Stereoselective total synthesis of ophiocerin D from d-xylose

A stereoselective total synthesis of ophiocerin D is reported by a combination of a ‘chiron’ approach and an asymmetric synthesis, from d-xylose. Of the four stereogenic centers, the vic diols C3/C4 and C5/C6 were obtained by Sharpless asymmetric dihydroxylation and from d-xylose, respectively.

Total synthesis of ophiocerin D from d-xylose is reported.Figure optionsDownload as PowerPoint slide

(2R,3S,4R,5S)-3-(Benzyloxy)-4,5-bis(methoxymethoxy)-2-methyl-tetrahydro-2H-pyranC17H26O6[α]D = −100.7 (c 1.4, CHCl3)Source of chirality: d-xyloseAbsolute configuration: (2R,3S,4R,5S)

(2R,3S,4R,5S)-4,5-Bis(methoxymethoxy)-2-methyl-tetrahydro-2H-pyran-3-yl-but-2-yn-oateC14H22O7[α]D = +13.5 (c 0.2, CHCl3)Source of chirality: d-xyloseAbsolute configuration: (2R,3S,4R,5S)

(Z)-[(2R,3S,4R,5S)-4,5-Bis(methoxymethoxy)-2-methyl-tetrahydro-2H-pyran-3-yl)-but-2-enoateC14H24O7[α]D = +34.4 (c 0.2, CHCl3)Source of chirality: d-xyloseAbsolute configuration: (2R,3S,4R,5S)

Ophiocerin-DC10H16O5[α]D = +38.4 (c 0.1, CHCl3)Source of chirality: d-xyloseAbsolute configuration: (2R,3S,4R,5S)

(4R,5R,E)-Methyl 4-(benxyloxy)-5-hydroxyhex-2-enoateC14H18O4[α]D = −22.8 (c 1.2, CHCl3)Source of chirality: d-xyloseAbsolute configuration: (4R,5R)

(2R,3R,4R,5R)-4-(Benzyloxy)-5-(tert-butyldimethylsilyloxy)-2,3-bis(methoxymethoxy)hexan-1-olC23H42O7Si[α]D = −30.4 (c 2.4, CHCl3)Source of chirality: d-xyloseAbsolute configuration: (2R,3R,4R,5R)

(2R,3R,4R,5R)-Methyl 4-(benzyloxy)-5-(tert-butyldimethylsilyloxy)-2,3-dihydroxy hexanoateC20H34O6Si[α]D = +12.8 (c 1.5, CHCl3)Source of chirality: d-xyloseAbsolute configuration: (2R,3R,4R,5R)