3,4,6-tri-O-benzyl-2,5-anhydro-D-allose dimethylacetal | 37699-01-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3,4,6-tri-O-benzyl-2,5-anhydro-D-allose dimethylacetal
• CAS: 37699-01-7
• 化学式: C₂₉H₃₄O₆
• 分子量: 478.585
• InChiKey: YDWAAWCVTAVKQK-BIYDSLDMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.76
• 重原子数：
  35.0
• 可旋转键数：
  13.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  55.38
• 氢给体数：
  0.0
• 氢受体数：
  6.0

反应信息

• 作为产物：
  描述：

  甲醇 、 perbenzylated D-cellobial 在 thallium(III) nitrate 作用下， 反应 8.0h， 以90%的产率得到3,6-di-O-benzyl-4-O-(2,3,4,6-tetra-O-benzyl-β-D-glucopyranosyl)-2,5-anhydro-D-mannose dimethylacetal
  参考文献：
  名称：

  Stereoselective synthesis of tetrahydrofurans and linear methyl enol-ethers from glycals

  摘要：

  The O-benzyl derivatives of 1,5-anhydro-2-deoxy-D-arabino-hex-1-enitol (D-glucal, 1), 1,5-anhydro-2,6-dideoxy-L-arabino-hex-1-enitol (L-rhamnal, 7), and I,5-anhydro-2-deoxy-D-lyxo-hex-1-enitol (D-galactal, 9), underwent stereoselectively a ring contraction by treatment with thallium(II:I) nitrate (TTN) in MeOH, giving respectively the dimethylacetal derivatives of 3,4,6-tri-O-benzyl-2,5-anhydro-D-mannose, 3,4-di-O-benzyl-6-deoxy-2,5-anhydro-L-mannose (8) and 3,4,6-tri-O-benzyl-2,5-anhydro-D-talose (10).Conversely, the protected glycals 1, 7 and 9, underwent the ring opening reaction by action of the TTN-NaBH4, reagent in MeOH, providing the enantiomerically pure methyl enol-ethers 3,4,6-tri-O-benzyl-2-deoxy-1-O-methyl-D-arabino-hex-1-enitol, 3,4-di-O-benzyl-2,6-dideoxy-1-O-methyl-L-arabino-hex-1-enitol and 3,4,6-tri-O-benzyl-2-deoxy-1-O-methyl-D-lyxo-hex-1-enitol. The perbenzylated glycosyl-glycals, such as 3,4-di-O-benzyl-6-O-(2,3,4,6-tetra-O-benzyl-beta-D-glucopyranosyl)-1,5-anhydro-2-deoxy-D-arabino-hex-1-enitol (cellobial) (16), 3,6-di-O-benzyl-4-O-(2,3,4,6-tetra-O-benzyl-beta-D-galactopyranosyl)-1,5-anhydro-2-deoxy-D-arabino-hex-1-enitol (lactal) (19) and 3,4-di-O-benzyl-6-O-(2,3,4,6-tetra-O-benzyl-alpha-D-galactopyranosyl)-1,5-anhydro-2-deoxy-D-arabino-hex-1-enitol (melibial) (22), showed the same reactivity as the corresponding glycals by reaction with TTN in MeOH, resulting selectively in the ring contracted compounds at the glycal moiety. The reaction with TTN-NaBH4, in MeOH, carried out on 16, 19 and 22, led to the formation of the open chain derivatives at the glycal site. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0008-6215(97)10062-3