methyl-3-O-benzyl-2,6-didesoxy-β-L-lyxo-hexopyranoside | 63592-82-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl-3-O-benzyl-2,6-didesoxy-β-L-lyxo-hexopyranoside
• 英文别名: (2S,3S,4S,6R)-4-Benzyloxy-6-methoxy-2-methyl-tetrahydro-pyran-3-ol；methyl 3-O-benzyl-2,6-dideoxy-α-L-lyxo-hexopyranoside；methyl 2,6-dideoxy-3-O-benzyl-α-D-lyxo-hexopyranoside
• CAS: 63592-82-5；85230-78-0；90762-83-7；98750-47-1；107908-97-4；112612-41-6；131013-43-9
• 化学式: C₁₄H₂₀O₄
• 分子量: 252.31
• InChiKey: SVCVRKBFJZCARA-SULVTUCISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.71
• 重原子数：
  18.0
• 可旋转键数：
  4.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  47.92
• 氢给体数：
  1.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  methyl-3-O-benzyl-2,6-didesoxy-β-L-lyxo-hexopyranoside 在 吡啶 、 4-二甲氨基吡啶 、 氢氧化钾 、 N-溴代丁二酰亚胺(NBS) 、 18-冠醚-6 、 四丁基碘化铵 、 triethylamine tris(hydrogen fluoride) 、 zinc(II) iodide 作用下， 以 四氢呋喃 、 二氯甲烷 、 乙腈 为溶剂， 反应 3.5h， 生成 4-O-Acetyl-3-(3-O-benzyl-2,6-dideoxy-4-O-methyl-α-D-lyxo-pyranosyl)-2,6-dideoxy-β-D-lyxo-pyranose
  参考文献：
  名称：

  A highly stereoselective synthesis of the AB disaccharide unit of olivomycin A

  摘要：

  A highly stereoselective synthesis of the AB disaccharide (4c) of olivomycin A is described. The synthesis features the double asymmetric allylboration of alpha,beta-dialkoxy aldehyde 8 using tartrate allylboronate (S,S)-9, which provides triol derivative 10 with the correct relative and absolute stereochemistry for utilization in syntheses of the A and B monosaccharides. The derived diol benzyl ether 11 was converted into 3-hydroxy-2-deoxy-lyxo-pyranoside 16 and thioglycoside 18 via the intermediacy of alpha-methyl 2-deoxy-lyxo-pyranoside 14-alpha, and then 16 and 18 were coupled in CH2Cl2 at 23-degrees-C by using Nicolaou's NBS thioglycosidation procedure to give the alpha,alpha-disaccharide 4a with > 6:1 selectivity. Difficulties encountered in the hydrolysis or activation of the methyl glycoside function of 4a prompted the synthesis to be revised by using intermediates containing more easily deprotected anomeric silyl (TBDMS) ethers. Diol 11 was thus selectivity monosilylated to give 21, which was smoothly converted via 2-deoxy-lyxo-pyranose 23 into thioglycoside 18 and 2-deoxypyranoside 27, which possesses a TBMDS protecting group at the anomeric center. Intermediates 18 and 27 were coupled again by using the Nicolaou methodology in a CH3CN-THF cosolvent mixture at -42-degrees-C to give the AB disaccharide TBDMS acetal 4b with greater-than-or-equal-to 20:1 selectivity. Deprotection of the anomeric TBDMS acetal by using Et3NH+F- in CH3CN then completed the synthesis of the olivomycin AB disaccharide unit 4c.

  DOI：

  10.1021/jo00004a054
• 作为产物：
  描述：

  溴甲苯 在 sodium hydride 、 臭氧 、 溶剂黄146 、 乙酰氯 作用下， 反应 29.0h， 生成 methyl-3-O-benzyl-2,6-didesoxy-β-L-lyxo-hexopyranoside
  参考文献：
  名称：

  A highly stereoselective synthesis of the AB disaccharide unit of olivomycin A

  摘要：

  A highly stereoselective synthesis of the AB disaccharide (4c) of olivomycin A is described. The synthesis features the double asymmetric allylboration of alpha,beta-dialkoxy aldehyde 8 using tartrate allylboronate (S,S)-9, which provides triol derivative 10 with the correct relative and absolute stereochemistry for utilization in syntheses of the A and B monosaccharides. The derived diol benzyl ether 11 was converted into 3-hydroxy-2-deoxy-lyxo-pyranoside 16 and thioglycoside 18 via the intermediacy of alpha-methyl 2-deoxy-lyxo-pyranoside 14-alpha, and then 16 and 18 were coupled in CH2Cl2 at 23-degrees-C by using Nicolaou's NBS thioglycosidation procedure to give the alpha,alpha-disaccharide 4a with > 6:1 selectivity. Difficulties encountered in the hydrolysis or activation of the methyl glycoside function of 4a prompted the synthesis to be revised by using intermediates containing more easily deprotected anomeric silyl (TBDMS) ethers. Diol 11 was thus selectivity monosilylated to give 21, which was smoothly converted via 2-deoxy-lyxo-pyranose 23 into thioglycoside 18 and 2-deoxypyranoside 27, which possesses a TBMDS protecting group at the anomeric center. Intermediates 18 and 27 were coupled again by using the Nicolaou methodology in a CH3CN-THF cosolvent mixture at -42-degrees-C to give the AB disaccharide TBDMS acetal 4b with greater-than-or-equal-to 20:1 selectivity. Deprotection of the anomeric TBDMS acetal by using Et3NH+F- in CH3CN then completed the synthesis of the olivomycin AB disaccharide unit 4c.

  DOI：

  10.1021/jo00004a054