(1R,2R,3R,9R,9aS)-1,2,3-tri-O-benzyl-1,2,3,9-tetrahydroxyquinolizidine | 180323-13-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 喹嗪类
• 英文名称: (1R,2R,3R,9R,9aS)-1,2,3-tri-O-benzyl-1,2,3,9-tetrahydroxyquinolizidine
• 英文别名: (1R,7R,8R,9R,9aS)-7,8,9-tris(phenylmethoxy)-2,3,4,6,7,8,9,9a-octahydro-1H-quinolizin-1-ol
• CAS: 180323-13-1
• 化学式: C₃₀H₃₅NO₄
• 分子量: 473.612
• InChiKey: MSZRZNSHPDOYBA-CMPUJJQDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  35
• 可旋转键数：
  9
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  51.2
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (1R,2R,3R,9R,9aS)-1,2,3-tri-O-benzyl-1,2,3,9-tetrahydroxyquinolizidine 在 palladium on activated charcoal 盐酸 、 氢气 作用下， 反应 48.0h， 以92%的产率得到(1R,2R,3R,9R,9aS)-1,2,3,9-tetrahydroxyquinolizidine
  参考文献：
  名称：

  新型多羟基喹oli嗪的合成：糖苷酶抑制吲哚并iz啶的环扩类似物

  摘要：

  两个多羟基喹oli嗪核苷（（1 R，2 R，3 R，9 S，9a R）-1,2,3,9-四羟基喹oli嗪9和（1 R，2 R，3 R，9 R，9a S -1， 2,3,9- tetrahydroxyquinolizidine 10，已经通过的还原性环化双合成15 α和15 β。喹诺9可以作为6- epicastanospermine或8 episwainsonine的环扩展的模拟观看，而10是一个环1,6,8a-triepicastanospermine或8a-episwainsonine的扩展类似物。

  DOI：

  10.1016/s0040-4039(00)61395-3
• 作为产物：
  描述：

  2,3,4-tri-O-benzyl-D-arabinopyranose 在 palladium on activated charcoal 三(2-氯乙基)胺 、 氢气 、 双(三甲基硅烷基)氨基钾 、 potassium carbonate 、 间氯过氧苯甲酸 、 三苯基膦 、 偶氮二甲酸二乙酯 作用下， 以 乙醚 、 乙醇 、 二氯甲烷 、 苯 为溶剂， -78.0~25.0 ℃ 、101.33 kPa 条件下， 反应 66.0h， 生成 (1R,2R,3R,9R,9aS)-1,2,3-tri-O-benzyl-1,2,3,9-tetrahydroxyquinolizidine
  参考文献：
  名称：

  新型多羟基喹oli嗪的合成：糖苷酶抑制吲哚并iz啶的环扩类似物

  摘要：

  两个多羟基喹oli嗪核苷（（1 R，2 R，3 R，9 S，9a R）-1,2,3,9-四羟基喹oli嗪9和（1 R，2 R，3 R，9 R，9a S -1， 2,3,9- tetrahydroxyquinolizidine 10，已经通过的还原性环化双合成15 α和15 β。喹诺9可以作为6- epicastanospermine或8 episwainsonine的环扩展的模拟观看，而10是一个环1,6,8a-triepicastanospermine或8a-episwainsonine的扩展类似物。

  DOI：

  10.1016/s0040-4039(00)61395-3

文献信息

• Synthesis of novel polyhydroxylated quinolizidines: Ring expanded analogs of glycosidase inhibitory indolizidines
  作者：William H. Pearson、Erik J. Hembre

  DOI：10.1016/s0040-4039(00)61395-3

  日期：1993.12

  2R,3R,9R,9aS-1,2,3,9-tetrahydroxyquinolizidine 10, have been synthesized by the reductive double cyclization of 15α and 15β. Quinolizidine 9 can be viewed either as a ring expanded analog of 6-epicastanospermine or of 8-episwainsonine, while 10 is a ring expanded analog of 1,6,8a-triepicastanospermine or of 8a-episwainsonine.

  两个多羟基喹oli嗪核苷（（1 R，2 R，3 R，9 S，9a R）-1,2,3,9-四羟基喹oli嗪9和（1 R，2 R，3 R，9 R，9a S -1， 2,3,9- tetrahydroxyquinolizidine 10，已经通过的还原性环化双合成15 α和15 β。喹诺9可以作为6- epicastanospermine或8 episwainsonine的环扩展的模拟观看，而10是一个环1,6,8a-triepicastanospermine或8a-episwainsonine的扩展类似物。
• Synthesis of Tetrahydroxyquinolizidines:  Ring-Expanded Analogs of the Mannosidase Inhibitor Swainsonine
  作者：William H. Pearson、Erik J. Hembre

  DOI：10.1021/jo960609b

  日期：1996.1.1

  The indolizidine azasugar swainsonine (1) is an important inhibitor of mannosidase II and has shown antitumor and immunomodulatory activity. A comparison of the structure of swainsonine and D-mannopyranose shows that swainsonine lacks the C(4) hydroxymethine group of mannose. Ring-expanded quinolizidine analogs 4 of swainsonine were prepared where the ''missing'' hydroxymethine group was incorporated into the pyrrolidine ring of swainsonine between C(1) and C(8a). The quinolizidine analogs 4 resemble both D-mannopyranose and the related azasugar deoxymannojirimycin, a selective inhibitor of the glycoprotein processing enzyme mannosidase I. D-Arabinose was converted into the omega-halo azidoalkene 13, which was subjected to thermolysis, a strategy which had been successful in an earlier synthesis of swainsonine itself. Rather than the desired quinolizidine 4, the pyridinium ion 16 was produced. An alternate synthesis of all four C(9)/C(9a) diastereomers of 4 was developed which relied on the reductive double-alkylation of epoxides bearing remote azido and chloro groups. Thus, reduction of compounds 21 alpha, 21 beta, 26, and 27 resulted in the formation of the quinolizidines 22, 23, 28, and 29, which were deprotected to give the quinolizidine analogs of swainsonine (9S,9aR)-4, (9R,9aS)-4, (9S,9aS)-4, and (9R,9aR)-4, respectively. An alternate synthesis of(9R,9aR)-4 involving the reductive N-alkylation of a cyclic imine was also developed. None of the quinolizidines showed significant glycosidase activity in screens against mannosidases, glucosidases, or fucosidases. Speculation on the significance of these findings is presented.