methyl 2-acetamido-3,4-di-O-benzyl-2-deoxy-α-D-gluco-hexodialdo-1,5-pyranoside | 213487-05-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 2-acetamido-3,4-di-O-benzyl-2-deoxy-α-D-gluco-hexodialdo-1,5-pyranoside
• 英文别名: N-[(2S,3R,4R,5S,6S)-6-formyl-2-methoxy-4,5-bis(phenylmethoxy)oxan-3-yl]acetamide
• CAS: 213487-05-9
• 化学式: C₂₃H₂₇NO₆
• 分子量: 413.47
• InChiKey: VKSVTNSXLVLRAL-JLMDMGSGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  30
• 可旋转键数：
  9
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.39
• 拓扑面积：
  83.1
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  methyl 2-acetamido-3,4-di-O-benzyl-2-deoxy-α-D-gluco-hexodialdo-1,5-pyranoside 在 palladium dihydroxide sodium hydroxide 、 (R)-(+)-Alpine-Borane-d 、 氢气 、 双氧水 、 对甲苯磺酸 作用下， 以 乙醇 、 溶剂黄146 、 N,N-二甲基甲酰胺 为溶剂， 25.0 ℃ 、344.73 kPa 条件下， 反应 59.0h， 生成 methyl (6R)-(6-2H1)-4,6-O-benzylidene-2-deoxy-2-N-acetamido-α-D-glucose
  参考文献：
  名称：

  Stereoselective Preparation of Deuterium-Labeled Sugars:  (6R)-(6-²H₁)-N-Acetylglucosamine Derivatives

  摘要：

  The preparation of methyl (6R)-(6-H-2(1))-2-deoxy-2-N-acetamido-alpha-D-glucose (8 alpha-d) and methyl (6R)-(6-H-2(1))-2-deoxy-2-N-acetamido-beta-D-glucose (8 beta-d) is described. The key step in the synthesis was the stereoselective reduction of a C6-aldehydo-GlcNAc derivative with (R)-(+)-Alpine-Borane-d. Reduction of either methyl 6-aldehydo-3,4-di-O-benzyl-alpha-GlcNAc (6 alpha) or methyl 6-aldehydo-3,4-di-O-benzyl-beta-GlcNAc (6 beta) using (R)-(+)-Alpine-Borane-d in CH2Cl2 was significantly more stereoselective (>15:1 stereoselectivity for both anomers) than was reduction with NaBD4 in MeOH. The absolute stereochemistry at C6 of the deuterated GlcNAc derivatives was determined from H-1 NMR analysis of the conformationally locked sugars, methyl (6R)-(6-H-2(1))-4,6-O-benzylidene-2-deoxy-2 N-acetamido-alpha-D-glucose (9 alpha-d) and methyl (6R)-(6-H-2(1))-4,6-O-benzylidene-2-deoxy-2- beta-D-glucose (9 beta-d). Comparison of (3)J(H5,H6) values and H-1-H-1 NOEs for the nondeuterated and deuterated benzylidene derivatives showed that reduction with (R)-(+)-Alpine-Borane-d gave the (6R)-(6-H-2(1)) epimer as the major product for both the GlcNAc alpha and beta methyl glycosides. This stereoselective reduction enabled the H-1 NMR signals for the prochiral H6 and H6' protons in a series of GlcNAc derivatives to be assigned.

  DOI：

  10.1021/jo980781a
• 作为产物：
  描述：

  methyl 3,4-di-O-benzyl-6-O-triphenylmethyl-2-acetamido-2-deoxy-a-D-glucopyranoside 在 草酰氯 、 氢溴酸 、 二甲基亚砜 、 三乙胺 作用下， 以 二氯甲烷 、 溶剂黄146 为溶剂， 反应 0.58h， 生成 methyl 2-acetamido-3,4-di-O-benzyl-2-deoxy-α-D-gluco-hexodialdo-1,5-pyranoside
  参考文献：
  名称：

  Stereoselective Preparation of Deuterium-Labeled Sugars:  (6R)-(6-²H₁)-N-Acetylglucosamine Derivatives

  摘要：

  The preparation of methyl (6R)-(6-H-2(1))-2-deoxy-2-N-acetamido-alpha-D-glucose (8 alpha-d) and methyl (6R)-(6-H-2(1))-2-deoxy-2-N-acetamido-beta-D-glucose (8 beta-d) is described. The key step in the synthesis was the stereoselective reduction of a C6-aldehydo-GlcNAc derivative with (R)-(+)-Alpine-Borane-d. Reduction of either methyl 6-aldehydo-3,4-di-O-benzyl-alpha-GlcNAc (6 alpha) or methyl 6-aldehydo-3,4-di-O-benzyl-beta-GlcNAc (6 beta) using (R)-(+)-Alpine-Borane-d in CH2Cl2 was significantly more stereoselective (>15:1 stereoselectivity for both anomers) than was reduction with NaBD4 in MeOH. The absolute stereochemistry at C6 of the deuterated GlcNAc derivatives was determined from H-1 NMR analysis of the conformationally locked sugars, methyl (6R)-(6-H-2(1))-4,6-O-benzylidene-2-deoxy-2 N-acetamido-alpha-D-glucose (9 alpha-d) and methyl (6R)-(6-H-2(1))-4,6-O-benzylidene-2-deoxy-2- beta-D-glucose (9 beta-d). Comparison of (3)J(H5,H6) values and H-1-H-1 NOEs for the nondeuterated and deuterated benzylidene derivatives showed that reduction with (R)-(+)-Alpine-Borane-d gave the (6R)-(6-H-2(1)) epimer as the major product for both the GlcNAc alpha and beta methyl glycosides. This stereoselective reduction enabled the H-1 NMR signals for the prochiral H6 and H6' protons in a series of GlcNAc derivatives to be assigned.

  DOI：

  10.1021/jo980781a

文献信息

• Homologation of methyl 2-azido- and 2-acetamido-3,4-di-O-benzyl-2-deoxy-d-hexopyranosides with allyloxymethylmagnesium chloride
  作者：Barbara Grzeszczyk、Aleksander Zamojski

  DOI：10.1016/s0008-6215(01)00078-7

  日期：2001.5

  Methyl 2-azido-2-deoxy-hexodialdo-1,5-pyranosides of the alpha-, beta -D-gluco and alpha -D-manno configuration as well as methyl 2-acetamido-2-deoxy-hexodialdo-1,5-pyranosides of the alpha- and beta -D-gluco configuration, protected at positions 3 and 4 with O-benzyl groups were reacted with an excess of allyloxymethylmagnesium or (phenyldimethylsilyl)methylmagnesium chlorides to afford mixtures of C-6 stereoisomeric heptopyranosides. Configuration of the products separated by column chromatography was assigned by H-1 NMR data. (C) 2001 Elsevier Science Ltd. All rights reserved.
• Stereoselective Preparation of Deuterium-Labeled Sugars:  (6<i>R</i>)-(6-²H₁)-<i>N</i>-Acetylglucosamine Derivatives
  作者：Margaret L. Falcone-Hindley、Jeffery T. Davis

  DOI：10.1021/jo980781a

  日期：1998.8.1

  The preparation of methyl (6R)-(6-H-2(1))-2-deoxy-2-N-acetamido-alpha-D-glucose (8 alpha-d) and methyl (6R)-(6-H-2(1))-2-deoxy-2-N-acetamido-beta-D-glucose (8 beta-d) is described. The key step in the synthesis was the stereoselective reduction of a C6-aldehydo-GlcNAc derivative with (R)-(+)-Alpine-Borane-d. Reduction of either methyl 6-aldehydo-3,4-di-O-benzyl-alpha-GlcNAc (6 alpha) or methyl 6-aldehydo-3,4-di-O-benzyl-beta-GlcNAc (6 beta) using (R)-(+)-Alpine-Borane-d in CH2Cl2 was significantly more stereoselective (>15:1 stereoselectivity for both anomers) than was reduction with NaBD4 in MeOH. The absolute stereochemistry at C6 of the deuterated GlcNAc derivatives was determined from H-1 NMR analysis of the conformationally locked sugars, methyl (6R)-(6-H-2(1))-4,6-O-benzylidene-2-deoxy-2 N-acetamido-alpha-D-glucose (9 alpha-d) and methyl (6R)-(6-H-2(1))-4,6-O-benzylidene-2-deoxy-2- beta-D-glucose (9 beta-d). Comparison of (3)J(H5,H6) values and H-1-H-1 NOEs for the nondeuterated and deuterated benzylidene derivatives showed that reduction with (R)-(+)-Alpine-Borane-d gave the (6R)-(6-H-2(1)) epimer as the major product for both the GlcNAc alpha and beta methyl glycosides. This stereoselective reduction enabled the H-1 NMR signals for the prochiral H6 and H6' protons in a series of GlcNAc derivatives to be assigned.