phenyl 2,6-di-O-benzyl-1-thio-β-D-glucopyranoside | 864966-93-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: phenyl 2,6-di-O-benzyl-1-thio-β-D-glucopyranoside
• 英文别名: (2R,3S,4S,5R,6S)-5-phenylmethoxy-2-(phenylmethoxymethyl)-6-phenylsulfanyloxane-3,4-diol
• CAS: 864966-93-8
• 化学式: C₂₆H₂₈O₅S
• 分子量: 452.571
• InChiKey: QXNBRIJJCCWLMY-RTJMFUJLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  32
• 可旋转键数：
  9
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  93.4
• 氢给体数：
  2
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  phenyl 2,6-di-O-benzyl-1-thio-β-D-glucopyranoside 在 三氟甲磺酸 吡啶 、 4-二甲氨基吡啶 、 N-碘代丁二酰亚胺 作用下， 以 二氯甲烷 为溶剂， 反应 14.0h， 生成 phenyl 2,3,4-tri-O-benzyl-6-O-(2,6-di-O-benzyl-3,4-di-O-tert-butyldimethylsilyl-β-D-glucopyranosyl)-1-thio-β-D-glucopyranoside
  参考文献：
  名称：

  “Super Armed” Glycosyl Donors:  Conformational Arming of Thioglycosides by Silylation

  摘要：

  Glycosyl donors protected with bulky silyl protective groups (tert-butyldimethylsilyl, TBS), on the 2-, 3-, and 4-OH groups were found to have superior reactivity compared with benzylated thioglucosides. The enhanced reactivity is explained by the stereoelectronic effects associated with the conformational change induced by the silylation. A TBS silylated thioglucoside donor has axial OR groups, whereas a benzylated thioglucoside has equatorial OR groups, leading to much more favorable charge-dipole interactions in the transition state. This concept could be used to create "super armed" glucosyl, mannosyl, rhamnosyl, and galactosyl donors, which could cross-couple with the armed acceptors, phenyl 2,3,4-tri-O- benzyl-beta-D-thioglucoside or phenyl 2,3,6-tri-O-benzyl-beta-D-thioglucoside, to give the corresponding armed disaccharides in good to excellent yields.

  DOI：

  10.1021/ja071955l
• 作为产物：
  描述：

  1-硫代-b-D-吡喃葡萄糖苷对甲苯酯 在 camphor-10-sulfonic acid 、 sodium hydride 、 三氟乙酸 、 原甲酸三甲酯 作用下， 以 甲醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 26.17h， 生成 phenyl 2,6-di-O-benzyl-1-thio-β-D-glucopyranoside
  参考文献：
  名称：

  Stereocontrolled Formation of β-Glucosides and Related Linkages in the Absence of Neighboring Group Participation:  Influence of a trans-Fused 2,3-O-Carbonate Group

  摘要：

  [GRAPHICS]Phenyl 4,6-di-O-benzyl-2,3-O-carbonyl-beta-D-glucothiopyranoside and the regiosiomeric phenyl 2,6-di-O-benzyl-3,4-O-carbonyl-beta-D-glucothiopyranoside were prepared and studied as glucosyl donors at -60 degrees C in dichloromethane with preactivation by 1-benzenesulfinyl piperidine before addition of the acceptor alcohol. The 2,3-O-carbonate protected donor showed moderate to excellent beta-selectivity under these conditions depending on the acceptor employed, thereby providing a means for 1,2-trans-equatorial glycosidic bonds without recourse to neighboring group participation and its associated problem of ortho ester formation. In contrast, the 3,4-O-carbonate protected donor showed moderate to no beta-selectivity under the conditions employed. The results obtained in this study with carbonate protected glucopyranosyl donors are contrasted with those obtained previously in the manno- and rhamnopyranosyl series when the 2,3-O-carbonate protected is (x-selective and the 3,4-O-carbonate is beta-selective.

  DOI：

  10.1021/jo0508999

文献信息

• Organotin-catalyzed regioselective benzylation of carbohydrate trans-diols
  作者：Hengfu Xu、Ying Zhang、Hai Dong、Yuchao Lu、Yuxin Pei、Zhichao Pei

  DOI：10.1016/j.tetlet.2017.08.043

  日期：2017.10

  approach to regioselective benzylation of carbohydrate trans-diols was developed, where 0.1 equiv. of Bu2SnCl2 and 0.1 equiv. of TBABr were used as the catalysts and 2.0 equiv. of BnCl was used as the benzylation reagent. In most cases, similar or better benzylation regioselectivities and isolated yields were obtained by using catalytic amounts of Bu2SnCl2, rather than stoichiometric amounts of organotin

  开发了一种方便的方法，用于碳水化合物反式二醇的区域选择性苄化，其中0.1当量。的Bu 2 SnCl 2和0.1当量 使用TBABr 2的催化剂作为催化剂，当量为2.0当量。将BnCl 2用作苄基化试剂。在大多数情况下，通过使用催化量的Bu 2 SnCl 2而不是所需化学计量的有机锡试剂，可获得相似或更好的苄基化区域选择性和分离的产率。
• Stereocontrolled Formation of β-Glucosides and Related Linkages in the Absence of Neighboring Group Participation:  Influence of a <i>trans</i>-Fused 2,3-<i>O</i>-Carbonate Group
  作者：David Crich、Prasanna Jayalath

  DOI：10.1021/jo0508999

  日期：2005.9.1

  [GRAPHICS]Phenyl 4,6-di-O-benzyl-2,3-O-carbonyl-beta-D-glucothiopyranoside and the regiosiomeric phenyl 2,6-di-O-benzyl-3,4-O-carbonyl-beta-D-glucothiopyranoside were prepared and studied as glucosyl donors at -60 degrees C in dichloromethane with preactivation by 1-benzenesulfinyl piperidine before addition of the acceptor alcohol. The 2,3-O-carbonate protected donor showed moderate to excellent beta-selectivity under these conditions depending on the acceptor employed, thereby providing a means for 1,2-trans-equatorial glycosidic bonds without recourse to neighboring group participation and its associated problem of ortho ester formation. In contrast, the 3,4-O-carbonate protected donor showed moderate to no beta-selectivity under the conditions employed. The results obtained in this study with carbonate protected glucopyranosyl donors are contrasted with those obtained previously in the manno- and rhamnopyranosyl series when the 2,3-O-carbonate protected is (x-selective and the 3,4-O-carbonate is beta-selective.
• “Super Armed” Glycosyl Donors:  Conformational Arming of Thioglycosides by Silylation
  作者：Christian Marcus Pedersen、Lars Ulrik Nordstrøm、Mikael Bols

  DOI：10.1021/ja071955l

  日期：2007.7.1

  Glycosyl donors protected with bulky silyl protective groups (tert-butyldimethylsilyl, TBS), on the 2-, 3-, and 4-OH groups were found to have superior reactivity compared with benzylated thioglucosides. The enhanced reactivity is explained by the stereoelectronic effects associated with the conformational change induced by the silylation. A TBS silylated thioglucoside donor has axial OR groups, whereas a benzylated thioglucoside has equatorial OR groups, leading to much more favorable charge-dipole interactions in the transition state. This concept could be used to create "super armed" glucosyl, mannosyl, rhamnosyl, and galactosyl donors, which could cross-couple with the armed acceptors, phenyl 2,3,4-tri-O- benzyl-beta-D-thioglucoside or phenyl 2,3,6-tri-O-benzyl-beta-D-thioglucoside, to give the corresponding armed disaccharides in good to excellent yields.