methyl (2R,4R,5S,6R)-4,5-bis(benzyloxy)-6-((benzyloxy)methyl)tetrahydro-2H-pyran-2-carboxylate | 119005-71-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl (2R,4R,5S,6R)-4,5-bis(benzyloxy)-6-((benzyloxy)methyl)tetrahydro-2H-pyran-2-carboxylate
• 英文别名: methyl (2R,4R,5S,6R)-4,5-bis(phenylmethoxy)-6-(phenylmethoxymethyl)oxane-2-carboxylate
• CAS: 119005-71-9
• 化学式: C₂₉H₃₂O₆
• 分子量: 476.569
• InChiKey: MUNDXEUCPZYKDN-HPQIJTKRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  35
• 可旋转键数：
  12
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.34
• 拓扑面积：
  63.2
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  methyl (2R,4R,5S,6R)-4,5-bis(benzyloxy)-6-((benzyloxy)methyl)tetrahydro-2H-pyran-2-carboxylate 在 sodium hydroxide 、 sodium hexamethyldisilazane 、 三氟乙酸 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 4.25h， 生成 (2R,4R,5S,6R)-2-(carboxymethyl)-4,5-bis(phenylmethoxy)-6-(phenylmethoxymethyl)oxane-2-carboxylic acid
  参考文献：
  名称：

  Synthesis of 2-deoxy-α- and -β-D-arabino-hexopyranosyl phosphonic acids and related compounds; analogues of early intermediates in the shikimate pathway

  摘要：

  Treatment of 1-O-acetyl-3,4,6-tri-O-benzyl-2-deoxy-D-arabino-hexopyranose 18 with trimethyl phosphite in the presence of trimethylsilyl triflate gave a separable mixture of dimethyl (3,4,6-tri-O-benzyl-alpha-D-arabino-hexopyranosyl)phosphonate 19 (35%) and the beta-anomer 20 (60%). The diethyl analogue of compound 20 could be prepared stereoselectively from tributyl (3,4,6-tri-O-benzyl-2-deoxy-beta-D-arabino-hexopyranosyl)stannane 21 and diethyl chlorophosphate.Reaction of 1,3,4,6-tetra-O-acetyl-2-deoxy-D-arabino-hexopykanose 23 with trimethyl phosphite and trimethylsilyl triflate gave dimethyl (3,4,6-tri-O-acetyl-2-deoxy-alpha-D-arabino-hexopyranosyl)phosphonate 25 and the beta-anomer 27 with some alpha-selectivity. Deprotection of compounds 25 and 27 gave the phosphonic acids 11 and 12 respectively. The esters 25 and 27 could be converted into methyl 3,4,6-tri-O-acetyl-2-deoxy-1-(dimethoxyphosphoryl)-beta-D-arabino-hexopyranoside 31 by free-radical bromination followed by methanolysis, and diethyl [3,4,6-tri-O-(tert-butyldiphenylsilyl)-2-deoxy-D -arabino-hex-1-enopyranosyl)phosphonate 33 was prepared by interaction of the 1-lithioglucal with diethyl chlorophosphate.Metallation of stannane 21 and reaction with methyl chloroformate gave methyl 2,6-anhydro-4,5,7-tri-O-benzyl-3-deoxy-D-gluco-heptonate 35 which could be alkylated with tert-butyl bromoacetate to give, after deprotection, 3,7-anhydro-3-carboxy-2,4-dideoxy-D-gluco-octonic acid 14.

  DOI：

  10.1039/p19960000431
• 作为产物：
  描述：

  1-O-acetyl-3,4,6-tri-O-benzyl-2-deoxy-D-arabino-hexopyranose 在 三氟化硼乙醚 、 sodium methylate 作用下， 以 甲醇 、 乙腈 为溶剂， 反应 14.25h， 生成 methyl (2R,4R,5S,6R)-4,5-bis(benzyloxy)-6-((benzyloxy)methyl)tetrahydro-2H-pyran-2-carboxylate
  参考文献：
  名称：

  Regioselective synthesis of naphthoquinone/naphthoquinol–carbohydrate hybrids by [4 + 2] anionic annulations and studies on their cytotoxicity

  摘要：

  一种新颖的方法用于合成萘醌/萘醌醇-碳水化合物混合物，其中Hauser环化反应被描述为关键的合成步骤。

  DOI：

  10.1039/c6ob02154a

文献信息

• An In-Depth Study on Ring-Closing Metathesis of Carbohydrate-Derived α-Alkoxyacrylates:  Efficient Syntheses of DAH, KDO, and 2-Deoxy-β-KDO
  作者：Koen F. W. Hekking、Marcel A. H. Moelands、Floris L. van Delft、Floris P. J. T. Rutjes

  DOI：10.1021/jo060913x

  日期：2006.8.1

  Novel, efficient synthetic pathways to DAH, KDO, and 2-deoxy-β-KDO are described. Ring-closing metathesis (RCM) of highly functionalized α-alkoxyacrylate fragments resulted in a series of synthetically versatile oxygen heterocyclic intermediates. Further functionalization of the resulting enol ether double bond and subsequent deprotection provided the natural products in high overall yields, starting

  描述了通往DAH，KDO和2-deoxy-β-KDO的新颖，有效的合成途径。高度官能化的α-烷氧基丙烯酸酯片段的闭环复分解（RCM）导致了一系列合成上通用的氧杂环中间体。从可商购的被保护的糖开始，所得烯醇醚双键的进一步官能化和随后的脱保护以高的总收率提供了天然产物。
• A concise synthesis of 3-deoxy-2-O-methyl-4,5,7-tri-O-benzyl-D-arabino-heptulosonic acid and related compounds from 3,4,6-tri-O-benzyl-D-glucal
  作者：David Crich、Timothy J. Ritchie

  DOI：10.1039/c39880000985

  日期：——

  A concise, de novo synthesis of the 3-deoxyulosonic acid glycosyl donors (14) and (15) from trio-O-benzyl-D-glucal and their transformation into the corresponding O-methyl glycosides is described.

  描述了由三-O-苄基-D-葡糖的3-脱氧核糖酸糖基供体（14）和（15）的简明的从头合成，以及它们向相应的O-甲基糖苷的转化。
• Crich, David; Ritchie, Timothy J., Journal of the Chemical Society. Perkin transactions I, 1990, # 4, p. 945 - 954
  作者：Crich, David、Ritchie, Timothy J.

  DOI：——

  日期：——
• CRICH, DAVID;RITCHIE, TIMOTHY J., J. CHEM. SOC. PT 1. PERKIN TRANS.,(1990) N, C. 945-954
  作者：CRICH, DAVID、RITCHIE, TIMOTHY J.

  DOI：——

  日期：——
• CRICH, DAVID; RITCHIE, TIMOTHY, J. CHEM. SOC. CHEM. COMMUN., N15, 1988, 985-986
  作者：CRICH, DAVID、 RITCHIE, TIMOTHY

  DOI：——

  日期：——