4R,6R)

(1S,5R)-5-(tert-Butyldiphenylsilyloxymethyl)cyclohex-2-enolC23H30O2Si[α]D28=-18.8 (c 0.3, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (1S,5R)

(1R,2S,4R,6S)-4-(tert-butyldiphenylsilyloxymethyl)bicyclo[4.1.0]heptan-2-olC24H32O2Si[α]D28=-34.2 (c 1.0, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (1R,2S,4R,6S)

(1R,2S,4R,6S)-4-(Hydroxymethyl)bicyclo[4.1.0]heptan-2-olC8H14O2[α]D28=-9.8 (c 1.0, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (1R,2S,4R,6S)

(1S,2S,4S,6R)-4-(tert-Butyldiphenylsilyloxymethyl)-7-oxa-bicyclo[4.1.0]heptan-2-olC23H30O3Si[α]D28=-17.3 (c 1.0, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (1S,2S,4S,6R)

(1S,2S,3S,5S)-5-(Hydroxymethyl)cyclohexane-1,2,3-triolC7H14O4[α]D28=-6.2 (c 0.5, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (1S,2S,3S,5S)

(1R,5R)-1-tert-Butyldimethylsilyloxy-5-(tertbutyldimethylsilyloxymethyl)cyclohex-2-eneC29H44O2Si2[α]D28=-44.2 (c 1.0, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (1R,5R)

(1S,2R,4S,6R)-2-tert-Butyldimethylsilyloxy-4-(tertbutyldiphenylsilyloxymethyl)-7-oxa-bicyclo[4.1.0]heptaneC29H44O3Si2[α]D28=-31.9 (c 1.0, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (1S,2R,4S,6R)

(1R,2R,3S,5R)-5-(Hydroxymethyl)cyclohexane-1,2,3-triolC7H14O4[α]D28=+7.4 (c 1.0, H2O)Source of chirality: asymmetric synthesisAbsolute configuration: (1R,2R,3S,5R)

(1R,5R)-5-(tert-Butyldiphenylsilyloxymethyl)cyclopent-2-enolC22H28O2Si[α]D28=+22.5 (c 1.0, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (1R,5R)

(1S,5R)-5-(tert-Butyldiphenylsilyloxymethyl)cyclopent-2-enolC22H28O2Si[α]D28=+5.3 (c 1.0, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (1S,5R)

(1S,2S,3R,5R)-3-(tert-Butyldiphenylsilyloxymethyl)-6-oxa-bicyclo[3.1.0]hexan-2-olC22H28O3Si[α]D28=+12.3 (c 1.0, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (1S,2S,3R,5R)

(1R,2S,3R,5S)-3-(tert-Butyldiphenylsilyloxymethyl)-6-oxa-bicyclo[3.1.0]hexan-2-olC22H28O3Si[α]D28=+22.1 (c 1.0, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (1R,2S,3R,5S)

(1S,2R,3S,4R)-4-(Hydroxymethyl)cyclopentane-1,2,3-triolC6H12O4[α]D28=+8.35 (c 1.0, H2O)Source of chirality: asymmetric synthesisAbsolute configuration: (1S,2R,3S,4R)

(1R,2S,3S,4R)-4-(Hydroxymethyl)cyclopentane-1,2,3-triolC6H12O4[α]D28=+12.1 (c 1.0, H2O)Source of chirality: asymmetric synthesisAbsolute configuration: (1R,2S,3S,4R)

(1R,2R,3R,5S)-3-(tert-Butyldiphenylsilyloxymethyl)-6-oxa-bicyclo[3.1.0]hexan-2-olC22H28O3Si[α]D28=+22.0 (c 1.0, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (1R,2R,3R,5S)