Methyl 2,3,4-tri-O-benzyl-7,8-dideoxy-L-glycero-α-D-gluco-oct-7-enopyranoside | 103597-23-5

• 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-7,8-dideoxy-L-glycero-α-D-gluco-oct-7-enopyranoside
• 英文别名: (1S)-1-[(2R,3S,4S,5R,6S)-6-methoxy-3,4,5-tris(phenylmethoxy)oxan-2-yl]prop-2-en-1-ol
• CAS: 103597-23-5
• 化学式: C₃₀H₃₄O₆
• 分子量: 490.596
• InChiKey: ROJJHGZTXDZFQU-FKZASGQMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  36
• 可旋转键数：
  12
• 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-7,8-dideoxy-L-glycero-α-D-gluco-oct-7-enopyranoside 在 四氧化锇 、 水 、 sodium hydride 、 N-甲基吗啉氧化物 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 、 叔丁醇 为溶剂， 反应 72.0h， 生成 (2S,3S)-3-Benzyloxy-3-((2R,3S,4S,5R,6S)-3,4,5-tris-benzyloxy-6-methoxy-tetrahydro-pyran-2-yl)-propane-1,2-diol
  参考文献：
  名称：

  Jarosz; Kozlowska, Polish Journal of Chemistry, 1996, vol. 70, # 1, p. 45 - 53

  摘要：

  DOI：
• 作为产物：
  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 catalyst 氢气 作用下， 以 甲苯 为溶剂， 生成 Methyl 2,3,4-tri-O-benzyl-7,8-dideoxy-L-glycero-α-D-gluco-oct-7-enopyranoside
  参考文献：
  名称：

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

  摘要：

  DOI：

文献信息

• Construction of the Octose 8-Phosphate Intermediate in Lincomycin A Biosynthesis: Characterization of the Reactions Catalyzed by LmbR and LmbN
  作者：Eita Sasaki、Chia-I Lin、Ke-Yi Lin、Hung-wen Liu

  DOI：10.1021/ja308221z

  日期：2012.10.24

  Lincomycin A is a potent antimicrobial agent noted for its unusual C1 methylmercapto-substituted 8-carbon sugar. Despite its long clinical history for the treatment of Gram-positive infections, the biosynthesis of the C-8-sugar, methylthiolincosamide (MTL), is poorly understood. Here, we report our studies of the two initial enzymatic steps in the MTL biosynthetic pathway leading to the identification of D-erythro-D-gluco-octose 8-phosphate as a key intermediate. Our experiments demonstrate that this intermediate is formed via a transaldol reaction catalyzed by LmbR using D-fructose 6-phosphate or D-sedoheptulose 7-phosphate as the C-3 donor and D-ribose 5-phosphate as the C-5 acceptor. Subsequent 1,2-isomerization catalyzed by LmbN converts the resulting 2-keto C-8-sugar (octulose 8-phosphate) to octose 8-phosphate. These results provide, for the first time, in vitro evidence for the biosynthetic origin of the C-8 backbone of MTL.
• 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
  作者：Stanislas Czernecki、Stefan Horns、Jean-Marc Valery

  DOI：10.1021/jo00108a030

  日期：1995.2

  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%).
• Ring-closing metathesis as a new strategy for the C–C coupling of monosaccharide derivatives via silicon tethering
  作者：Michael Lobbel、Peter Köll

  DOI：10.1016/s0957-4166(99)00504-2

  日期：2000.2

  Suitable carbohydrate-derived terminal olefins have been coupled by ring-closing metathesis reaction following a silicon tethering strategy, generating very long contiguous chains of carbon atoms each equipped with specific stereochemistry and functionality. (C) 2000 Elsevier Science Ltd. All rights reserved.
• Jarosz; Skora; Kosciolowska, Polish Journal of Chemistry, 1999, vol. 73, # 11, p. 1797 - 1802
  作者：Jarosz、Skora、Kosciolowska

  DOI：——

  日期：——
• Jarosz; Kozlowska, Polish Journal of Chemistry, 1996, vol. 70, # 1, p. 45 - 53
  作者：Jarosz、Kozlowska

  DOI：——

  日期：——