phenyl 2,3,4,6-tetra-O-benzyl-1-thio-β-D-glucopyranoside S-oxide | 117307-17-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: phenyl 2,3,4,6-tetra-O-benzyl-1-thio-β-D-glucopyranoside S-oxide
• 英文别名: phenyl 2,3,4,6-tetra-O-benzyl-1-thio-β-D-glucopyranoside sulfoxide；phenylsulfenyl 2,3,4,6-tetra-O-benzyl-β-D-glucopyranoside；(2R,3R,4S,5R,6S)-3,4,5-Tris(benzyloxy)-2-((benzyloxy)methyl)-6-(phenylsulfinyl)tetrahydro-2H-pyran；(2S,3R,4S,5R,6R)-2-(benzenesulfinyl)-3,4,5-tris(phenylmethoxy)-6-(phenylmethoxymethyl)oxane
• CAS: 117307-17-2
• 化学式: C₄₀H₄₀O₆S
• 分子量: 648.82
• InChiKey: SZCBPJJRURAJJH-IUOJASHRSA-N

物化性质

• 沸点：
  777.6±60.0 °C(Predicted)
• 密度：
  1.26±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.4
• 重原子数：
  47
• 可旋转键数：
  15
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  82.4
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  phenyl 2,3,4,6-tetra-O-benzyl-1-thio-β-D-glucopyranoside S-oxide 在 lithium diisopropyl amide 作用下， 生成
  参考文献：
  名称：

  Direct Lithiation of glycals. Synthesis of C-2 branched sugars

  摘要：

  DOI：

  10.1016/s0040-4039(00)84896-0
• 作为产物：
  描述：

  (2R,3R,4S,5R,6S)-2-(acetoxymethyl)-6-(phenylthio)tetrahydro-2H-pyran-3,4,5-triyl triacetate 在 sodium hydroxide 、 H⁺ resin 、 四丁基高氯酸铵 、 双氧水 、 sodium methylate 、 乙酸酐 、 silica gel 作用下， 以 二氯甲烷 为溶剂， 反应 23.0h， 生成 phenyl 2,3,4,6-tetra-O-benzyl-1-thio-β-D-glucopyranoside S-oxide
  参考文献：
  名称：

  The efficient synthesis of a bis-glycosylated steroid drug transport reagent: Methyl 3-β-amino-7α, 12α-di(1′α-glucosyl)-5β-cholate (TC002)

  摘要：

  The drug transport reagent, methyl 3-beta-amino-7 alpha, 12 alpha-di(1'alpha-glucosyl)-5 beta-cholate (TC002) I was prepared in 15% overall yield from pentaacetyl glucose and methyl cholate. Pentaacetyl glucose was converted to glucosyl sulfoxide 2 in 56% overall yield. Methyl cholate was converted to methyl 3-beta-azido cholate 3 in 67% yield. Bis-glycosylation of 3 with 2 followed by a single step reduction provided 1. (C) 1997 Elsevier Science Ltd.

  DOI：

  10.1016/s0960-894x(97)00410-1

文献信息

• The Total Synthesis of Moenomycin A
  作者：James G. Taylor、Xuechen Li、Markus Oberthür、Wenjiang Zhu、Daniel E. Kahne

  DOI：10.1021/ja065907x

  日期：2006.11.1

  Moenomycin A is the only known natural antibiotic that inhibits bacterial cell wall synthesis by binding to the transglycosylases that catalyze formation of the carbohydrate chains of peptidoglycan. We report here the total synthesis of moenomycin A using the sulfoxide glycosylation method. A newly discovered byproduct of sulfoxide reactions was isolated that resulted in substantial loss of the glycosyl

  Moenomycin A 是唯一一种已知的天然抗生素，它通过与催化肽聚糖碳水化合物链形成的转糖基酶结合来抑制细菌细胞壁合成。我们在这里报告了使用亚砜糖基化方法对 moenomycin A 的全合成。分离出一种新发现的亚砜反应副产物，该副产物导致糖基受体的大量损失。介绍了一种抑制这种副产物的通用方法，它使糖基化能够有效地进行。亚砜糖基化的反向添加协议也证明在构建一些糖苷键时必不可少。合成路线灵活，可以构建衍生物以进一步分析莫诺霉素 A 的作用机制。
• AuCl3-AgOTf promoted O-glycosylation using anomeric sulfoxides as glycosyl donors at room temperature
  作者：Ashokkumar Palanivel、Ande Chennaiah、Sateesh Dubbu、Asadulla Mallick、Yashwant D. Vankar

  DOI：10.1016/j.carres.2016.11.012

  日期：2017.1

  glycosyl donors using AuCl3/AgOTf reagent system has been described. Under optimal reaction conditions, both armed and disarmed glycosyl sulfoxide donors were found to react with a range of primary, secondary, and tertiary alcohol acceptors, and sugar derived glycosyl acceptors to afford the corresponding glycosides in moderate to good yields with predictable selectivity. The reactions are quick (20-60 min)

  已经描述了使用AuCl3 / AgOTf试剂系统将亚砜活化为糖基供体。在最佳反应条件下，发现武装和解除武装的糖基亚砜供体都与一定范围的伯，仲和叔醇受体和糖衍生的糖基受体反应，以中等到良好的产率提供了可预测的选择性的相应糖苷。反应快速（20-60分钟），在室温下容易进行，并且反应条件可耐受酸敏感性基团。
• Sulfenate Intermediates in the Sulfoxide Glycosylation Reaction
  作者：Jeff Gildersleeve、Robert A. Pascal、Daniel Kahne

  DOI：10.1021/ja980827h

  日期：1998.6.1

  The sulfoxide glycosylation reaction works remarkably well for many difficult glycosylations. We attribute this in part to the fact that an extremely reactive intermediate can be generated rapidly under mild conditions at low temperature. We find that anomeric sulfenates can be formed in the reaction and that these intermediates impede glycosylation at low temperature. A mechanism for sulfenate formation

  对于许多困难的糖基化，亚砜糖基化反应非常有效。我们将这部分归因于这样一个事实，即在低温温和条件下可以快速生成极富反应性的中间体。我们发现在反应中可以形成异头次磺酸盐，并且这些中间体在低温下会阻碍糖基化。提出了亚磺酸盐形成的机制，并提出了尽量减少亚磺酸盐形成的策略。还研究了异头亚磺酸盐的能量学和反应性。下面描述的机理研究也对其他糖基化反应有影响。
• Synthesis of methylene bridged C-disaccharides
  作者：Bernd Giese、Monika Hoch、Clemens Lamberth、Richard R. Schmidt

  DOI：10.1016/s0040-4039(00)80300-7

  日期：1988.1

  Addition of glycosyl radicals to the α-methylene lactones 8 obtained from the corresponding glycopyranosyl phenylsulfoxides 5a,b in convenient two step procedures provides methylene bridged C-disaccharides in high diastereoselectivities. Thus, after reduction of the lactone moiety the methylene bridged analogs 9–11 of kojibiose, ristobiose, and α-L-fucopyranosyl (1→2)-D-galactose, respectively, were

  在方便的两步方法中，将糖基基团加到由相应的吡喃葡萄糖基苯基亚砜5a，b得到的α-亚甲基内酯8上，可以高非对映选择性地形成亚甲基桥连的C-二糖。因此，在内酯部分还原后，分别获得了曲霉二糖，李斯托二糖和α-L-富双核糖基（1→2）-D-半乳糖的亚甲基桥接类似物9-11。
• Stereoselective Synthesis of the Core Structure of the Nephritogenoside Glycopeptide
  作者：Hong Zhang、Yali Wang、René Thürmer、Mark Meisenbach、Wolfgang Voelter

  DOI：10.1002/jlac.199719970910

  日期：1997.9

  readily accessible phenylsulfinyl glycoside proved to be an excellent glycosyl donor, leading to high yields and good selectivity. The extremely mild conditions utilized in glycosylation reactions allow trityl and other sensitive protecting groups to be used for temporary protection. The fact that phenyl thioglycosides function as glycosyl acceptors during the coupling reaction and can easily be transformed

  报道了使用苯基亚磺酰基方法在肾上腺皮质激素单元中构建O-糖苷键的新策略。容易获得的苯亚磺酰基糖苷被证明是出色的糖基供体，导致高收率和良好的选择性。糖基化反应中使用的极其温和的条件允许将三苯甲基和其他敏感的保护基团用于临时保护。苯基硫代糖苷在偶联反应过程中起糖基受体的作用，并且可以通过转化为苯基亚硫酰基糖苷而容易地转化为糖基供体，这一事实使得能够以非常方便的方式制备复杂的寡糖。