(2R,3S,4R,5Z)-1-azido-2,3,4-tri(benzyloxy)-9-chloro-5-nonene | 154813-31-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (2R,3S,4R,5Z)-1-azido-2,3,4-tri(benzyloxy)-9-chloro-5-nonene
• 英文别名: [(Z,2R,3S,4R)-1-azido-9-chloro-2,4-bis(phenylmethoxy)non-5-en-3-yl]oxymethylbenzene
• CAS: 154813-31-7
• 化学式: C₃₀H₃₄ClN₃O₃
• 分子量: 520.071
• InChiKey: HBLJPHIVYUUXDS-ACXZVCLOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.1
• 重原子数：
  37
• 可旋转键数：
  17
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  42
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (2R,3S,4R,5Z)-1-azido-2,3,4-tri(benzyloxy)-9-chloro-5-nonene 在 palladium dihydroxide 、 palladium on activated charcoal 咪唑 、 盐酸 、 sodium tetrahydroborate 、 四氧化锇 、 草酰氯 、 氢气 、 potassium carbonate 、 sodium hydrogensulfite 、 二甲基亚砜 、 N-甲基吗啉氧化物 、 三乙胺 作用下， 以 四氢呋喃 、 甲醇 、 乙醇 、 乙酸乙酯 、 N,N-二甲基甲酰胺 为溶剂， 反应 146.92h， 生成 (1R,2R,3R,9R,9aR)-1,2,3,9-tetrahydroxyquinolizidine
  参考文献：
  名称：

  Synthesis of Tetrahydroxyquinolizidines:  Ring-Expanded Analogs of the Mannosidase Inhibitor Swainsonine

  摘要：

  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.

  DOI：

  10.1021/jo960609b
• 作为产物：
  描述：

  (Z)-(2R,3S,4R)-2,3,4-tris(benzyloxy)-9-chloro-5-nonen-1-ol 在 三(2-氯乙基)胺 、 三苯基膦 、 偶氮二甲酸二乙酯 作用下， 以 苯 为溶剂， 反应 0.5h， 以84%的产率得到(2R,3S,4R,5Z)-1-azido-2,3,4-tri(benzyloxy)-9-chloro-5-nonene
  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

• Azidomercurations of Alkenes:  Mercury-Promoted Schmidt Reactions
  作者：William H. Pearson、Daniel A. Hutta、Wen-kui Fang

  DOI：10.1021/jo001181q

  日期：2000.12.1

  the mercury-promoted Schmidt reaction has several advantages. First, the acid-promoted Schmidt reaction of azido-alkenes requires that the intermediate carbocations be tertiary, allylic, benzylic, or propargylic. The mercury-promoted method has no such limitation; thus even 1,2-disubstituted alkenes may be used. Second, the mercury-promoted method is milder, allowing the presence of acid-sensitive functionality

  当用高氯酸汞或三氟甲磺酸汞处理时，带有适当处理的烯烃的叠氮化物会生成双环亚胺离子。施密特反应的这一新形式是通过叠氮化物捕获汞离子中间体而产生的氨基重氮离子，该氨基重氮离子发生1,2移位而生成亚氨基离子（例如10-> 16-> 17- -> 18）。然后可以进行亚胺离子的还原以产生胺。与早期的质子酸促进叠氮基烯烃的分子内Schmidt反应的工作相比，汞促进的Schmidt反应具有许多优点。首先，叠氮基烯烃的酸促施密特反应要求中间碳阳离子为叔，烯丙基，苄基或炔丙基。汞促进的方法没有这种限制。因此，即使是1 可以使用2-二取代的烯烃。其次，汞促进的方法较为温和，允许存在酸敏感的官能团。通常使用三氟甲磺酸的质子形式在其官能团耐受性上受到限制。第三，尽管在酸促进的施密特反应中经常在环化/重排之前观察到碳正离子重排，但是汞促进的方法避免了这个问题。第四，在重排过程中汞基的存在可能会改变1,2-迁移的区