methyl 2-acetamido-3,4-di-O-benzyl-2-deoxy-β-D-glucopyranoside | 69892-53-1

• 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-β-D-glucopyranoside
• 英文别名: N-[(2R,3R,4R,5S,6R)-6-(hydroxymethyl)-2-methoxy-4,5-bis(phenylmethoxy)oxan-3-yl]acetamide
• CAS: 69892-53-1
• 化学式: C₂₃H₂₉NO₆
• 分子量: 415.486
• InChiKey: AAKAUOBGYOAJKZ-GNJRFXKQSA-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 2-acetamido-3,4-di-O-benzyl-2-deoxy-β-D-glucopyranoside 在 palladium dihydroxide sodium hydroxide 、 草酰氯 、 (R)-(+)-Alpine-Borane-d 、 氢气 、 双氧水 、 二甲基亚砜 、 三乙胺 作用下， 以 乙醇 、 溶剂黄146 为溶剂， -78.0~25.0 ℃ 、344.73 kPa 条件下， 反应 41.75h， 生成 methyl (6R)-(6-2H1)-2-deoxy-2-N-acetamido-β-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-2-acetamido-3,4-di-O-benzyl-6-O-trityl-2-deoxy-β-D-glucopyranosid 在 氢溴酸 作用下， 以 二氯甲烷 、 溶剂黄146 为溶剂， 反应 0.05h， 以100%的产率得到methyl 2-acetamido-3,4-di-O-benzyl-2-deoxy-β-D-glucopyranoside
  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

• Dimethylformamide-Modulated Kdo Glycosylation for Stereoselective Synthesis of α-Kdo Glycosides
  作者：Qixin Lou、Qingting Hua、Liangliang Zhang、You Yang

  DOI：10.1021/acs.orglett.9b04509

  日期：2020.2.7

  the stereoselective synthesis of the α-linked Kdo glycosides is developed. Glycosylation of the readily available peracetylated Kdo ortho-hexynylbenzoate with common acceptor alcohols using SPhosAuNTf2 as a promoter and DMF as a modulating molecule afforded a range of Kdo glycosides with good α-selectivities. Furthermore, the present method is effectively applied in the latent-active synthesis of the

  开发了一种简单而直接的DMF调节的α-选择性Kdo糖基化方法，用于α-连接的Kdo糖苷的立体选择性合成。使用SPhosAuNTf2作为促进剂和DMF作为调节分子，用常见的受体醇对容易获得的全乙酰化Kdo邻己炔基苯甲酸酯进行糖基化，得到了一系列具有良好α选择性的Kdo糖苷。此外，本发明方法有效地应用于潜在地合成在还原端带有连接子的α-连接的二-Kdo糖苷。最后，在低温NMR中对Kdo亚胺离子的首次观察为DMF调节的α-选择性Kdo糖基化的合理机理提供了证据。
• Synthesis of the First Tricomponent Bisubstrate Analogue That Exhibits Potent Inhibition against GlcNAc:β-1,4-Galactosyltransferase
  作者：Hironobu Hashimoto、Tsuyoshi Endo、Yasuhiro Kajihara

  DOI：10.1021/jo962235s

  日期：1997.4.1
• 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.