phenyl 2,3,4,6-tetra-O-benzyl-1-thio-α-D-mannopyranoside

• 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-α-D-mannopyranoside
• 英文别名: a-D-Mannopyranoside, phenyl 2,3,4,6-tetrakis-O-(phenylMethyl)-1-thio-；(2R,3R,4S,5S,6R)-3,4,5-tris(phenylmethoxy)-2-(phenylmethoxymethyl)-6-phenylsulfanyloxane
• 化学式: C₄₀H₄₀O₅S
• 分子量: 632.821
• InChiKey: IKCMSYGNAFDJNX-WUXZAEFSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.9
• 重原子数：
  46
• 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：
  71.4
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  phenyl 2,3,4,6-tetra-O-benzyl-1-thio-α-D-mannopyranoside 在 N-溴代丁二酰亚胺(NBS) 、 水 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 二氯甲烷 、 丙酮 为溶剂， 生成 2,3,4,6-tetra-O-benzyl-α-D-mannopyranosyl trichloroacetimidate
  参考文献：
  名称：

  Some Aspects of Selectivity in the Reaction of Glycosyl Donors*

  摘要：

  Some advantages, disadvantages, and anomalies of various donors in glycosidations are discussed. By studying several two-component donor/acceptor-diol reactions, it is shown that regiopreferences are not very sensitive to the type of donor used. However, in competitive glycosidations within a given type of donor and between different types of donor, it is shown that regio- and chemoselectivities must be indexed to donor reactivity.

  DOI：

  10.1080/07328300500176528
• 作为产物：
  描述：

  benzyl 2-((((2S,3S,4S,5R,6R)-3,4,5-tris(benzyloxy)-6-((benzyloxy)methyl)tetrahydro-2H-pyran-2-yl)oxy)methyl)benzoate 在 palladium on activated charcoal 2,6-二叔丁基-4-甲基吡啶 、 4 A molecular sieve 、 ammonium acetate 、 氢气 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 2.5h， 生成 phenyl 2,3,4,6-tetra-O-benzyl-1-thio-α-D-mannopyranoside
  参考文献：
  名称：

  2'-羧基苄基糖苷：用于C-糖基化和转化为其他糖基供体的糖基供体。

  摘要：

  各种糖基受体与2'-羧基苄基（CB）2,3,4,6-四-O-苄基-β-D-吡喃葡萄糖苷和CB 2,3,4,6-四-O-苄基-α-的糖基化D-甘露糖吡喃糖苷作为糖基供体仅或主要以良好的收率提供了α-C-糖苷。CB糖苷也被转化为其他众所周知的糖基供体，相应的苯基硫代糖苷和糖基氟化物衍生物。

  DOI：

  10.1016/j.carres.2006.03.014
• 作为试剂：
  描述：

  3,4,6-tri-O-benzoyl-β-D-mannopyranose 1,2-(pent-4-enyl orthobenzoate) 、 1,2,3,4-tetra-O-methyl-α-D-glucopyranose 在 N-碘代丁二酰亚胺 、 phenyl 2,3,4,6-tetra-O-benzyl-1-thio-α-D-mannopyranoside 作用下， 以65%的产率得到methyl 2,3,4-tri-O-methyl-6-O-(2,3,4,6-tetra-O-benzoyl-α-D-mannopyranosyl)-α-D-glucopyranoside
  参考文献：
  名称：

  Some Aspects of Selectivity in the Reaction of Glycosyl Donors*

  摘要：

  Some advantages, disadvantages, and anomalies of various donors in glycosidations are discussed. By studying several two-component donor/acceptor-diol reactions, it is shown that regiopreferences are not very sensitive to the type of donor used. However, in competitive glycosidations within a given type of donor and between different types of donor, it is shown that regio- and chemoselectivities must be indexed to donor reactivity.

  DOI：

  10.1080/07328300500176528

文献信息

• Glycosylations Directed by the Armed-Disarmed Effect with Acceptors Containing a Single Ester Group
  作者：Thomas H. Schmidt、Robert Madsen

  DOI：10.1002/ejoc.200700347

  日期：2007.8

  A selective glycosylation reaction controlled by the armed-disarmed effect is described by the use of phenyl thioglycosides. The donor thioglycoside is fully protected with benzyl ethers while the acceptor thioglycoside contains benzyl ethers at position 2 and 3 and a strongly electron-withdrawing pentafluorobenzoate ester group at position 6. The coupling can be performed with galactose, glucose,

  通过使用苯基硫糖苷描述了由武装-解除武装效应控制的选择性糖基化反应。供体硫糖苷被苄基醚完全保护，而受体硫糖苷在 2 位和 3 位包含苄基醚，在 6 位包含一个强吸电子的五氟苯甲酸酯基团。偶联可以用半乳糖、葡萄糖、甘露糖和邻苯二甲酰亚胺保护葡萄糖胺以良好的产率提供相应的 1,4-连接的二糖。如果添加另一个受体和更多的促进剂，这些二糖可以作为糖基供体在同一个锅中进行额外的偶联反应。这样，可以在一次操作中实现两次连续的糖基化以提供三糖。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)
• Visible Light Enables Aerobic Iodine Catalyzed Glycosylation
  作者：Matthias Krumb、Tobias Lucas、Till Opatz

  DOI：10.1002/ejoc.201900143

  日期：2019.7.31

  and readily available photocatalyst was developed. Oxygen serves as a green and cost‐efficient terminal oxidant and irradiation is performed with a common household LED bulb. The scope of this glycosylation protocol was investigated in the synthesis of O‐glycosides with yields up to 95 %.

  开发了一种通用的方案，该方案使用碘作为廉价且容易获得的光催化剂来光诱导硫糖苷的催化活化。氧气是一种绿色且具有成本效益的终端氧化剂，并且使用普通的家用LED灯泡进行辐照。在O-糖苷的合成中研究了这种糖基化方案的范围，产率高达95％。
• Stereocontrolled glycoside synthesis by activation of glycosyl sulfone donors with scandium(<scp>iii</scp>) triflate
  作者：Amandine Xolin、Romain Losa、Aicha Kaid、Cédric Tresse、Jean-Marie Beau、François-Didier Boyer、Stéphanie Norsikian

  DOI：10.1039/c7ob02792c

  日期：——

  The activation of aryl glycosyl sulfone donors has been achieved using scandium(III) triflate and has led to the selective preparation of α-mannosides resulting from a post-glycosylation anomerization.

  使用三氟甲磺酸scan （III）已经实现了芳基糖基砜供体的活化，并导致了由糖基化后的异构化反应产生的α-甘露糖苷的选择性制备。
• IPy₂BF₄/HF-Pyridine:  A New Combination of Reagents for the Transformation of Partially Unprotected Thioglycosides and <i>n</i>-Pentenyl Glycosides to Glycosyl Fluorides
  作者：J. Cristóbal López、Paloma Bernal-Albert、Clara Uriel、Serafín Valverde、Ana M. Gómez

  DOI：10.1021/jo7018653

  日期：2007.12.1

  The combination of bis(pyridinium)iodonium (I) tetrafluoroborate (IPy2BF4), and hydrogen fluoride pyridine (HF-py) forms an iodine monofluoride (IF) synthetic equivalent that can be used in the preparation of partially unprotected glycosyl fluorides from partially unprotected n-pentenyl glycosides and thioglycosides, thus avoiding the need for the protection/deprotection steps normally required in

  四氟硼酸双（吡啶）碘鎓（I）（IPy 2 BF 4）和氟化氢吡啶（HF-py）的组合形成碘一氟化物（IF）合成等价物，可用于制备部分未保护的糖基氟化物部分未保护的正戊烯基糖苷和巯基糖苷，因此避免了通常需要在该转化中进行的保护/去保护步骤。
• DIDMH in combination with triflic acid - A new promoter system for thioglycoside glycosyl donors
  作者：Mads Heuckendorff、Henrik H. Jensen

  DOI：10.1016/j.carres.2017.11.012

  日期：2018.1

  We have explored the possibility of using 1,3-diiodo-5,5-dimethylhydantoin (DIDMH) as an alternative to N-iodosuccinimide (NIS) for activation of glycosyl donors of the thioglycoside type in various glycosylation reactions. DIDMH was found to match NIS when it comes to the capability to activate thioglycosides and provide glycosylation products in good yields. Notably, with the two equivalents of reactive

  我们已经探索了在各种糖基化反应中使用1,3-二碘-5,5-二甲基乙内酰脲（DIDMH）替代N-碘琥珀酰亚胺（NIS）来活化硫代糖苷类型糖基供体的可能性。在激活硫糖苷和提供高收率糖基化产物的能力方面，发现DIDMH与NIS相匹配。值得注意的是，每个DIDMH分子具有两个当量的反应性碘鎓离子，因此只需添加较少的质量即可使该活化剂在经济上成为NIS的替代原子。此外，发现DIDMH可以在储存数周后保持稳定，并且价格与NIS相当。掌握了这些知识后，我们因此鼓励糖类社区考虑使用DIDMH在糖基化反应中激活硫糖苷。