ethyl 4-azido-3-O-benzyl-2-O-(bromoacetyl)-4,6-dideoxy-1-thio-β-D-glucopyranoside | 872333-46-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: ethyl 4-azido-3-O-benzyl-2-O-(bromoacetyl)-4,6-dideoxy-1-thio-β-D-glucopyranoside
• 英文别名: [(2S,3R,4S,5R,6R)-5-azido-2-ethylsulfanyl-6-methyl-4-phenylmethoxyoxan-3-yl] 2-bromoacetate
• CAS: 872333-46-5
• 化学式: C₁₇H₂₂BrN₃O₄S
• 分子量: 444.349
• InChiKey: VWDWRCVBDNRZMP-UFRBAHOGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.6
• 重原子数：
  26
• 可旋转键数：
  9
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.59
• 拓扑面积：
  84.4
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  ethyl 4-azido-3-O-benzyl-2-O-(bromoacetyl)-4,6-dideoxy-1-thio-β-D-glucopyranoside 、 5-methoxycarbonylpentyl 2,4-di-O-benzyl-α-L-rhamnopyranosyl-(1->3)-2,4-di-O-benzyl-α-L-rhamnopyranosyl-(1->2)-3,4-di-O-benzyl-α-L-rhamnopyranoside 在 N-碘代丁二酰亚胺 、 4 A molecular sieve 、 silver trifluoromethanesulfonate 作用下， 以 二氯甲烷 为溶剂， 以84%的产率得到5-methoxycarbonylpentyl 4-azido-3-O-benzyl-2-O-bromoacetyl-4,6-dideoxy-β-D-glucopyranosyl-(1->3)-2,4-di-O-benzyl-α-L-rhamnopyranosyl-(1->3)-2,4-di-O-benzyl-α-L-rhamnopyranosyl-(1->2)-3,4-di-O-benzyl-α-L-rhamnopyranoside
  参考文献：
  名称：

  与炭疽芽孢杆菌外孢子的合成四糖侧链有关的免疫原。

  摘要：

  将已知的甲基2-O-乙酰基-3,4-二-O-苄基-1-硫代-α-L-鼠李糖吡喃糖苷（3）转化为相应的5-甲氧基羰基戊基糖苷4，其被去乙酰化。产物5用作起始的糖基受体，以构建两个侧接苯甲酰基或苄基的HO-3（III）的三鼠李糖苷糖基受体，分别是化合物10和29 [除HO-3（III）外，均得到充分保护，α -L-Rha-（1-> 3）-alpha-L-Rha-（1-> 2）-alpha-L-Rha-1-O-（CH2）5COOCH3]。当将它们用乙基4-叠氮基-3-O-苄基-4,6-二脱氧-2-O-溴乙酰基-1-硫代β-D-吡喃葡萄糖苷糖基化时（18），只有苄基化的糖基受体29给出了良好的收率。所需的四糖30。α和β连接的产物，以及相应的原酸酯23，当用带有2-O-溴乙酰基保护基的糖基供体进行10个糖基化时，几乎以相等的量形成α-β。在O-2为30时脱保护，然后进一步使分子官能化并整体脱保护，

  DOI：

  10.1016/j.bmc.2007.03.057
• 作为产物：
  描述：

  methyl 4-azido-3-O-benzyl-4,6-dideoxy-α-D-glucopyranoside 在 硫酸 、 三氟化硼乙醚 、 溶剂黄146 、 1,1,3,3-四甲基脲 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 生成 ethyl 4-azido-3-O-benzyl-2-O-(bromoacetyl)-4,6-dideoxy-1-thio-β-D-glucopyranoside
  参考文献：
  名称：

  Synthesis of the tetrasaccharide side chain of the major glycoprotein of the Bacillus anthracis exosporium

  摘要：

  An alpha-glycoside of the tetrasaccharide sequence beta-Ant-(1 -> 3)-alpha-L-Rhap-(1 -> 3)-alpha-L-Rhap-(1 -> 2)-alpha-L-Rhap whose aglycon allows conjugation to suitable carriers was synthesized. The NMR characteristics of the compound are virtually identical with those of the alpha-anomer of the tetrasaccharide isolated from the major glycoprotein of the Bacillus anthracis exosporium. Thus, the correct structure of the natural product has been proven by chemical synthesis. (c) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.bmcl.2005.10.056

文献信息

• Studies towards a Conjugate Vaccine for Anthrax: Synthesis of the Tetrasaccharide Side Chain of theBacillus anthracis Exosporium
  作者：Roberto Adamo、Rina Saksena、Pavol Kováč

  DOI：10.1002/hlca.200690106

  日期：2006.6

  The first synthesis of β-L-glycoside 17 of the tetrasaccharide β-Ant-(1  3)-α-L-Rhap-(1  3)-α-L-Rhap-(1  2)-L-Rhap is described (Schemes 1–3). Its spacer can be functionalized to make it amenable to conjugation to proteins by different conjugation methods. The synthesis was performed in a stepwise manner starting from the aglycon-bearing terminal saccharide with thioglycosides as glycosyl donors. To

  的第一合成β -L糖苷17的四糖的β -Ant-（1 3） - α -L-鼠李对-（1→3） - α -L-鼠李对-（1 2）-L-鼠李p描述（方案1-3）。可以将其间隔物官能化以使其适于通过不同的缀合方法与蛋白质缀合。从带有糖苷配基的末端糖与硫糖苷作为糖基供体开始，以逐步的方式进行合成。为了连接上游末端蔗糖残基，用乙基4-叠氮基-3- O-苄基-2- O糖基化组装的连接子的三糖。-（溴乙酰基）-4，6-二脱氧-1-硫代-β -D-吡喃葡萄糖苷（11）。如此获得的四糖的进一步官能化，然后脱保护，得到目标物质17。具有相同间隔子的17个子结构的合成，即β -L-Rha p -1- O-（CH 2）5 COOMe（21），α -L-Rha p-（1 2）-β -L-Rha p -1- O-（CH 2）5 COOMe（22）和α -L-Rha p还描述了-（1 3）-α -L-Rha p-（1 2）-β
• Synthesis of the β anomer of the spacer-equipped tetrasaccharide side chain of the major glycoprotein of the Bacillus anthracis exosporium
  作者：Roberto Adamo、Rina Saksena、Pavol Kováč

  DOI：10.1016/j.carres.2005.09.015

  日期：2005.12

  The glycoside of the tetrasaccharide sequence beta-Ant-(1 -> 3)-alpha-L-Rhap-(1 -> 3)-alpha-L-Rhap-(1 -> 2)-L-Rhap, whose aglycon allows conjugation to proteins, was synthesized for the first time. A stepwise synthetic approach was applied with thioglycosides as glycosyl donors, and the beta anomer of the compound was obtained equipped with a spacer group whose further transformation allows conjugation to suitable carriers. To synthesize the beta-anthrosyl linkage with high stereoselectivity, a linker-equipped rhamnotriose derivative was glycosylated with ethyl 4-azido-3-O-benzyl-2-O-bromoacetyl-4,6-dideoxy-1-thio-beta-D-glucopyranoside. Further functionalization of the tetrasaccharide thus obtained, followed by deprotection, gave the target Substance. (c) 2005 Elsevier Ltd. All rights reserved.
• Synthesis of the tetrasaccharide side chain of the major glycoprotein of the Bacillus anthracis exosporium
  作者：Rina Saksena、Roberto Adamo、Pavol Kováč

  DOI：10.1016/j.bmcl.2005.10.056

  日期：2006.2

  An alpha-glycoside of the tetrasaccharide sequence beta-Ant-(1 -> 3)-alpha-L-Rhap-(1 -> 3)-alpha-L-Rhap-(1 -> 2)-alpha-L-Rhap whose aglycon allows conjugation to suitable carriers was synthesized. The NMR characteristics of the compound are virtually identical with those of the alpha-anomer of the tetrasaccharide isolated from the major glycoprotein of the Bacillus anthracis exosporium. Thus, the correct structure of the natural product has been proven by chemical synthesis. (c) 2005 Elsevier Ltd. All rights reserved.
• Immunogens related to the synthetic tetrasaccharide side chain of the Bacillus anthracis exosporium
  作者：Rina Saksena、Roberto Adamo、Pavol Kováč

  DOI：10.1016/j.bmc.2007.03.057

  日期：2007.6

  The known methyl 2-O-acetyl-3,4-di-O-benzyl-1-thio-alpha-L-rhamnopyranoside (3) was converted to the corresponding 5-methoxycarbonylpentyl glycoside 4 which was deacetylated. The product 5 was used as the initial glycosyl acceptor to construct two trirhamnoside glycosyl acceptors having HO-3(III) flanked by either benzoyl or benzyl groups, compounds 10 and 29, respectively [fully protected, except HO-3(III)

  将已知的甲基2-O-乙酰基-3,4-二-O-苄基-1-硫代-α-L-鼠李糖吡喃糖苷（3）转化为相应的5-甲氧基羰基戊基糖苷4，其被去乙酰化。产物5用作起始的糖基受体，以构建两个侧接苯甲酰基或苄基的HO-3（III）的三鼠李糖苷糖基受体，分别是化合物10和29 [除HO-3（III）外，均得到充分保护，α -L-Rha-（1-> 3）-alpha-L-Rha-（1-> 2）-alpha-L-Rha-1-O-（CH2）5COOCH3]。当将它们用乙基4-叠氮基-3-O-苄基-4,6-二脱氧-2-O-溴乙酰基-1-硫代β-D-吡喃葡萄糖苷糖基化时（18），只有苄基化的糖基受体29给出了良好的收率。所需的四糖30。α和β连接的产物，以及相应的原酸酯23，当用带有2-O-溴乙酰基保护基的糖基供体进行10个糖基化时，几乎以相等的量形成α-β。在O-2为30时脱保护，然后进一步使分子官能化并整体脱保护，