p-tolyl N-benzyl-2-amino-6-O-benzyl-2,3-N,O-carbonyl-2-deoxy-1-thio-β-D-glucopyranoside | 1352653-35-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: p-tolyl N-benzyl-2-amino-6-O-benzyl-2,3-N,O-carbonyl-2-deoxy-1-thio-β-D-glucopyranoside
• 英文别名: p-tolyl N-benzyl-2-amino-6-O-benzyl-2-N,3-O-carbonyl-2-deoxy-1-thio-β-D-glucopyranoside；(3aR,4S,6R,7S,7aR)-3-benzyl-7-hydroxy-4-(4-methylphenyl)sulfanyl-6-(phenylmethoxymethyl)-4,6,7,7a-tetrahydro-3aH-pyrano[3,4-d][1,3]oxazol-2-one
• CAS: 1352653-35-0
• 化学式: C₂₈H₂₉NO₅S
• 分子量: 491.608
• InChiKey: LFRZOLCFQAZGKN-ACFIUOAZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 重原子数：
  35
• 可旋转键数：
  8
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.32
• 拓扑面积：
  93.5
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  p-tolyl N-benzyl-2-amino-6-O-benzyl-2,3-N,O-carbonyl-2-deoxy-1-thio-β-D-glucopyranoside 在 吡啶 作用下， 以 二氯甲烷 、 二氯甲烷-D2 为溶剂， 反应 4.0h， 生成 triflyl 2-N-benzyl-6-O-benzyl-2,3-N,O-carbonyl-4-O-chloroacetyl-2-deoxy-α-D-glucopyranoside
  参考文献：
  名称：

  Electrochemical generation of 2,3-oxazolidinone glycosyl triflates as an intermediate for stereoselective glycosylation

  摘要：

  用低温电化学氧化从硫代糖苷生成带有2,3-噁唑啉醇保护基的糖基三氟甲磺酸酯。糖基三氟甲磺酸酯与醇在低温下反应，选择性地形成相应的糖苷β-选择性产物。然而，在高温反应条件下，在无碱存在的情况下观察到α-选择性。原位生成的三氟甲磺酸促进β-产物向α-产物的异构化。

  DOI：

  10.3762/bjoc.8.52
• 作为产物：
  描述：

  p-tolyl N-benzyl-2-amino-4,6-O-benzylidene-2,3-N,O-carbonyl-2-deoxy-1-thio-β-D-glucopyranoside 在 三乙基硅烷 、 三氟乙酸 作用下， 以 二氯甲烷 为溶剂， 反应 1.33h， 以80%的产率得到p-tolyl N-benzyl-2-amino-6-O-benzyl-2,3-N,O-carbonyl-2-deoxy-1-thio-β-D-glucopyranoside
  参考文献：
  名称：

  Joined use of oxazolidinone and desymmetric amino protection: a new strategy for protection of glucosamine

  摘要：

  Joined use of N-benzyl oxazolidinone and N-benzyl-N-benzyloxycarbonyl (N-BnCbz) desymmetric amino-protecting function is reported. The new synthetic approach enables the facile preparation of type I and type 2 LacNAc disaccharides in satisfactory yields. One-pot deprotection of N-BnCbz and O-benzyl ether is achieved by hydrogenolysis under mild conditions. (C) 2010 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2010.02.021

文献信息

• Substituent effects in endocyclic cleavage–recyclization anomerization reaction of pyranosides
  作者：Shino Manabe、Kazuyuki Ishii、Hiroko Satoh、Yukishige Ito

  DOI：10.1016/j.tet.2011.09.059

  日期：2011.12

  Pyranosides with 2,3-trans carbamate or 2,3-trans carbonate groups are anomerized under mild acidic conditions via endocyclic cleavage reaction. In order to understand the nature of the anomerization reaction via the endocyclic cleavage recyclization process, the substituent effects at various positions were investigated. (C) 2011 Elsevier Ltd. All rights reserved.
• Joined use of oxazolidinone and desymmetric amino protection: a new strategy for protection of glucosamine
  作者：Shih-Che Lin、Chin-Sheng Chao、Chiu-Ching Chang、Kwok-Kong T. Mong

  DOI：10.1016/j.tetlet.2010.02.021

  日期：2010.4

  Joined use of N-benzyl oxazolidinone and N-benzyl-N-benzyloxycarbonyl (N-BnCbz) desymmetric amino-protecting function is reported. The new synthetic approach enables the facile preparation of type I and type 2 LacNAc disaccharides in satisfactory yields. One-pot deprotection of N-BnCbz and O-benzyl ether is achieved by hydrogenolysis under mild conditions. (C) 2010 Elsevier Ltd. All rights reserved.
• Electrochemical generation of 2,3-oxazolidinone glycosyl triflates as an intermediate for stereoselective glycosylation
  作者：Toshiki Nokami、Akito Shibuya、Yoshihiro Saigusa、Shino Manabe、Yukishige Ito、Jun-ichi Yoshida

  DOI：10.3762/bjoc.8.52

  日期：——

  Glycosyl triflates with a 2,3-oxazolidinone protecting group were generated from thioglycosides by low-temperature electrochemical oxidation. The glycosyl triflates reacted with alcohols to give the corresponding glycosides β-selectively at low temperatures. However, α-selectivity was observed in the absence of base at elevated reaction temperatures. In situ generated triflic acid promotes the isomerization of β-products to α-products.

  用低温电化学氧化从硫代糖苷生成带有2,3-噁唑啉醇保护基的糖基三氟甲磺酸酯。糖基三氟甲磺酸酯与醇在低温下反应，选择性地形成相应的糖苷β-选择性产物。然而，在高温反应条件下，在无碱存在的情况下观察到α-选择性。原位生成的三氟甲磺酸促进β-产物向α-产物的异构化。