(2S,3S,4R)-1-benzyl-3,4-bis(benzyloxy)-2-(benzyloxymethyl)-5-methylenepiperidine | 1161011-52-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 哌啶类
• 英文名称: (2S,3S,4R)-1-benzyl-3,4-bis(benzyloxy)-2-(benzyloxymethyl)-5-methylenepiperidine
• 英文别名: (2S,3S,4R)-1-benzyl-3,4-bis(benzyloxy)-2-(benzyloxymethyl)-5-C-methylene piperidine；(2S,3S,4R)-1-benzyl-5-methylidene-3,4-bis(phenylmethoxy)-2-(phenylmethoxymethyl)piperidine
• CAS: 1161011-52-4
• 化学式: C₃₅H₃₇NO₃
• 分子量: 519.684
• InChiKey: XCFADWZPHAWUHP-XFQWPLCWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.8
• 重原子数：
  39
• 可旋转键数：
  12
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.26
• 拓扑面积：
  30.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (2S,3S,4R)-1-benzyl-3,4-bis(benzyloxy)-2-(benzyloxymethyl)-5-methylenepiperidine 在 三氯化硼 作用下， 以 正庚烷 、 二氯甲烷 为溶剂， 反应 24.0h， 以82%的产率得到(2S,3S,4R)-1-benzyl-2-(hydroxymethyl)-5-C-methylene-piperidine-3,4-diol
  参考文献：
  名称：

  InCl3–CH3CN–H2O: an efficient catalyst-solvent combination for the synthesis of Perlin aldehydes and related compounds. Application in the synthesis of unnatural l-azasugars

  摘要：

  InCl3-CH3CN-H2O has been found to be an efficient catalyst-solvent combination for the synthesis of Perlin aldehydes and related compounds. While acetylated glycals afforded the Perlin aldehydes directly with InCl3 and water, benzylated glycals on the other hand provided the hemiacetals under identical condition. The methodology reports a non-mercurial approach to Perlin aldehydes. Noteworthy is that this reaction is more facile as well as highly selective with glycals possessing a hydroxyl as a leaving group than with a benzyloxy group. Extension of this reaction to 2-C-hydroxymethyl glycals resulted in the formation of the corresponding hemiacetals, which were further transformed in to unsaturated azasugars with an exo-methylene group at C-2 position. Glycosidase inhibition studies reveal that these compounds display selectivity in inhibiting glucosidases rather than galactosidases. (C) 2010 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2010.11.050
• 作为产物：
  描述：

  (3R,4S,5R)-3,4,6-tris(benzyloxy)-2-methylenehexane-1,5-diol 在 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 28.0h， 生成 (2S,3S,4R)-1-benzyl-3,4-bis(benzyloxy)-2-(benzyloxymethyl)-5-methylenepiperidine
  参考文献：
  名称：

  InCl3–CH3CN–H2O: an efficient catalyst-solvent combination for the synthesis of Perlin aldehydes and related compounds. Application in the synthesis of unnatural l-azasugars

  摘要：

  InCl3-CH3CN-H2O has been found to be an efficient catalyst-solvent combination for the synthesis of Perlin aldehydes and related compounds. While acetylated glycals afforded the Perlin aldehydes directly with InCl3 and water, benzylated glycals on the other hand provided the hemiacetals under identical condition. The methodology reports a non-mercurial approach to Perlin aldehydes. Noteworthy is that this reaction is more facile as well as highly selective with glycals possessing a hydroxyl as a leaving group than with a benzyloxy group. Extension of this reaction to 2-C-hydroxymethyl glycals resulted in the formation of the corresponding hemiacetals, which were further transformed in to unsaturated azasugars with an exo-methylene group at C-2 position. Glycosidase inhibition studies reveal that these compounds display selectivity in inhibiting glucosidases rather than galactosidases. (C) 2010 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2010.11.050

文献信息

• Facile Aza-Claisen Rearrangement of Glycals: Application in the Synthesis of 1-Deoxy-L-iminosugars
  作者：Preeti Gupta、Yashwant D. Vankar

  DOI：10.1002/ejoc.200801301

  日期：——

  2-C-Methylene-N-glycosyl amides have been obtained from 2-(hydroxymethyl)glycals through a facile aza-Claisen rearrangement. This rearrangement has also been utilized in the synthesis of L-allo-deoxynojirimycin, a moderate inhibitor of human lysosomal α-mannosidase (IC50 = 64 μM), and two new C-5-(hydroxymethyl) analogues of L-altro-deoxynojirimycin and L-ido-deoxynojirimycin.(© Wiley-VCH Verlag GmbH

  2-C-亚甲基-N-糖基酰胺已通过简单的氮杂-克莱森重排从 2-（羟甲基）糖基中获得。这种重排也被用于合成 L-allo-deoxynojirimycin，一种人溶酶体 α-甘露糖苷酶的中度抑制剂 (IC50 = 64 μM)，以及 L-altro-deoxynojirimycin 的两种新的 C-5-（羟甲基）类似物和L-ido-脱氧野尻霉素。（© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009）