methyl (4-O-benzoyl-2,3,6-tri-O-benzyl-α-D-glucopyranosyl)-(1→6)-2,3,4-tri-O-benzyl-α-D-glucopyranoside | 1352827-06-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl (4-O-benzoyl-2,3,6-tri-O-benzyl-α-D-glucopyranosyl)-(1→6)-2,3,4-tri-O-benzyl-α-D-glucopyranoside
• 英文别名: methyl O-(2,3,6-tri-O-benzyl-4-O-benzoyl-D-glucopyranosyl)-(1→6)-2,3,4-tri-O-benzyl-α-D-glucopyranoside；methyl 2,3,4-tri-O-benzyl-6-O-(4-O-benzoyl-2,3,6-tri-O-benzyl-β-D-glucopyranosyl)-α-D-glucopyranoside；methyl 6-O-(4-O-benzoyl-2,3,6-tri-O-benzyl-α-D-glucopyranosyl)-2,3,4-tri-O-benzyl-α-D-glucopyranoside；Bn(-2)[Bn(-3)][Bz(-4)][Bn(-6)]Glc(a1-6)[Bn(-2)][Bn(-3)][Bn(-4)]a-Glc1Me；[(2R,3R,4S,5R,6S)-6-[[(2R,3R,4S,5R,6S)-6-methoxy-3,4,5-tris(phenylmethoxy)oxan-2-yl]methoxy]-4,5-bis(phenylmethoxy)-2-(phenylmethoxymethyl)oxan-3-yl] benzoate
• CAS: 1352827-06-5
• 化学式: C₆₂H₆₄O₁₂
• 分子量: 1001.18
• InChiKey: KTNIISGQHLIJOA-GJQWJABHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.7
• 重原子数：
  74
• 可旋转键数：
  26
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  119
• 氢给体数：
  0
• 氢受体数：
  12

反应信息

• 作为产物：
  描述：

  (2R,3R,4S,5R,6S)-2-(acetoxymethyl)-6-(phenylthio)tetrahydro-2H-pyran-3,4,5-triyl triacetate 在 吡啶 、 三乙基硅烷 、 4-二甲氨基吡啶 、 1-(苯基亚硫酰基)哌啶 、 2,4,6-三叔丁基吡啶 、 sodium methylate 、 sodium hydride 、 三氟乙酸 作用下， 以 甲醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 2.0h， 生成 methyl (4-O-benzoyl-2,3,6-tri-O-benzyl-β-D-glucopyranosyl)-(1→6)-2,3,4-tri-O-benzyl-α-D-glucopyranoside 、 methyl (4-O-benzoyl-2,3,6-tri-O-benzyl-α-D-glucopyranosyl)-(1→6)-2,3,4-tri-O-benzyl-α-D-glucopyranoside
  参考文献：
  名称：

  Directing effect by remote electron-withdrawing protecting groups at O-3 or O-4 position of donors in glucosylations and galactosylations

  摘要：

  Glucosylations and galactosylations of various acceptors with donors possessing an electronwithdrawing benzylsulfonyl, benzoyl, or acetyl group at the O-3 or O-4 position were performed. A beta-directing effect by the benzylsulfonyl group at O-3 of the glucosyl donors and by the benzylsulfonyl and acyl groups at O-4 of the glucosyl donors was observed. In contrast, acyl groups at O-3 of the glucosyl donors and acyl groups at O-3 and O-4 of the galactosyl donors exhibited an alpha-directing effect. The alpha-directing effect is partly considered to remote participation of the acyl groups, whereas the beta-directing effect is somewhat attributed to the S(N)2-like reaction of the acceptor with the glycosyl triflate or the contact ion pair, which is stabilized by remote electron-withdrawing groups. Further evidence for the stability of the alpha-glycosyl triflates was determined by a low-temperature NMR study. (C) 2015 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2015.06.014

文献信息

• Halobenzoyl groups in glycosylation: effect on stereoselectivity and reactivity of glycosyl donors
  作者：S. Visansirikul、J. P. Yasomanee、A. V. Demchenko

  DOI：10.1007/s11172-015-0987-2

  日期：2015.5

  Described herein is the synthesis and evaluation of a series of glycosyl donors equipped with halobenzoyl substituents at O(4) and O(6) to study their properties in glycosylations. Among possible effects that may include carbonyl participation or H-bond mediated aglycone delivery, our results indicate that halobenzoyls act via a different mode.

  本文描述的是一系列在 O(4) 和 O(6) 处配备卤代苯甲酰基取代基的糖基供体的合成和评估，以研究它们在糖基化中的特性。在可能包括羰基参与或 H 键介导的苷元传递的可能影响中，我们的结果表明卤代苯甲酰基通过不同的模式起作用。
• Glycosidation of Thioglycosides in the Presence of Bromine: Mechanism, Reactivity, and Stereoselectivity
  作者：Sophon Kaeothip、Jagodige P. Yasomanee、Alexei V. Demchenko

  DOI：10.1021/jo2019174

  日期：2012.1.6

  Elaborating on previous studies by Lemieux for highly reactive "armed" bromides, we discovered that beta-bromide of the superdisarmed (2-O-benzyl-3,4,6-tri-O-benzoyl) series can be directly obtained from the thioglycoside precursor. When this bromide is glycosidated, alpha-glycosides form exclusively; however, the yields of such transformations may be low due to the competing anomerization into alpha-bromide that is totally unreactive under the established reaction conditions.
• Effect of Remote Picolinyl and Picoloyl Substituents on the Stereoselectivity of Chemical Glycosylation
  作者：Jagodige P. Yasomanee、Alexei V. Demchenko

  DOI：10.1021/ja307355n

  日期：2012.12.12

  O-Picolinyl and O-picoloyl groups at remote positions (C-3, C-4, and C-6) can mediate glycosylation reactions by providing high or even complete facial selectivity for the attack of the glycosyl acceptor. The set of data presented herein offers a strong evidence of the intermolecular H-bond tethering between the glycosyl donor and glycosyl acceptor counterparts while providing a practical new methodology for the synthesis of either 1,2-cis or 1,2-trans linkages. Challenging glycosidic linkages including alpha-gluco, beta-manno, and beta-rhamno have seen obtained with high or complete stereocontrol.
• Directing effect by remote electron-withdrawing protecting groups at O-3 or O-4 position of donors in glucosylations and galactosylations
  作者：Ju Yuel Baek、Hea-Won Kwon、Se Jin Myung、Jung Jun Park、Mi Young Kim、Dominea C.K. Rathwell、Heung Bae Jeon、Peter H. Seeberger、Kwan Soo Kim

  DOI：10.1016/j.tet.2015.06.014

  日期：2015.8

  Glucosylations and galactosylations of various acceptors with donors possessing an electronwithdrawing benzylsulfonyl, benzoyl, or acetyl group at the O-3 or O-4 position were performed. A beta-directing effect by the benzylsulfonyl group at O-3 of the glucosyl donors and by the benzylsulfonyl and acyl groups at O-4 of the glucosyl donors was observed. In contrast, acyl groups at O-3 of the glucosyl donors and acyl groups at O-3 and O-4 of the galactosyl donors exhibited an alpha-directing effect. The alpha-directing effect is partly considered to remote participation of the acyl groups, whereas the beta-directing effect is somewhat attributed to the S(N)2-like reaction of the acceptor with the glycosyl triflate or the contact ion pair, which is stabilized by remote electron-withdrawing groups. Further evidence for the stability of the alpha-glycosyl triflates was determined by a low-temperature NMR study. (C) 2015 Elsevier Ltd. All rights reserved.