3,4,6-tri-O-benzyl-2,5-anhydro-D-mannose dimethylacetal | 129116-33-2

• 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-mannose dimethylacetal
• 英文别名: (2S,3S,4R,5R)-2-(dimethoxymethyl)-3,4-bis(phenylmethoxy)-5-(phenylmethoxymethyl)oxolane
• CAS: 129116-33-2
• 化学式: C₂₉H₃₄O₆
• 分子量: 478.585
• InChiKey: YDWAAWCVTAVKQK-VIJSPRBVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  35
• 可旋转键数：
  13
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  55.4
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  3,4,6-tri-O-benzyl-2,5-anhydro-D-mannose dimethylacetal 在 盐酸 、 sodium tetrahydroborate 、 sodium hydride 、 丙酮 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 7.25h， 生成 1,3,4,6-Tetra-O-benzyl-2,5-anhydro-D-mannitol
  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
• 作为产物：
  描述：

  甲醇 、 Tf(-2)[Bn(-3)][Bn(-4)][Bn(-6)]Glc1Me 在 吡啶 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 0.08h， 以97%的产率得到3,4,6-tri-O-benzyl-2,5-anhydro-D-mannose dimethylacetal
  参考文献：
  名称：

  Asymmetric cyclopropanation of allylic ethers: cleavage and regeneration of the chiral auxiliary

  摘要：

  The ring contraction reaction of 2-O-(trifluoromethyl)sulfonyl]oxy]-beta-D-glucopyranosides and their corresponding a-anomers is reported. The rearrangement was shown to occur under extremely mild basic conditions to allow isolation of acid-sensitive optically active substituted cyclopropylmethanols. The chiral auxiliary can be regenerated by converting the C-glucofuranoside, byproduct of the rearrangement, into tri-O-benzyl-D-glucal (two steps).

  DOI：

  10.1021/jo00056a028

文献信息

• Stereoselective Thallium-induced Ring Contraction of Glycals
  作者：Dana H. Braithwaite、CedricW. Holzapfel、D. Bradley G. Williams

  DOI：10.1039/a807128d

  日期：——

  Various glycals, treated with Tl(NO3)3·3H2O under mild conditions in an acetonitrile–methanol solvent mixture, underwent ring contraction in a stereoselective fashion, affording stable acetal products.

  在温和条件下，在乙腈-甲醇溶剂混合物中用Tl（NO 3）3 ·3H 2 O处理的各种糖，以立体选择性方式进行环收缩，得到稳定的乙缩醛产物。