2-(trimethylsilyl)ethyl 3-O-allyl-4-O-(2,3-di-O-benzoyl-6-O-benzyl-β-D-glucopyranosyl)-2,6-di-O-benzyl-β-D-galactopyranoside | 192706-04-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-(trimethylsilyl)ethyl 3-O-allyl-4-O-(2,3-di-O-benzoyl-6-O-benzyl-β-D-glucopyranosyl)-2,6-di-O-benzyl-β-D-galactopyranoside
• CAS: 192706-04-0
• 化学式: C₅₅H₆₄O₁₃Si
• 分子量: 961.191
• InChiKey: KWJHDTQHUKZEDA-OCHXRKBKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.58
• 重原子数：
  69.0
• 可旋转键数：
  24.0
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  146.67
• 氢给体数：
  1.0
• 氢受体数：
  13.0

反应信息

• 作为反应物：
  描述：

  Acetic acid (2R,3R,4R,5R,6S)-4,5-bis-benzyloxy-6-bromo-2-methyl-tetrahydro-pyran-3-yl ester 、 2-(trimethylsilyl)ethyl 3-O-allyl-4-O-(2,3-di-O-benzoyl-6-O-benzyl-β-D-glucopyranosyl)-2,6-di-O-benzyl-β-D-galactopyranoside 在 molecular sieve 、 silver silicate 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 以35%的产率得到2-(trimethylsilyl)ethyl 4-O-[(4-O-acetyl-2,3-di-O-benzyl-β-L-rhamnopyranosyl)-2,3-di-O-benzoyl-6-O-benzyl-β-D-glucopyranosyl]-3-O-alyl-2,6-di-O-benzyl-β-D-galactopyranoside
  参考文献：
  名称：

  Synthesis of a Single Repeat Unit of Type VIII Group BStreptococcusCapsular Polysaccharide¹

  摘要：

  We have synthesized a single repeat unit of type VIII Group B Streptococcus capsular polysaccharide, the structure of which is {L-Rhap(beta 1-->4)-D-Glcp(beta 1-->4) [Neu5Ac(alpha 2-->3)]-D-Galp(beta 1-->4}(n). The synthesis presented three significant synthetic challenges namely: the L-Rhap(beta 1-->4)-D-Glcp bond, the Neu5Ac(alpha 2-->3)-D-Galp bond and 3,4-D-Galp branching. The L-Rhap bond was constructed in 60% yield (alpha:beta l:1.2) using 4-O-acetyl-2, 3-di-O-benzoyl-alpha-L-rhamnopyranosyl bromide 6 as donor, silver silicate as promotor and 6-O-benzyl-2,3-di-O-benzoyl-1-thio-beta-D-glucopyranoside as acceptor to yield disaccharide 18. The Neu5Ac(alpha 2-->3) linkage was synthesized in 66% yield using methyl [phenyl 5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-2-thio-D-glycero-D-galacto-nonulopyranosid]onate as donor and triol 2-(trimethylsilyl) ethyl 6-O-benzyl-beta-D-galactopyranoside as acceptor to give disaccharide 21. The 3,4-D-Galp branching was achieved by regioselective glycosylation of disaccharide diol 21 by disaccharide 18 in 28% yield to give protected tetrasaccharide 22. Tetrasaccharide 22 was deprotected to give as its 2-(trimethylsilyl)ethyl glycoside the title compound 1a. In addition the 2-(trimethylsilyl)ethyl group was cleaved and the tetrasaccharide coupled by glycosylation (via tetrasaccharide trichloroacetimidate) to a linker suitable for conjugation.

  DOI：

  10.1080/07328309708007324
• 作为产物：
  描述：

  2-(trimethylsilyl)ethyl 4,6-O-benzylidene-β-D-galactopyranoside 在 盐酸 、 N-碘代丁二酰亚胺 、 molecular sieve 、 三氟甲磺酸 、 四丁基溴化铵 、 sodium hydride 、 二正丁基氧化锡 、 sodium cyanoborohydride 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 29.0h， 生成 2-(trimethylsilyl)ethyl 3-O-allyl-4-O-(2,3-di-O-benzoyl-6-O-benzyl-β-D-glucopyranosyl)-2,6-di-O-benzyl-β-D-galactopyranoside
  参考文献：
  名称：

  Synthesis of a Single Repeat Unit of Type VIII Group BStreptococcusCapsular Polysaccharide¹

  摘要：

  We have synthesized a single repeat unit of type VIII Group B Streptococcus capsular polysaccharide, the structure of which is {L-Rhap(beta 1-->4)-D-Glcp(beta 1-->4) [Neu5Ac(alpha 2-->3)]-D-Galp(beta 1-->4}(n). The synthesis presented three significant synthetic challenges namely: the L-Rhap(beta 1-->4)-D-Glcp bond, the Neu5Ac(alpha 2-->3)-D-Galp bond and 3,4-D-Galp branching. The L-Rhap bond was constructed in 60% yield (alpha:beta l:1.2) using 4-O-acetyl-2, 3-di-O-benzoyl-alpha-L-rhamnopyranosyl bromide 6 as donor, silver silicate as promotor and 6-O-benzyl-2,3-di-O-benzoyl-1-thio-beta-D-glucopyranoside as acceptor to yield disaccharide 18. The Neu5Ac(alpha 2-->3) linkage was synthesized in 66% yield using methyl [phenyl 5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-2-thio-D-glycero-D-galacto-nonulopyranosid]onate as donor and triol 2-(trimethylsilyl) ethyl 6-O-benzyl-beta-D-galactopyranoside as acceptor to give disaccharide 21. The 3,4-D-Galp branching was achieved by regioselective glycosylation of disaccharide diol 21 by disaccharide 18 in 28% yield to give protected tetrasaccharide 22. Tetrasaccharide 22 was deprotected to give as its 2-(trimethylsilyl)ethyl glycoside the title compound 1a. In addition the 2-(trimethylsilyl)ethyl group was cleaved and the tetrasaccharide coupled by glycosylation (via tetrasaccharide trichloroacetimidate) to a linker suitable for conjugation.

  DOI：

  10.1080/07328309708007324