(2S,3S)-{[2-(tert-butyldiphenylsilanyloxymethyl)-5-ethoxytetrahydrofuran-3-yl]difluoromethyl}phosphonothioic acid O,O-diethyl ester | 496048-32-9

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: (2S,3S)-{[2-(tert-butyldiphenylsilanyloxymethyl)-5-ethoxytetrahydrofuran-3-yl]difluoromethyl}phosphonothioic acid O,O-diethyl ester
• 英文别名: [[(2S,3S)-2-[[tert-butyl(diphenyl)silyl]oxymethyl]-5-ethoxyoxolan-3-yl]-difluoromethyl]-diethoxy-sulfidophosphanium
• CAS: 496048-32-9
• 化学式: C₂₈H₄₁F₂O₅PSSi
• 分子量: 586.753
• InChiKey: VYQDQKMADSWHKH-LHJLODMPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.31
• 重原子数：
  38
• 可旋转键数：
  14
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  47.2
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  (2S,3S)-{[2-(tert-butyldiphenylsilanyloxymethyl)-5-ethoxytetrahydrofuran-3-yl]difluoromethyl}phosphonothioic acid O,O-diethyl ester 在 吡啶 、 T(TMS)2 、 四氯化钛 作用下， 生成 (4S,5S)-5-{[tert-butyl(diphenyl)silyl]methyl}-4-[(diethoxyphosphorothioyl)(difluoro)methyl]tetrahydrofuran-2-yl acetate
  参考文献：
  名称：

  N-Glycosylation of 2,3-Dideoxyfuranose Derivatives Having Difluoro-methylene-phosphonate and -phosphonothioate Functionality at the 3α-Position

  摘要：

  TiCl4介导的N-糖苷化反应对2,3-脱氧核糖糖苷进行研究，这些糖苷在3α位具有二氟亚甲基磷酸酯或磷酸硫酯功能团，与硅基化的嘧啶类化合物反应。磷酸酯功能团是一个良好的指向基团，能够以高的差异选择性诱导α-N-糖苷化，得到α-N-3-嘧啶核苷酸类似物13。磷酸硫酯是一个有效的功能团，可以以良好的差异选择性生成β-N-1-嘧啶核苷酸类似物18a-c。核苷酸类似物18a经过MCPBA氧化处理后，经水相后处理转化为胸腺苷-3¢-磷酸的二氟亚甲基磷酸酯类似物20。

  DOI：

  10.1055/s-2002-34218
• 作为产物：
  描述：

  叔丁基二苯基氯硅烷 在 劳森试剂 、 咪唑 、 硝酸铵 、 硼烷四氢呋喃络合物 作用下， 以 四氢呋喃 、 乙醇 、 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 反应 27.5h， 生成 (2S,3S)-{[2-(tert-butyldiphenylsilanyloxymethyl)-5-ethoxytetrahydrofuran-3-yl]difluoromethyl}phosphonothioic acid O,O-diethyl ester
  参考文献：
  名称：

  N-Glycosylation of 2,3-dideoxyfuranose derivatives having a (diethoxyphosphorothioyl)difluoromethyl group at the 3α-position

  摘要：

  Lewis acid-mediated N-glycosylation of 2,3-dideoxyribofunanosides having a (diethoxyphosphorothioyl)difluoromethyl group at the 3alpha-position with silylated nucleobases was examined. The phosphorothioyldifluoromethyl was found to be an effective functional group for the diastereoselective synthesis of beta-N-1-pyrimidine-nucleotide analogues 26 and 28-30. However, the method was not useful for the diastereoselective synthesis of adenine nucleotide analogues. The nucleotide analogue 26 was transformed to the difluoromethylene-phosphonate analogue 31 of thymidine-3'-phosphate by oxidation with m-CPBA, followed by aqueous. work-up. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2003.09.069

文献信息

• N-Glycosylation of 2,3-Dideoxyfuranose Derivatives Having Difluoro-methylene-phosphonate and -phosphonothioate Functionality at the 3α-Position
  作者：Tsutomu Yokomatsu、Tetsuo Murano、Soichiro Muroyama、Shiroshi Shibuya

  DOI：10.1055/s-2002-34218

  日期：——

  TiCl4-Mediated N-glycosylation of 2,3-dideoxyribofunanosides having a difluoromethylene-phosphonate or -phosphonothioate functional group at the 3α-position with silylated pyrimidines was examined. The phosphonate functional was a good directing group to induce α-N-glycosylation for α-N 3-pyrimidine-nucleotide analogue 13 in high diastereoselectivity. The phosphonothioate was an effective functional group to give β-N 1-pyrimidine-nucleotide analogues 18a-c with good diastereoselectivity. The nucleotide analogue 18a was transformed to the difluoromethylenephosphonate analogue 20 of thymidine-3¢-phosphate by oxidation with MCPBA, followed by aqueous work-up.

  TiCl4介导的N-糖苷化反应对2,3-脱氧核糖糖苷进行研究，这些糖苷在3α位具有二氟亚甲基磷酸酯或磷酸硫酯功能团，与硅基化的嘧啶类化合物反应。磷酸酯功能团是一个良好的指向基团，能够以高的差异选择性诱导α-N-糖苷化，得到α-N-3-嘧啶核苷酸类似物13。磷酸硫酯是一个有效的功能团，可以以良好的差异选择性生成β-N-1-嘧啶核苷酸类似物18a-c。核苷酸类似物18a经过MCPBA氧化处理后，经水相后处理转化为胸腺苷-3¢-磷酸的二氟亚甲基磷酸酯类似物20。
• N-Glycosylation of 2,3-dideoxyfuranose derivatives having a (diethoxyphosphorothioyl)difluoromethyl group at the 3α-position
  作者：Tetsuo Murano、Yoko Yuasa、Soichiro Muroyama、Tsutomu Yokomatsu、Shiroshi Shibuya

  DOI：10.1016/j.tet.2003.09.069

  日期：2003.11

  Lewis acid-mediated N-glycosylation of 2,3-dideoxyribofunanosides having a (diethoxyphosphorothioyl)difluoromethyl group at the 3alpha-position with silylated nucleobases was examined. The phosphorothioyldifluoromethyl was found to be an effective functional group for the diastereoselective synthesis of beta-N-1-pyrimidine-nucleotide analogues 26 and 28-30. However, the method was not useful for the diastereoselective synthesis of adenine nucleotide analogues. The nucleotide analogue 26 was transformed to the difluoromethylene-phosphonate analogue 31 of thymidine-3'-phosphate by oxidation with m-CPBA, followed by aqueous. work-up. (C) 2003 Elsevier Ltd. All rights reserved.