2,3,4,6-tetra-O-benzyl-1-thio-β-D-galactopyranose | 857892-47-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2,3,4,6-tetra-O-benzyl-1-thio-β-D-galactopyranose
• 英文别名: (2S,3R,4S,5S,6R)-3,4,5-tris(phenylmethoxy)-6-(phenylmethoxymethyl)oxane-2-thiol
• CAS: 857892-47-8
• 化学式: C₃₄H₃₆O₅S
• 分子量: 556.723
• InChiKey: LJMMNXCZSYDRSR-YODGASFJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6
• 重原子数：
  40
• 可旋转键数：
  13
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  47.2
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  2,3,4,6-tetra-O-benzyl-1-thio-β-D-galactopyranose 在 叔丁基亚磺酰氯 、 三乙胺 作用下， 以 甲苯 为溶剂， 反应 0.33h， 以55%的产率得到(3R,4S,5S,6R)-3,4,5-Tris-benzyloxy-6-benzyloxymethyl-tetrahydro-pyran-2-thione
  参考文献：
  名称：

  从1-硫代糖一锅法合成碳水化合物硫代内酯

  摘要：

  为碳水化合物thionolactones的从合成的一般和高效的一锅法相应的1- thiosugar是描述涉及一中间的糖基的形成小号-叔丁基硫代亚磺酸酯在原位治疗与市售硫醇的叔丁基亚磺酰氯在室温下甲苯，然后热解。该方法还可用于直接从硫醇生成反应性硫醛和硫酮，这些硫醇和硫酮可用合适的二烯就地捕获。

  DOI：

  10.1016/j.tetlet.2008.05.145
• 作为产物：
  描述：

  triphenylmethyl 2,3,4,6-tetra-O-benzyl-1-thio-β-D-galactopyranoside 在 三乙基硅烷 、 三氟乙酸 作用下， 以 二氯甲烷 为溶剂， 反应 0.17h， 以88%的产率得到2,3,4,6-tetra-O-benzyl-1-thio-β-D-galactopyranose
  参考文献：
  名称：

  2-Haloethyl 1-Thioglycosides as New Tools in Glycoside Syntheses. Part 1: Preparation, Characteristics, General Reactions

  摘要：

  2-卤乙基1-硫代糖苷在2-卤乙基功能被银盐或Lewis酸激活时是优秀的离去基团。这些硫代糖苷可以在原始Černý路线上合成，或者为了更复杂的糖苷合成需求与之更兼容，在通过2-(2-四氢吡喃-2-氧基)乙基糖苷或三苯基1-硫代糖苷的逐步程序中合成。糖苷化反应的初始步骤可能通过硫代环氧离子进行，这对于它们在糖苷合成中作为离去基团的反应性增加具有责任。描述了这种新系统在二糖合成中的反应性和选择性的基本特征。

  DOI：

  10.1135/cccc20041843

文献信息

• Efficient Synthesis of Methylene <i>exo</i>-Glycals:  Another Use of Glycosylthiomethyl Chlorides
  作者：Xiangming Zhu、Ying Jin、John Wickham

  DOI：10.1021/jo0623843

  日期：2007.3.1

  A new approach to the synthesis of methylene exo-glycals is described. Oxidation of glycosylthiolmethyl chloride (GTM-Cl) with mCPBA afforded the corresponding glycosylchloromethyl sulfone in almost quantitative yield, which underwent KOtBu-induced Ramberg−Bäcklund rearrangement to furnish the desired methylene exo-glycal in excellent yield.

  描述了合成亚甲基外-糖的新方法。用m CPBA氧化糖基硫醇基甲基氯（GTM-Cl），以几乎定量的收率得到相应的糖基氯甲基砜，其经历了KO tBu诱导的Ramberg-Bäcklund重排以优异的产率提供了所需的亚甲基外糖。
• Exploring the Native Chemical Ligation Concept for Highly Stereospecific Glycosylation Reactions
  作者：Kim Le Mai Hoang、Yaguang Bai、Xin Ge、Xue-Wei Liu

  DOI：10.1021/jo400020q

  日期：2013.6.7

  Various O-alkyl glycosides were obtained in a highly stereospecific manner with retention of configuration at the anomeric center. Our method has customized native chemical ligation concept for glycoconjugates synthesis, utilizing a meticulously controlled activating system. To explain the origin of stereoselective preference, an S(N)i mechanism was proposed and corroborated by computational calculations.
• MMTr as an efficient anomeric S-protecting group for the synthesis of glycosyl thiols
  作者：Xiangming Zhu

  DOI：10.1016/j.tetlet.2006.09.003

  日期：2006.11

  The 4-monomethoxytrityl (MMTr) group was introduced in high yields to anomeric sulfhydryl functions using commercially available MMTrCl. Significantly, it is stable to a variety of reaction conditions, including acids and bases, and is removable under very mild acidic conditions, which are compatible with the presence of a number of other acid-labile hydroxyl protecting groups. The successful preparation of seven glycosyl thiols indicates that MMTr has potential application for the synthesis of complex 1-thiosugars. (c) 2006 Elsevier Ltd. All rights reserved.
• 2-Haloethyl 1-Thioglycosides as New Tools in Glycoside Syntheses. Part 1: Preparation, Characteristics, General Reactions
  作者：Andreas Krüger、Jutta Pyplo-Schnieders、Hartmut Redlich、Pär Winkelmann

  DOI：10.1135/cccc20041843

  日期：——

  2-Haloethyl 1-thioglycosides are excellent leaving groups when the 2-haloethyl function is activated with silver salts or Lewis acids. These thioglycosides can be synthesized on the original Černý route or for better compatibility with the needs of a more complex glycoside synthesis, in stepwise procedures via 2-(2-tetrahydropyran-2-yloxy)ethyl glycosides or trityl 1-thioglycosides. The initial step in glycosidation reaction presumably proceeds via a thiiranium ion, which is responsible for their increased reactivity compared with normal thioethers as leaving groups in glycoside syntheses. Basic features of this new system with respect to reactivity and selectivity in disaccharide syntheses are described.

  2-卤乙基1-硫代糖苷在2-卤乙基功能被银盐或Lewis酸激活时是优秀的离去基团。这些硫代糖苷可以在原始Černý路线上合成，或者为了更复杂的糖苷合成需求与之更兼容，在通过2-(2-四氢吡喃-2-氧基)乙基糖苷或三苯基1-硫代糖苷的逐步程序中合成。糖苷化反应的初始步骤可能通过硫代环氧离子进行，这对于它们在糖苷合成中作为离去基团的反应性增加具有责任。描述了这种新系统在二糖合成中的反应性和选择性的基本特征。
• One-pot synthesis of carbohydrate thionolactones from 1-thiosugars
  作者：Brendan L. Wilkinson、Antony J. Fairbanks

  DOI：10.1016/j.tetlet.2008.05.145

  日期：2008.8

  commercially available tert-butylsulfinyl chloride in toluene at room temperature, followed by thermolysis. The method can also be used to generate reactive thioaldehydes and thioketones directly from thiols, which can be trapped in situ with a suitable diene.

  为碳水化合物thionolactones的从合成的一般和高效的一锅法相应的1- thiosugar是描述涉及一中间的糖基的形成小号-叔丁基硫代亚磺酸酯在原位治疗与市售硫醇的叔丁基亚磺酰氯在室温下甲苯，然后热解。该方法还可用于直接从硫醇生成反应性硫醛和硫酮，这些硫醇和硫酮可用合适的二烯就地捕获。