methyl (6R)-(6-2H1)-3,4-di-O-benzyl-2-deoxy-2-N-acetamido-α-D-glucose | 213487-06-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl (6R)-(6-2H1)-3,4-di-O-benzyl-2-deoxy-2-N-acetamido-α-D-glucose
• 英文别名: N-[(2S,3R,4R,5S,6R)-6-[(R)-deuterio(hydroxy)methyl]-2-methoxy-4,5-bis(phenylmethoxy)oxan-3-yl]acetamide
• CAS: 213487-06-0
• 化学式: C₂₃H₂₉NO₆
• 分子量: 416.478
• InChiKey: AAKAUOBGYOAJKZ-JLPDPCOTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  30
• 可旋转键数：
  9
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  86.2
• 氢给体数：
  2
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  methyl (6R)-(6-2H1)-3,4-di-O-benzyl-2-deoxy-2-N-acetamido-α-D-glucose 在 palladium dihydroxide 氢气 作用下， 以 乙醇 、 溶剂黄146 为溶剂， 反应 24.0h， 以85%的产率得到methyl (6R)-(6-2H1)-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 sodium hydroxide 、 草酰氯 、 (R)-(+)-Alpine-Borane-d 、 氢溴酸 、 双氧水 、 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 17.58h， 生成 methyl (6R)-(6-2H1)-3,4-di-O-benzyl-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

文献信息

• 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.