S-tert-butyl 2,3-O-benzyl-4,6-O-benzylidene-1-thio-β-D-mannopyranoside

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: S-tert-butyl 2,3-O-benzyl-4,6-O-benzylidene-1-thio-β-D-mannopyranoside
• 英文别名: (2R,4aR,6S,7S,8S,8aR)-6-tert-butylsulfanyl-2-phenyl-7,8-bis(phenylmethoxy)-4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3]dioxine
• 化学式: C₃₁H₃₆O₅S
• 分子量: 520.69
• InChiKey: RVLVVZYJGOFCLG-FBLDLFPLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.7
• 重原子数：
  37
• 可旋转键数：
  9
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  71.4
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  S-tert-butyl 2,3-O-benzyl-4,6-O-benzylidene-1-thio-β-D-mannopyranoside 在 硼烷四氢呋喃络合物 、 yttrium(III) trifluoromethanesulfonate 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 、 甲醇 为溶剂， 反应 2.17h， 以94%的产率得到tert-butyl 2,3,4-tri-O-benzyl-1-thio-β-D-mannopyranoside
  参考文献：
  名称：

  硫化物存在下萘甲基醚的氢解裂解

  摘要：

  借助于一系列用苄基醚和2-萘甲基甲基醚的组合保护的模型硫醚或含巯基糖苷的多元醇，证明了后者在经常发生催化剂中毒的硫化物的存在下，在氢解条件下易于选择性地裂解。这些结果表明，当在硫醚型官能团存在的情况下预期进行氢解脱保护时，可以在合成方案中使用2-萘甲基甲醚代替苄基醚。

  DOI：

  10.1016/j.carres.2017.06.011
• 作为产物：
  描述：

  叔丁基硫醇 、 S-phenyl 2,3-O-benzyl-4,6-O-benzylidene-1-deoxy-1-thia-α-D-mannopyranoside S-oxide 在 2,6-二叔丁基-4-甲基吡啶 、 三氟甲磺酸酐 作用下， 以 二氯甲烷 为溶剂， 反应 2.5h， 以77%的产率得到S-tert-butyl 2,3-O-benzyl-4,6-O-benzylidene-1-thio-β-D-mannopyranoside
  参考文献：
  名称：

  Direct Stereoselective Synthesis of β-Thiomannosides

  摘要：

  A highly diastereoselective synthesis of beta-thiomannopyranosides is described in which S-phenyl 2,3-di-0-benzyl-4,6-O-benzylidene-1-deoxy-1-thia-alpha-D-mannopyranoside S-oxide is treated with triflic anhydride and 2,6-di-tert-butyl-4-methylpyridine in CH2Cl2 at -78 degrees C leading to the formation of an intermediate alpha-mannosyl triflate. Addition of primary, secondary, or tertiary thiols then leads to the beta-thiomannosides, by an S(N)2-like displacement, in good yield and with excellent stereoselectivity. Deprotection is achieved either by Birch reduction or by Zemplen deacetylation, of the acetyl protected aglycons, followed by hydrogenolysis over Pearlman's catalyst. The assignment of configuration of the beta-thiomannopyranosides is discussed in terms of the chemical shift of the mannose H5 resonance and the (1)J(CH) of the mannose anomeric carbon.

  DOI：

  10.1021/jo9914667

文献信息

• Hydrogenolytic cleavage of naphthylmethyl ethers in the presence of sulfides
  作者：Philip O. Adero、Dean R. Jarois、David Crich

  DOI：10.1016/j.carres.2017.06.011

  日期：2017.9

  2-naphthylmethyl ethers it is demonstrated that the latter are readily cleaved selectively under hydrogenolytic conditions in the presence of the frequently catalyst-poisoning sulfides. These results suggest the possibility of employing 2-naphthylmethyl ethers in place of benzyl ethers in synthetic schemes when hydrogenolytic deprotection is anticipated in the presence of thioether type functionality.

  借助于一系列用苄基醚和2-萘甲基甲基醚的组合保护的模型硫醚或含巯基糖苷的多元醇，证明了后者在经常发生催化剂中毒的硫化物的存在下，在氢解条件下易于选择性地裂解。这些结果表明，当在硫醚型官能团存在的情况下预期进行氢解脱保护时，可以在合成方案中使用2-萘甲基甲醚代替苄基醚。
• Direct Stereoselective Synthesis of β-Thiomannosides
  作者：David Crich、Hongmei Li

  DOI：10.1021/jo9914667

  日期：2000.2.1

  A highly diastereoselective synthesis of beta-thiomannopyranosides is described in which S-phenyl 2,3-di-0-benzyl-4,6-O-benzylidene-1-deoxy-1-thia-alpha-D-mannopyranoside S-oxide is treated with triflic anhydride and 2,6-di-tert-butyl-4-methylpyridine in CH2Cl2 at -78 degrees C leading to the formation of an intermediate alpha-mannosyl triflate. Addition of primary, secondary, or tertiary thiols then leads to the beta-thiomannosides, by an S(N)2-like displacement, in good yield and with excellent stereoselectivity. Deprotection is achieved either by Birch reduction or by Zemplen deacetylation, of the acetyl protected aglycons, followed by hydrogenolysis over Pearlman's catalyst. The assignment of configuration of the beta-thiomannopyranosides is discussed in terms of the chemical shift of the mannose H5 resonance and the (1)J(CH) of the mannose anomeric carbon.