castanospermine | 140386-64-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吲哚里西啶
• 英文名称: castanospermine
• 英文别名: Rel-(1R,6R,7S,8S,8aS)-octahydroindolizine-1,6,7,8-tetraol；(1R,6R,7S,8S,8aS)-1,2,3,5,6,7,8,8a-octahydroindolizine-1,6,7,8-tetrol
• CAS: 140386-64-7
• 化学式: C₈H₁₅NO₄
• 分子量: 189.211
• InChiKey: JDVVGAQPNNXQDW-HEIBUPTGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -2.2
• 重原子数：
  13
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  84.2
• 氢给体数：
  4
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  乙酸酐 、 castanospermine 在 吡啶 、 4-二甲氨基吡啶 作用下， 反应 24.0h， 以31 mg的产率得到(1R,6R,7S,8S,8aS)-octahydroindolizine-1,6,7,8-tetrayl tetraacetate
  参考文献：
  名称：

  羧基苄基作为CH烯丙基氧化中的O-亲核试剂：（-）-Castanospermine的全合成

  摘要：

  据报道，钯介导的第一个带有Cbz基团的C-H烯丙基氧化是O-亲核试剂。发现这种转变是由稀土金属三氟甲磺酸盐Yb（OTf）3或Sc（OTf）3促进的。提出了可能的催化循环。该反应用于合成d-木糖衍生的恶唑烷酮，恶唑烷酮是一种多功能中间体，可进一步用于非天然（-）-castanospermine的立体选择性合成中。用PhSeBr将关键中间体环化，得到所需的双环支架。在另一种途径中，使用硼氢化/氧化，然后进行DPPA介导的环化。

  DOI：

  10.1021/ol501730p
• 作为产物：
  描述：

  (1R,6R,7S,8S,8aS)-1,6,7,8-Tetra-O-benzyloctahydroindolizine 在 palladium on activated charcoal 盐酸 、 氢气 作用下， 以 甲醇 为溶剂， 反应 48.0h， 以91%的产率得到castanospermine
  参考文献：
  名称：

  Stereocontrolled total synthesis of the unnatural enantiomers of castanospermine and 1-epi-castanospermine

  摘要：

  A concise practical synthesis (13 steps, ca. 10-12% overall yield) of the unnatural enantiomer of castanospermine ((-)-1) and its 1-epimer 2 from 2,3,4-tri-O-benzyl-D-xylose (3) is described. Key steps in the synthesis are two organometal aldehyde additions, vinylation of 3 to 4 and allylation of 6a to 11, both of which proceed with a considerably high degree of stereocontrol. The fused ring system is generated from the acyclic amino polyol derivative 16a by two successive S(N)2-type cyclizations. Notably, the annulation of the six-membered ring makes use of tetravalent phosphonium reagents (Appel or Mitsunobu type) which cyclize the amino alcohol 22a/b directly to 23a/b without need for N-deprotection and O-activation manipulations.

  DOI：

  10.1021/jo00037a043

文献信息

• COMBINATION OF A GLYCOSYLATION INHIBITOR WITH ONE CAR CELL THERAPY FOR TREATING CANCER
  申请人：OSPEDALE SAN RAFFAELE S.R.L.

  公开号：US20210290646A1

  公开（公告）日：2021-09-23

  The present invention relates to at least one glycosylation inhibitor for use in combination with CAR cell therapy. Preferably, the glycosylation inhibitor improves the therapeutic potential of the CAR cell therapy. The invention also relates to a pharmaceutical composition and to population or subpopulation of CAR cell that has been contacted with at least one glycosylation inhibitor.
• Stereocontrolled total synthesis of the unnatural enantiomers of castanospermine and 1-epi-castanospermine
  作者：Johann Mulzer、Henrietta Dehmlow、Juergen Buschmann、Peter Luger

  DOI：10.1021/jo00037a043

  日期：1992.5

  A concise practical synthesis (13 steps, ca. 10-12% overall yield) of the unnatural enantiomer of castanospermine ((-)-1) and its 1-epimer 2 from 2,3,4-tri-O-benzyl-D-xylose (3) is described. Key steps in the synthesis are two organometal aldehyde additions, vinylation of 3 to 4 and allylation of 6a to 11, both of which proceed with a considerably high degree of stereocontrol. The fused ring system is generated from the acyclic amino polyol derivative 16a by two successive S(N)2-type cyclizations. Notably, the annulation of the six-membered ring makes use of tetravalent phosphonium reagents (Appel or Mitsunobu type) which cyclize the amino alcohol 22a/b directly to 23a/b without need for N-deprotection and O-activation manipulations.
• Carboxybenzyl Group as an <i>O</i>-Nucleophile in the C–H Allylic Oxidation: Total Synthesis of (−)-Castanospermine
  作者：Michał Malik、Grzegorz Witkowski、Sławomir Jarosz

  DOI：10.1021/ol501730p

  日期：2014.7.18

  triflates: Yb(OTf)3 or Sc(OTf)3. A possible catalytic cycle is proposed. This reaction was applied in the synthesis of a d-xylose derived oxazolidinon, a versatile intermediate used further in the stereoselective synthesis of unnatural (−)-castanospermine. Cyclization of the key intermediate with PhSeBr afforded the desired bicyclic scaffold. In an alternative route, hydroboration/oxidation followed

  据报道，钯介导的第一个带有Cbz基团的C-H烯丙基氧化是O-亲核试剂。发现这种转变是由稀土金属三氟甲磺酸盐Yb（OTf）3或Sc（OTf）3促进的。提出了可能的催化循环。该反应用于合成d-木糖衍生的恶唑烷酮，恶唑烷酮是一种多功能中间体，可进一步用于非天然（-）-castanospermine的立体选择性合成中。用PhSeBr将关键中间体环化，得到所需的双环支架。在另一种途径中，使用硼氢化/氧化，然后进行DPPA介导的环化。