ethyl 6-O-[(tert-butyl)diphenylsilyl]-2,3-di-O-isopropylidene-1-thio-α-D-mannopyranoside | 316188-13-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: ethyl 6-O-[(tert-butyl)diphenylsilyl]-2,3-di-O-isopropylidene-1-thio-α-D-mannopyranoside
• 英文别名: ethyl 1-thio-2,3-di-O-isopropylidene-6-O-tert-butyldiphenylsilyl-α-D-mannopyranoside
• CAS: 316188-13-3
• 化学式: C₂₇H₃₈O₅SSi
• 分子量: 502.747
• InChiKey: QTJJAQOUTSVGHX-WJGLBBAVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.92
• 重原子数：
  34.0
• 可旋转键数：
  7.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  57.15
• 氢给体数：
  1.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  ethyl 6-O-[(tert-butyl)diphenylsilyl]-2,3-di-O-isopropylidene-1-thio-α-D-mannopyranoside 在 吡啶 、 咪唑 、 4 A molecular sieve 、 氢氟酸 、 四丁基氟化铵 、 水 、 sodium hydride 、 溶剂黄146 、 三乙胺 、 三氟甲烷磺酸甲酯 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 甲苯 、 乙腈 为溶剂， 反应 37.5h， 生成 (2'R,3'R) Ethyl 4-O-benzyl-6-O-tert-butyldimethylsilyl-2-O-chloroacetyl-3-O-(4-O-chloroacetyl-2,3-O-(2',3'-dimethoxybutane-2',3'-diyl)-6-O-(2,3,4,6-tetra-O-benzyl-α-D-galactopyranosyl)-α-D-galactopyranosyl)-1-thio-α-D-mannopyranoside
  参考文献：
  名称：

  Baeschlin, Daniel K.; Chaperon, Andre R.; Green, Luke G., Chemistry - A European Journal, 2000, vol. 6, # 1, p. 172 - 186

  摘要：

  DOI：
• 作为产物：
  描述：

  ethyl 1-thio-6-O-tert-butyldiphenylsilyl-α-D-mannopyranoside 生成 ethyl 6-O-[(tert-butyl)diphenylsilyl]-2,3-di-O-isopropylidene-1-thio-α-D-mannopyranoside
  参考文献：
  名称：

  合成中的双螺合酮（第5部分）：使用差异激活的糖基供体和受体进行寡糖合成的新机会

  摘要：

  双螺酮保护的硫糖苷的反应活性使其成为寡糖合成的有用的新前体，如制备布鲁氏锥虫变体表面糖蛋白共有的受保护的五糖单元所示。

  DOI：

  10.1016/s0040-4039(00)61375-8

文献信息

• Synthesis of monodeoxy analogues of the trisaccharide α-d-Glcp-(1→3)-α-d-Manp-(1→2)-α-d-ManpOMe recognised by Calreticulin/Calnexin
  作者：Emiliano Gemma、Martina Lahmann、Stefan Oscarson

  DOI：10.1016/j.carres.2006.03.015

  日期：2006.7

  Six (3,4,4',6',3" or 6")-monodeoxy analogues of the title trisaccharide (1-6) have been prepared utilising monodeoxy monosaccharide precursors. The reducing end deoxy derivatives were synthesised by N-iodosuccinimide/silver trifluoromethanesulfonate (NIS/AgOTf)-promoted couplings of a common disaccharide thioglycoside donor 10 to suitably protected monodeoxy acceptors 9 and 12, affording trisaccharides, which after deprotection yielded target structures 1 and 2. The non-reducing end deoxy derivatives could similarly be produced by halide-assisted glycosylations of a common disaccharide acceptor 17 with monodeoxy glycosyl bromide donors (obtained from thioglycosides 18 and 20) to yield, after removal of protecting groups, target trisaccharides 3 and 4. The analogues with the deoxy function in the middle mannose residue, were obtained through orthogonal halide-assisted coupling of tetrabenzyl-glucopyranosyl bromide to monodeoxy thioglycoside acceptors to give thioglycoside disaccharides, which subsequently were used as donors in NIS/AgOTf-promoted couplings to a common 2-hydroxy-mannose acceptor 15 to afford trisaccharides; deprotection yielded the final target compounds 5 and 6. (c) 2006 Elsevier Ltd. All rights reserved.
• ——
  作者：Gregor Lemanski、Thomas Ziegler

  DOI：10.1002/1522-2675(20001004)83:10<2655::aid-hlca2655>3.0.co;2-u

  日期：2000.10.4

  A series of prearranged glycosides 5, 17, 23, 28, 37 and 41, having a benzyl-protected 1-thiomannosyl donor linked through its positions 2, 3, 4 and 6 via succinate and malonate tethers, respectively, to positions 2, 3, and 6 of a benzyl glucopyranoside acceptor, were prepared by condensation of the respective mannosyl succinates and malonates with suitably protected benzyl glucopyranosides. The prearranged glycosides were intramolecularly coupled under various conditions to give the corresponding, tethered (1 --> 4)-linked disaccharides The yields and anomer ratios of the products of these couplings were interpreted in terms of the thermodynamic stability of the resulting disaccharides. In the case of prearranged glycoside 17, having positions 3 of both the donor and the acceptor linked by a succinate tether, a strong dependence of the diastereoselectivity of the intramolecular glycosylation on the activation procedure was observed. All other cases did not show a significant dependence of the outcome of the anomeric configuration in intramolecular glycosylation on the activation procedure or the solvent.