methyl-2,3,4-tri-O-benzyl-7,7,8,8-tetradehydro-7,8-dideoxy-β-L-glycero-D-gluco-octopyranoside | 103597-22-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl-2,3,4-tri-O-benzyl-7,7,8,8-tetradehydro-7,8-dideoxy-β-L-glycero-D-gluco-octopyranoside
• 英文别名: methyl 2,3,4-tri-O-benzyl-7,8-dideoxy-L-glycero-α-D-gluco-oct-7-ynopyranoside；Methyl 2,3,4-tri-O-benzyl-7,8-dideoxy-L-glycero-D-gluco-oct-7-ynopyranoside；(1S)-1-[(2R,3S,4S,5R,6S)-6-methoxy-3,4,5-tris(phenylmethoxy)oxan-2-yl]prop-2-yn-1-ol
• CAS: 103597-22-4
• 化学式: C₃₀H₃₂O₆
• 分子量: 488.58
• InChiKey: DEPWYGDFFRBGMF-FKZASGQMSA-N

物化性质

• 沸点：
  612.1±55.0 °C(Predicted)
• 密度：
  1.21±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  36
• 可旋转键数：
  11
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  66.4
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  methyl-2,3,4-tri-O-benzyl-7,7,8,8-tetradehydro-7,8-dideoxy-β-L-glycero-D-gluco-octopyranoside 在 palladium on activated charcoal 、 镍 吡啶 、 sodium periodate 、 四氧化锇 、 Zn(N₃)₂*Py₂ 、 偶氮二甲酸二异丙酯 、 氢气 、 potassium carbonate 、 三苯基膦 、 偶氮二甲酸二乙酯 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 甲苯 为溶剂， 25.0~45.0 ℃ 、101.33 kPa 条件下， 反应 43.33h， 生成 Methyl 6-(N-acetylamino)-6-deoxy-L-glycero-α-D-gluco-heptopyranosiduronic acid
  参考文献：
  名称：

  Chain-Extension of Carbohydrates. 5. Synthesis of the C-Glycosyl Amino Acid Moiety of Miharamycins Involving Stereocontrolled Ethynylation of Methyl 2,3,4-Tri-O-benzyl-.alpha.-D-gluco-hexodialdo-1,5-pyranoside

  摘要：

  A multistep synthesis of the C-glycosyl amino acid moiety of miharamycins from methyl 2,3,4-tri-O-benzyl-alpha-D-gluco-hexodialdo-1,5-pyranoside (1) is described, The ethynyl group was employed as a synthetic equivalent of the carboxylic acid function, In the key step, highly diastereoselective ethynylation of compound 1 with the Grignard reagent of (trimethylsilyl)acetylene in the presence of magnesium bromide followed by desilylation afforded acetylenic alcohols 4 and 5 (19:1). The L-glycero configuration at C(6) of the major isomer 4 was unambiguously proven by H-1 NMR of the 4,6-benzylidene derivative 9. The amino function was introduced at C(6) by reaction of 4 with zinc azide in the presence of triphenylphosphine and diisopropyl azodicarboxylate. Transformation of the resulting methyl 6-azido-2,3,4-tri-O-benzyl-6,7,8-trideoxy side (10) into methyl 6-(N-acetylamino)-2,3,4-tri-O-benzyl-6-deoxy-D-glycero-alpha-D-gluco-heptopyranosiduronic acid (17) was achieved by two different sequences of reactions: (1) oxidative cleavage of the triple bond, benzylation, reduction of the azido group, and N-acetylation or (2) reduction of the azido group, N-acetylation, oxidative cleavage of the triple bond, and treatment with phenyldiazomethane. The overall yield of the two sequences was different (41% versus 50%), showing the second method to be superior. Final debenzylation afforded methyl 6-(N-acetylamino)6-deoxy-L-glycero-alpha-D-gluco-heptopyranisoduronic acid (18). To prepare the epimeric amino acid derivative 28, the configuration at C(6) of 4 was inverted by a Mitsunobu reaction. The same sequence of reactions was applied to the so-obtained D-glycero isomer 5 and methyl 6-(N-acetyl-amino)-6-deoxy-L-glycero-alpha-D-gluco-heptopyranosiduronic acid (28) was obtained. In this case almost identical overall yields were obtained for the two different transformations of the azidoalkyne 20 to compound 28 (62% versus 63%).

  DOI：

  10.1021/jo00108a030
• 作为产物：
  描述：

  methyl 6-aldehydo-2,3,4-tri-O-benzyl-α-D-glucopyranoside 在 正丁基锂 、 四丁基氟化铵 、 magnesium bromide 作用下， 以 四氢呋喃 为溶剂， 反应 0.75h， 生成 methyl-2,3,4-tri-O-benzyl-7,7,8,8-tetradehydro-7,8-dideoxy-β-L-glycero-D-gluco-octopyranoside
  参考文献：
  名称：

  Chain-Extension of Carbohydrates. 5. Synthesis of the C-Glycosyl Amino Acid Moiety of Miharamycins Involving Stereocontrolled Ethynylation of Methyl 2,3,4-Tri-O-benzyl-.alpha.-D-gluco-hexodialdo-1,5-pyranoside

  摘要：

  A multistep synthesis of the C-glycosyl amino acid moiety of miharamycins from methyl 2,3,4-tri-O-benzyl-alpha-D-gluco-hexodialdo-1,5-pyranoside (1) is described, The ethynyl group was employed as a synthetic equivalent of the carboxylic acid function, In the key step, highly diastereoselective ethynylation of compound 1 with the Grignard reagent of (trimethylsilyl)acetylene in the presence of magnesium bromide followed by desilylation afforded acetylenic alcohols 4 and 5 (19:1). The L-glycero configuration at C(6) of the major isomer 4 was unambiguously proven by H-1 NMR of the 4,6-benzylidene derivative 9. The amino function was introduced at C(6) by reaction of 4 with zinc azide in the presence of triphenylphosphine and diisopropyl azodicarboxylate. Transformation of the resulting methyl 6-azido-2,3,4-tri-O-benzyl-6,7,8-trideoxy side (10) into methyl 6-(N-acetylamino)-2,3,4-tri-O-benzyl-6-deoxy-D-glycero-alpha-D-gluco-heptopyranosiduronic acid (17) was achieved by two different sequences of reactions: (1) oxidative cleavage of the triple bond, benzylation, reduction of the azido group, and N-acetylation or (2) reduction of the azido group, N-acetylation, oxidative cleavage of the triple bond, and treatment with phenyldiazomethane. The overall yield of the two sequences was different (41% versus 50%), showing the second method to be superior. Final debenzylation afforded methyl 6-(N-acetylamino)6-deoxy-L-glycero-alpha-D-gluco-heptopyranisoduronic acid (18). To prepare the epimeric amino acid derivative 28, the configuration at C(6) of 4 was inverted by a Mitsunobu reaction. The same sequence of reactions was applied to the so-obtained D-glycero isomer 5 and methyl 6-(N-acetyl-amino)-6-deoxy-L-glycero-alpha-D-gluco-heptopyranosiduronic acid (28) was obtained. In this case almost identical overall yields were obtained for the two different transformations of the azidoalkyne 20 to compound 28 (62% versus 63%).

  DOI：

  10.1021/jo00108a030

文献信息

• Inversion of configuration at the propargylic alcohol center in sugar acetylenes
  作者：Sławomir Jarosz、Joanna Głodek、Aleksander Zamojski

  DOI：10.1016/0008-6215(87)80192-1

  日期：1987.6
• Jarosz, Slawomir, Bulletin of the Polish Academy of Sciences: Chemistry, 1985, vol. 33, # 9-10, p. 391 - 396
  作者：Jarosz, Slawomir

  DOI：——

  日期：——
• JAROSZ, S.;GLODEK, J.;ZAMOJSKI, A., CARBOHYDR. RES., 163,(1987) N 2, 289-296
  作者：JAROSZ, S.、GLODEK, J.、ZAMOJSKI, A.

  DOI：——

  日期：——