(2S,3S,4S,5R,6R)-6-Benzyloxy-3,4,5-tris-(2,2-dimethyl-propionyloxy)-tetrahydro-pyran-2-carboxylic acid methyl ester | 188003-23-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (2S,3S,4S,5R,6R)-6-Benzyloxy-3,4,5-tris-(2,2-dimethyl-propionyloxy)-tetrahydro-pyran-2-carboxylic acid methyl ester
• 英文别名: methyl (2S,3S,4S,5R,6R)-3,4,5-tris(2,2-dimethylpropanoyloxy)-6-phenylmethoxyoxane-2-carboxylate
• CAS: 188003-23-8
• 化学式: C₂₉H₄₂O₁₀
• 分子量: 550.646
• InChiKey: IXMSLJSWJBHRSX-YKZCJQPKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.4
• 重原子数：
  39
• 可旋转键数：
  14
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.66
• 拓扑面积：
  124
• 氢给体数：
  0
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  (2S,3S,4S,5R,6R)-6-Benzyloxy-3,4,5-tris-(2,2-dimethyl-propionyloxy)-tetrahydro-pyran-2-carboxylic acid methyl ester 在 N-溴代丁二酰亚胺(NBS) 、 水 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 silver(l) oxide 、 scandium tris(trifluoromethanesulfonate) 作用下， 以 四氢呋喃 、 氘代氯仿 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 19.5h， 生成 2,2-Dimethyl-propionic acid (2S,3R,4R,5R)-5-benzyloxy-4-(2,2-dimethyl-propionyloxy)-2-methoxyoxalyl-tetrahydro-furan-3-yl ester
  参考文献：
  名称：

  Regio and stereoselective conversion of Δ4-uronic acids to l-Ido- and d-glucopyranosiduronic acids

  摘要：

  Synthesis of L-ido- and D-glucopyranosiduronic acids was performed starting from protected Delta(4)-uronic acids 3a-f. Bromination of the C-4,5 double bond provided the trans-diaxial bromohydrin derivatives 6a-d, which were converted to the corresponding epoxides 7a-d in high yields. Direct reduction of these epoxides using borane-tetrahydrofuran complex afforded the o-glucopyranosiduronic acids 9b-d, while Lewis acid rearrangment through the C-4 keto intermediate 10b-d afforded the L-idopyranosiduronic acids 11b-d. (C) 1997, Elsevier Science Ltd.

  DOI：

  10.1016/s0040-4039(96)02514-2
• 作为产物：
  描述：

  苄基beta-D-吡喃葡糖苷酸甲酯三乙酸酯 在 吡啶 、 sodium methylate 作用下， 以 甲醇 为溶剂， 反应 12.0h， 生成 (2S,3S,4S,5R,6R)-6-Benzyloxy-3,4,5-tris-(2,2-dimethyl-propionyloxy)-tetrahydro-pyran-2-carboxylic acid methyl ester
  参考文献：
  名称：

  Regio and stereoselective conversion of Δ4-uronic acids to l-Ido- and d-glucopyranosiduronic acids

  摘要：

  Synthesis of L-ido- and D-glucopyranosiduronic acids was performed starting from protected Delta(4)-uronic acids 3a-f. Bromination of the C-4,5 double bond provided the trans-diaxial bromohydrin derivatives 6a-d, which were converted to the corresponding epoxides 7a-d in high yields. Direct reduction of these epoxides using borane-tetrahydrofuran complex afforded the o-glucopyranosiduronic acids 9b-d, while Lewis acid rearrangment through the C-4 keto intermediate 10b-d afforded the L-idopyranosiduronic acids 11b-d. (C) 1997, Elsevier Science Ltd.

  DOI：

  10.1016/s0040-4039(96)02514-2

文献信息

• Glycosidation with a Disarmed Glycosyl Iodide:  Promotion and Scope
  作者：Jennifer A. Perrie、John R. Harding、Clare King、Deborah Sinnott、Andrew V. Stachulski

  DOI：10.1021/ol035475k

  日期：2003.11.1

  [reaction: see text] Glucuronyl iodide 1 has been studied in detail as a "disarmed" glycosyl donor. In a model reaction, using N-iodosuccinimide (NIS) as a promoter and 2-phenylethanol as acceptor, best results were obtained using NIS with I(2), followed by trimethylsilyltrifluoromethanesulfonate (TMSOTf). When a series of primary and secondary alcohols was glycosylated using these conditions, yields

  [反应：见正文]葡糖醛酸碘化物1作为“解除武装”的糖基供体已被详细研究。在模型反应中，使用N-碘代琥珀酰亚胺（NIS）作为促进剂，使用2-苯基乙醇作为受体，使用具有I（2），然后是三甲基甲硅烷基三氟甲磺酸盐（TMSOTf）的NIS可获得最佳结果。当使用这些条件将一系列伯醇和仲醇糖基化时，可获得60-83％的β-葡糖醛酸内酯。各种“非重”金属盐也有效地催化了模型反应，但导致了反应性较低的仲醇产生大量的α-产物。
• Conformational study of synthetic Δ4-uronate monosaccharides and glycosaminoglycan-derived disaccharides
  作者：Hélène G. Bazin、Ishan Capila、Robert J. Linhardt

  DOI：10.1016/s0008-6215(98)00118-9

  日期：1998.5

  carboxy group was protected as a methyl or benzyl ester, the anomeric hydroxyl group as a benzyl glycoside and the 2 and 3 hydroxyl groups were protected with different substitution patterns as both ester and ether derivatives. Disaccharides containing delta 4-uronates were prepared from heparin layses. Their carboxy group was unprotected or protected as a benzyl ester and the two hydroxyls in the uronate

  化学合成了十六种4-尿酸δ单糖。它们的羧基被保护为甲基或苄基酯，异头羟基被保护为苄基糖苷，而2和3个羟基分别被不同的取代方式保护为酯和醚衍生物。由肝素酶制备含4-尿酸δ的二糖。它们的羧基未被保护或被保护为苄基酯，并且在尿酸酯部分中的两个羟基是游离的，因为O-磺基衍生物或被酰化。通过检查质子间的邻位偶合常数，使用1 H NMR研究了这些不饱和尿酸盐单糖和二糖残基的构象。δ4-尿酸酯残基采用2H1或1H2构象。
• Glucuronidation of alcohols using the bromosugar–iodonium reagent method
  作者：Andrew V Stachulski

  DOI：10.1016/s0040-4039(01)01333-8

  日期：2001.9

  The glycosidation method introduced by Field, employing bromosugars as donors in conjunction with iodine, has been evaluated for glucuronidation. Despite the low donor ability of glucuronates, beta -glucuronides were obtained in 70-85% yield from a number of primary alcohols, and in 50-65% from two secondary alcohols, using the pivaloyl compound 11 with NIS as promoter. By contrast, the use of IBr or ICI as promoter gave mainly the alpha -glucuronides. (C) 2001 Elsevier Science Ltd. All rights reserved.
• Regio and stereoselective conversion of Δ4-uronic acids to l-Ido- and d-glucopyranosiduronic acids
  作者：Hélène G Bazin、Robert.J Kerns、Robert J Linhardt

  DOI：10.1016/s0040-4039(96)02514-2

  日期：1997.2

  Synthesis of L-ido- and D-glucopyranosiduronic acids was performed starting from protected Delta(4)-uronic acids 3a-f. Bromination of the C-4,5 double bond provided the trans-diaxial bromohydrin derivatives 6a-d, which were converted to the corresponding epoxides 7a-d in high yields. Direct reduction of these epoxides using borane-tetrahydrofuran complex afforded the o-glucopyranosiduronic acids 9b-d, while Lewis acid rearrangment through the C-4 keto intermediate 10b-d afforded the L-idopyranosiduronic acids 11b-d. (C) 1997, Elsevier Science Ltd.