N-((2R,4aR,6S,7S,8S,8aR)-7,8-bis(benzyloxy)-2-phenylhexahydropyrano[3,2-d][1,3]dioxin-6-yl)-2,2,2-trichloroacetamide | 1158857-80-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃二恶英
• 英文名称: N-((2R,4aR,6S,7S,8S,8aR)-7,8-bis(benzyloxy)-2-phenylhexahydropyrano[3,2-d][1,3]dioxin-6-yl)-2,2,2-trichloroacetamide
• CAS: 1158857-80-7
• 化学式: C₂₉H₂₈Cl₃NO₆
• 分子量: 592.903
• InChiKey: NRMUOYSXUBWUCL-NZQVLCFASA-N

物化性质

• 沸点：
  694.5±55.0 °C(predicted)
• 密度：
  1.40±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.48
• 重原子数：
  39.0
• 可旋转键数：
  8.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.34
• 拓扑面积：
  75.25
• 氢给体数：
  1.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  N-((2R,4aR,6S,7S,8S,8aR)-7,8-bis(benzyloxy)-2-phenylhexahydropyrano[3,2-d][1,3]dioxin-6-yl)-2,2,2-trichloroacetamide 、 L-苯丙氨酸甲酯 在 caesium carbonate 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 以88%的产率得到methyl (((2R,4aR,6S,7S,8S,8aR)-7,8-bis(benzyloxy)-2-phenylhexahydropyrano[3,2-d][1,3]dioxin-6-yl)carbamoyl)-L-phenylalaninate
  参考文献：
  名称：

  Stereoselective Rearrangement of Trichloroacetimidates: Application to the Synthesis of α-Glycosyl Ureas

  摘要：

  A new method for the stereoselective synthesis of alpha-glycosyl ureas, via nickel-catalyzed [1,3]-rearrangement of glycosyl trichloroacetimidates, has been developed. The alpha-stereoselectivity at the anomeric carbon of the resulting trichloroacetamides depends on the nature of the cationic nickel catalyst. This method is applicable to a number of trichloroacetimidate substrates. The alpha-glycosyl trichloroacetamides can be directly converted into alpha-glycosyl ureas in the presence of amines. In all cases, the stereochemical integrity at the urea linkages remains intact.

  DOI：

  10.1021/ol900670a
• 作为产物：
  描述：

  在 (1,2-bis(diphenylphosphino)ethane)nickel(II) chloride 、 silver trifluoromethanesulfonate 作用下， 以 二氯甲烷 为溶剂， 生成 、 N-((2R,4aR,6S,7S,8S,8aR)-7,8-bis(benzyloxy)-2-phenylhexahydropyrano[3,2-d][1,3]dioxin-6-yl)-2,2,2-trichloroacetamide
  参考文献：
  名称：

  Stereoselective Rearrangement of Trichloroacetimidates: Application to the Synthesis of α-Glycosyl Ureas

  摘要：

  A new method for the stereoselective synthesis of alpha-glycosyl ureas, via nickel-catalyzed [1,3]-rearrangement of glycosyl trichloroacetimidates, has been developed. The alpha-stereoselectivity at the anomeric carbon of the resulting trichloroacetamides depends on the nature of the cationic nickel catalyst. This method is applicable to a number of trichloroacetimidate substrates. The alpha-glycosyl trichloroacetamides can be directly converted into alpha-glycosyl ureas in the presence of amines. In all cases, the stereochemical integrity at the urea linkages remains intact.

  DOI：

  10.1021/ol900670a

文献信息

• Investigations of Scope and Mechanism of Nickel-Catalyzed Transformations of Glycosyl Trichloroacetimidates to Glycosyl Trichloroacetamides and Subsequent, Atom-Economical, One-Step Conversion to α-Urea-Glycosides
  作者：Matthew J. McKay、Nathaniel H. Park、Hien M. Nguyen

  DOI：10.1002/chem.201402433

  日期：2014.7.7

  to the corresponding α‐trichloroacetamides. The α‐selective nature of the conversion is controlled with a cationic nickel(II) catalyst, [Ni(dppe)(OTf)2] (dppe=1,2‐bis(diphenylphosphino)ethane, OTf=triflate). Mechanistic studies have identified the coordination of the nickel catalyst with the equatorial C2‐ether functionality of the α‐glycosyl trichloroacetimidate to be paramount for achieving an α‐stereoselective

  描述了用于制备 α-连接的尿素新糖缀合物和假寡糖的高度立体选择性方法的开发和机理研究。该两步程序首先在镍催化下将糖基三氯乙酰亚胺选择性转化为相应的 α-三氯乙酰胺。转化的 α 选择性由阳离子镍 (II) 催化剂 [Ni(dppe)(OTf) 2 ]（dppe=1,2-双（二苯基膦）乙烷，OTf=三氟甲磺酸盐）控制。机理研究已经确定了镍催化剂与赤道 C 2 的配位α-糖基三氯乙酰亚胺酯的-醚官能团对于实现α-立体选择性转化至关重要。交叉实验表明，该反应并非完全以分子内方式进行。该序列的第二步是通过在碳酸铯存在下与多种胺亲核试剂反应，将 α-糖基三氯乙酰胺产物直接转化为相应的 α-尿素糖苷。仅观察到 α-尿素产物的形成，因为反应在异头 C  N 键上完全保留立体化学完整性。