[(2R,3S,4S,5R,6R)-4,5-bis(phenylmethoxy)-6-(phenylmethoxymethyl)-2-pyridin-2-ylsulfonyloxan-3-yl]oxy-tert-butyl-dimethylsilane | 181506-87-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: [(2R,3S,4S,5R,6R)-4,5-bis(phenylmethoxy)-6-(phenylmethoxymethyl)-2-pyridin-2-ylsulfonyloxan-3-yl]oxy-tert-butyl-dimethylsilane
• CAS: 181506-87-6
• 化学式: C₃₈H₄₇NO₇SSi
• 分子量: 689.945
• InChiKey: VFYXGFTTWMJWCR-AHLMXRMGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.36
• 重原子数：
  48
• 可旋转键数：
  15
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.39
• 拓扑面积：
  102
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  [(2R,3S,4S,5R,6R)-4,5-bis(phenylmethoxy)-6-(phenylmethoxymethyl)-2-pyridin-2-ylsulfonyloxan-3-yl]oxy-tert-butyl-dimethylsilane 在 samarium diiodide 作用下， 以 四氢呋喃 、 乙腈 为溶剂， 生成 Methyl 4,6-di-O-benzoyl-3-O-benzyl-2-deoxy-2-C-<2-O-tert-butyldimethylsilyl-3,4,6-tri-O-benzyl-α-D-mannopyranosylmethyl(xanthateimidazole)>-α-D-mannopyranoside
  参考文献：
  名称：

  The stereospecific synthesis of methyl α-C-mannobioside: a potential inhibitor of M. tuberculosis binding to human macrophages

  摘要：

  The synthesis of the C-glycoside analogue of the mycobacteria capping disaccharide, Man alpha 1-2Man, employing a glycosyl organosamarium is described.

  DOI：

  10.1039/cc9960001661
• 作为产物：
  描述：

  叔丁基二甲硅基三氟甲磺酸酯 、 3,4,6-tri-O-benzyl-α-D-mannopyranosyl 2-pyridyl sulfone 在 4-二甲氨基吡啶 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 以78%的产率得到[(2R,3S,4S,5R,6R)-4,5-bis(phenylmethoxy)-6-(phenylmethoxymethyl)-2-pyridin-2-ylsulfonyloxan-3-yl]oxy-tert-butyl-dimethylsilane
  参考文献：
  名称：

  A General Approach to 1,2-trans-C-Glycosides via Glycosyl Samarium(III) Compounds

  摘要：

  DOI：

  10.1002/(sici)1521-3765(19980416)4:4<655::aid-chem655>3.3.co;2-w

文献信息

• Stereocontrolled Synthesis of α-<i>C</i>-Galactosamine Derivatives via Chelation-Controlled <i>C</i>-Glycosylation
  作者：Dominique Urban、Troels Skrydstrup、Jean-Marie Beau

  DOI：10.1021/jo971727h

  日期：1998.4.1

  or aldehydes under Barbier conditions led unexpectedly to the stereoselective synthesis of alpha-C-galactosamine derivatives in good yields. With carbonyl substrates, alpha:beta selectivities ranged from 20:1 to 5:1, and with aldehydes a stereoselectivity of approximately 5:1 was observed at C7 in favor of the S-isomer. The stereochemical preference of these C-glycosylation reactions is explained by

  在巴比尔条件下，二碘化sa通过酮或醛促进的二碘化mar还原的2-脱氧-2-乙酰氨基七乳糖基吡啶基砜α-5出乎意料地以高收率立体合成了α-C-半乳糖胺衍生物。对于羰基底物，α：β选择性范围为20：1至5：1，对于醛，在C7处观察到约5：1的立体选择性，有利于S-异构体。这些C-糖基化反应的立体化学偏好是通过α-定向异头糖基sa（III）化合物的中间体来解释的，该化合物通过金属离子与C2-乙酰氨基的螯合来稳定。
• Further studies in α-C-mannosylation promoted by samarium diiodide
  作者：Olivier Jarreton、Troels Skrydstrup、Jean-Marie Beau

  DOI：10.1016/s0040-4039(97)00206-2

  日期：1997.3

  Mannosyl pyridylsulfones with varying C2OH protecting groups were reacted with cyclohexanone in the presence of SmI2. With SiMe2tBu and Bn, high yields of an α-C-mannoside were obtained. In the former case no β-elimination was observed. The relative configuration of the major diastereomer obtained upon coupling with aldehydes was determined.

  在SmI 2的存在下，具有不同C2 = OH保护基的甘露糖基吡啶基砜与环己酮反应。使用SiMe 2 t Bu和Bn，可获得高收率的α - C-甘露糖苷。在前一种情况下，未观察到β-消除。确定了与醛偶联后获得的主要非对映异构体的相对构型。
• Samarium Diiodide PromotedC-Glycosylation: An Application to the Stereospecific Synthesis ofα-1,2-C-Mannobioside and Its Derivatives
  作者：Olivier Jarreton、Troels Skrydstrup、Juan-Félix Espinosa、Jesús Jiménez-Barbero、Jean-Marie Beau

  DOI：10.1002/(sici)1521-3765(19990201)5:2<430::aid-chem430>3.0.co;2-d

  日期：1999.2.1

  The synthesis of the C-glycoside analogue of the disaccharide Man(alpha 1-->2)Man has been achieved in a highly stereoselective and efficient manner employing an approach which closely parallels O-glycoside synthesis. The key step included the samarium diiodide reduction of mannosyl pyridylsulfone 18 in the presence of the C2-formyl branched mannoside derivative 17a to furnish the C-disaccharide derivative 19a in high yield. An intramolecular formyl group transfer reaction by means of 5-exo radical cyclization and concomitant fragmentation yielded aldehyde 17a stereospecifically. We also present a potentially viable alternative for the deoxygenation of sterically encumbered secondary alcohols. Attempts to extend this procedure to the synthesis of the C-trisaccharide of Man(alpha 1-->2)Man(alpha 1-->2)Man were frustrated by the inability of the disaccharide, pyridylsulfone derivative 43, to undergo coupling with carbonyl substrates upon treatment with SmI2, possibly owing to the sterically bulky C2 substituent.