(5SR,10SR)-methyl 7,9-dibromo-10-hydroxy-8-methoxy-1-oxa-2-azaspiro[4.5]deca-2,6,8-triene-3-carboxylate | 87580-09-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑啉类
• 英文名称: (5SR,10SR)-methyl 7,9-dibromo-10-hydroxy-8-methoxy-1-oxa-2-azaspiro[4.5]deca-2,6,8-triene-3-carboxylate
• 英文别名: methyl (6SR,5SR)-7,9-dibromo-6-hydroxy-8-methoxy-4-oxa-3-azaspiro[4.5]deca-2,7,9-triene-2-carboxylate；methyl 7,9-dibromo-10-hydroxy-8-methoxy-1-oxa-2-azaspiro[4.5]-deca-2,6,8-triene-3-carboxylate；methyl (5S,6S)-7,9-dibromo-6-hydroxy-8-methoxy-1-oxa-2-azaspiro[4.5]deca-2,7,9-triene-3-carboxylate
• CAS: 87580-09-4；87580-10-7
• 化学式: C₁₁H₁₁Br₂NO₅
• 分子量: 397.02
• InChiKey: BWARHGMOCWYQHN-MWLCHTKSSA-N

物化性质

• 熔点：
  134-136 °C
• 沸点：
  478.4±55.0 °C(Predicted)
• 密度：
  1.98±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  19
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  77.4
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (5SR,10SR)-methyl 7,9-dibromo-10-hydroxy-8-methoxy-1-oxa-2-azaspiro[4.5]deca-2,6,8-triene-3-carboxylate 在 四丁基高氯酸铵 、 二乙胺 作用下， 以 乙腈 为溶剂， 生成 methyl 7,9-dibromo-8-methoxy-6-oxo-1-oxa-2-azaspiro<4.5>deca-2,7,9-triene-3-carboxylate
  参考文献：
  名称：

  Ogamino, Takahisa; Ishikawa, Yuichi; Nishiyama, Shigeru, Heterocycles, 2003, vol. 61, p. 73 - 78

  摘要：

  DOI：
• 作为产物：
  描述：

  methyl 2-benzyloxyimino-3-(2'-benzyloxy-3,5-dibromo-4-methoxyphenyl)propionate 在 palladium on activated charcoal zinc(II) tetrahydroborate 、 氢气 、 thallium(III) trifluoroacetate 作用下， 以 1,4-二氧六环 、 乙醚 、 二氯甲烷 、 溶剂黄146 、 三氟乙酸 为溶剂， 反应 4.12h， 生成 (5SR,10SR)-methyl 7,9-dibromo-10-hydroxy-8-methoxy-1-oxa-2-azaspiro[4.5]deca-2,6,8-triene-3-carboxylate
  参考文献：
  名称：

  （±）-aeroothionin和（±）-homoaerothionin的总合成

  摘要：

  海绵状Aplysina aerophoba，A。fistularis和Verongia thiona的新型代谢产物aerothionin和homoaerothionin均以外消旋形式合成。

  DOI：

  10.1016/s0040-4039(00)86267-x

文献信息

• Total syntheses of subereamollines A and B
  作者：James W. Shearman、Rebecca M. Myers、James D. Brenton、Steven V. Ley

  DOI：10.1039/c0ob00636j

  日期：——

  The first total syntheses of (+)- and (−)-subereamollines A and B are reported. The enantiomeric forms of the natural products were obtained by preparative chiral HPLC separation of the corresponding racemates.

  首次报道了(+)-和(−)-subereamollines A和B的完整合成。这些天然产物的对映体形式通过相应外消旋体的制备性手性高效液相色谱分离获得。
• Total Synthesis, Structural Revision, and Biological Evaluation of Calafianin, a Marine Spiroisoxazoline from the Sponge,<i>Aplysina gerardogreeni</i>
  作者：Takahisa Ogamino、Rika Obata、Hiroshi Tomoda、Shigeru Nishiyama

  DOI：10.1246/bcsj.79.134

  日期：2006.1

  The reported structure of the natural calafianin (1) and its isomer in the epoxide region 13 were successfully synthesized through the cis- and trans-spiroisoxazoline compounds, which were produced by electrochemical oxidation of the hydroxyimino-phenol derivative 7, followed by Zn[BH4]2 reduction. Comparison of the spectroscopic data of the synthetic (±)-1 and (±)-13 resulted in structural revision of the natural calafianin to 13, possessing the trans-relationship between an epoxide and an oxygen of the isoxazoline. In addition, a significant difference of antimicrobial activity between 1 and 13 is discussed.

  报道的自然卡拉法宁（1）及其异构体在环氧区域13通过顺式和反式螺异噁唑啉化合物成功合成，这些化合物是通过对羟亚氨基苯酚衍生物7的电化学氧化产物，再经过Zn[BH4]2还原得到的。合成的（±）-1和（±）-13的光谱数据比较导致了对自然卡拉法宁结构的修订，确认其为13，具有环氧和异噁唑啉氧之间的反式关系。此外，还讨论了1和13之间抗菌活性显著差异。
• Total syntheses of (±)-aerothionin and (±)-homoaerothionin
  作者：Shigeru Nishiyama、Shosuke Yamamura

  DOI：10.1016/s0040-4039(00)86267-x

  日期：1983.1

  Both aerothionin and homoaerothionin, the novel metabolites of the sponges Aplysina aerophoba, A. fistularis and Verongia thiona, have been synthesized in racemic form.

  海绵状Aplysina aerophoba，A。fistularis和Verongia thiona的新型代谢产物aerothionin和homoaerothionin均以外消旋形式合成。
• Total Syntheses of (±)-Aerothionin, (±)-Homoaerothionin, and (±)-Aerophobin-1
  作者：Shigeru Nishiyama、Shosuke Yamamura

  DOI：10.1246/bcsj.58.3453

  日期：1985.12

  (±)-aerophobin-1 have been successfully synthesized using phenolic oxidation of the methyl pyruvate oxime derivative with thallium(III) trifluoroacetate as a key step. The stereostructure of aerophobin-2 has been also established by comparison of the 1H NMR spectrum with those of related compounds.

  (±)-Aerothionin、(±)-homoaerothionin 和 (±)-aerophobin-1 已成功合成，使用三氟乙酸铊 (III) 对丙酮酸甲酯肟衍生物的酚氧化作为关键步骤。通过将 1H NMR 光谱与相关化合物的光谱进行比较，还确定了 Aerophobin-2 的立体结构。
• Divergent and Concise Syntheses of Spiroisoxazolines: First Total Synthesis of 11-Deoxyfistularin-3
  作者：Prasanta Das、Ashton T. Hamme II

  DOI：10.1002/ejoc.201500603

  日期：2015.8

  A divergent and concise base-promoted Dieckmann-type keto-ester condensation strategy is demonstrated to generate two unique spiro[cyclohexadiene-isoxazoline] moieties. The consecutive di-bromination–elimination–bromination of the corresponding spiro moiety has been successfully utilized to furnish the desired core structure of many bromotyrosine derived spiroisoxazoline natural products. The spiroisoxazoline

  证明了一种发散且简洁的碱促进 Dieckmann 型酮酯缩合策略可生成两个独特的螺[环己二烯-异恶唑啉]部分。相应螺部分的连续二溴化-消除-溴化已成功用于提供许多溴酪氨酸衍生的螺异恶唑啉天然产物所需的核心结构。螺异恶唑啉酸进一步与所需的二胺偶联以完成 11-deoxyfistularin-3 的首次全合成。该策略可以作为先前开发的苯酚氧化脱芳构化螺环化的有效替代方案，作为合成此类天然产物的必要步骤。