4-methylphenyl 3,4,6-tri-O-benzyl-1-thio-β-D-glucopyranoside | 793672-55-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 4-methylphenyl 3,4,6-tri-O-benzyl-1-thio-β-D-glucopyranoside
• 英文别名: (2S,3R,4R,5R,6R)-2-(4-methylphenyl)sulfanyl-4,5-bis(phenylmethoxy)-6-(phenylmethoxymethyl)oxan-3-ol
• CAS: 793672-55-6
• 化学式: C₃₄H₃₆O₅S
• 分子量: 556.723
• InChiKey: FADNYQJXIQUXGW-NEPHXMAZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.2
• 重原子数：
  40
• 可旋转键数：
  12
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  82.4
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  4-methylphenyl 3,4,6-tri-O-benzyl-1-thio-β-D-glucopyranoside 在 bis(1,5-cyclooctadiene)diiridium(I) dichloride 2,6-二叔丁基-4-甲基吡啶 、 碘 、 silver trifluoromethanesulfonate 、 sodium carbonate 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 50.0h， 生成 4-methylphenyl 3,4,6-tri-O-benzyl-2-O-(2-iodo-1-(1,2:3,4-di-O-isopropylidene-α-D-galactopyranos-6-O-yl)ethyl)-1-thio-β-D-glucopyranoside
  参考文献：
  名称：

  Stereospecific Synthesis of 1,2-cis Glycosides by Vinyl-Mediated IAD

  摘要：

  (GRAPHICS)Stereospecific 1,2-cis glycosylation of 2-O-vinyl thioglycosides, synthesized from the corresponding alcohols by Ir-catalyzed transvinylation with vinyl acetate, is achieved by iodine-mediated tethering of a range of primary and secondary carbohydrate acceptors, followed by intramolecular aglycon delivery (IAD). The use of such an intramolecular glycosylation strategy furnishes the desired alpha-gluco and beta-manno disaccharides in an entirely stereoselective manner.

  DOI：

  10.1021/ol048427o
• 作为产物：
  描述：

  3,4,6-三苄氧基-D-葡萄烯糖 在 18-冠醚-6 、 二甲基二环氧乙烷 、 potassium carbonate 作用下， 以 丙酮 为溶剂， 反应 2.5h， 生成 4-methylphenyl 3,4,6-tri-O-benzyl-1-thio-β-D-glucopyranoside
  参考文献：
  名称：

  2- O-苯甲氧基羰基保护的糖基供体：碳酸盐介导的对映体辅助非对映选择性糖基化的复兴†

  摘要：

  通过恢复一个古老的想法，我们证明了烷氧基羰基可用于糖基化反应，以通过在O -2处的碳酸酯部分的参与来实现完全的立体控制。制备了各种苄氧羰基保护的糖基供体，并将其用于对碱不稳定的化合物进行有效的1，2-反式糖基化和糖基酯的合成。

  DOI：

  10.1039/c9cc07194f

文献信息

• 2-<i>O</i>-Benzyloxycarbonyl protected glycosyl donors: a revival of carbonate-mediated anchimeric assistance for diastereoselective glycosylation
  作者：Julia Weber、Dennis Svatunek、Simon Krauter、Gregor Tegl、Christian Hametner、Paul Kosma、Hannes Mikula

  DOI：10.1039/c9cc07194f

  日期：——

  idea, we demonstrate that alkoxycarbonyl groups can be used in glycosylation reactions to achieve full stereocontrol through participation of a carbonate moiety at O-2. Various benzyloxycarbonyl-protected glycosyl donors were prepared and used for efficient 1,2-trans glycosylation of base-labile compounds and the synthesis of glycosyl esters.

  通过恢复一个古老的想法，我们证明了烷氧基羰基可用于糖基化反应，以通过在O -2处的碳酸酯部分的参与来实现完全的立体控制。制备了各种苄氧羰基保护的糖基供体，并将其用于对碱不稳定的化合物进行有效的1，2-反式糖基化和糖基酯的合成。
• 2-<i>O</i>-<i>N</i>-Benzylcarbamoyl as a Protecting Group To Promote β-Selective Glycosylation and Its Applications in the Stereoselective Synthesis of Oligosaccharides
  作者：Yin-Jen Lu、Yen-Hsun Lai、You-Yu Lin、Yi-Chi Wang、Pi-Hui Liang

  DOI：10.1021/acs.joc.8b00047

  日期：2018.4.6

  This study examines the utility of the N-benzylcarbamoyl (BnCar) protecting group in glycosylation reactions of the parent O-2 protected carbohydrate donor. It was found that the BnCar group imparted exclusively β-selectivity with primary and secondary alcohols. A mechanistic study revealed the activated intermediate to be the glycosyl triflate in a skew conformation, which results in β-selective glycosylation

  这项研究研究了N-苄氨基甲酰基（BnCar）保护基在亲本O -2保护的碳水化合物供体的糖基化反应中的作用。发现BnCar基团仅赋予伯醇和仲醇β-选择性。一项机理研究表明，活化的中间体为偏构型的三氟甲磺酸糖基酯，可通过类似S N 2的途径导致β选择性糖基化。BnCar基团可以使用亚硝酸四丁铵容易地裂解，而不会影响酯和醚保护基。综上所述，这些结果表明BnCar可用于合成复杂的低聚糖，这项工作需要对各种保护基进行精细的化学区分。
• Total Synthesis of a Glycoglycerolipid from<i>Meiothermus taiwanensis</i>through a One-Pot Glycosylation Reaction and Exploration of its Immunological Properties
  作者：Bhaswati Ghosh、Yen-Hsun Lai、Yu-Yin Shih、Tapan Kumar Pradhan、Chun-Hung Lin、Kwok-Kong Tony Mong

  DOI：10.1002/asia.201300933

  日期：2013.12

  The total synthesis of a glycoglycerolipid isolate of Meiothermus taiwanensis and its truncated structural analogues is reported. Our synthesis employed DMF‐modulated and low‐concentration glycosylation reactions for the construction of α‐ and β‐glycosidic bonds in the absence of participating protecting groups. Further simplification of the synthesis was achieved by employing a low‐concentration one‐pot

  报道了台湾Meiothermus taiwanensis的糖甘油脂分离物及其截短的结构类似物的总合成。我们的合成方法是在没有保护基团参与的情况下，采用DMF调节的低浓度糖基化反应来构建α-和β-糖苷键。通过采用低浓度单锅糖基化程序，进一步简化了合成过程。初步的免疫学研究表明，一种截短的结构类似物抑制了THP-1单核细胞的细胞因子产生。
• Iterative α-Glycosylation Strategy for 2-Deoxy- and 2,6-Dideoxysugars: Application to the One-Pot Synthesis of Deoxysugar-Containing Oligosaccharides
  作者：Jiun-Han Chen、Jyh-Herng Ruei、Kwok-Kong Tony Mong

  DOI：10.1002/ejoc.201400006

  日期：2014.3

  This paper describes the development of an iterative and α-selective glycosylation method for 2-deoxyglycosyl and 2,6-dideoxythioglycoside donors based on the DMF modulation concept. We used NMR spectroscopy to probe the 2-deoxyglycosyl imidinium intermediate and elucidated the conditions to decrease the formation of glycal and thus to increase the reaction yields. Further elaboration of the glycosylation

  本文描述了基于 DMF 调制概念的 2-脱氧糖基和 2,6-二脱氧硫糖苷供体的迭代和 α-选择性糖基化方法的开发。我们使用 NMR 光谱来探测 2-脱氧糖基亚胺鎓中间体，并阐明了减少糖醛形成从而提高反应产率的条件。糖基化方法的进一步阐述为含 2-脱氧和 2,6-双脱氧糖苷的低聚糖的迭代一锅法合成打开了大门。
• Neighboring-Group Participation by C-2 Ether Functions in Glycosylations Directed by Nitrile Solvents
  作者：Chin-Sheng Chao、Ching-Yu Lin、Shaheen Mulani、Wei-Cheng Hung、Kwok-kong Tony Mong

  DOI：10.1002/chem.201100732

  日期：2011.10.17

  Ether‐protecting functions at C‐2 hydroxy groups have been found to play participating roles in glycosylations when the reactions are conducted in nitrile solvent mixtures. The participation mechanism is based on intramolecular interaction between the lone electron pair of the oxygen atom of the C‐2 ether function and the nitrile molecule when they are positioned in a cis configuration. A 1,2‐cis glycosyl

  当在腈溶剂混合物中进行反应时，已发现在C-2羟基处的醚保护功能在糖基化中起参与作用。参与机制基于C-2醚功能的氧原子的孤电子对和腈分子以顺式排列时的分子内相互作用。形成一个1,2-顺式糖基恶唑啉鎓中间体。这种参与，再加上糖基供体的异头作用，赋予糖基化较高的1,2-反式选择性。该概念的进一步应用导致了α-（1→5）-阿拉伯低聚物的高效制备。