(5S*,6R*)-methyl 7,9-dibromo-8-methoxy-6-oxo-1-oxa-2-azaspiro<4.5>deca-2,7,9-triene-3-carboxylate

• 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: (5S*,6R*)-methyl 7,9-dibromo-8-methoxy-6-oxo-1-oxa-2-azaspiro<4.5>deca-2,7,9-triene-3-carboxylate
• 英文别名: methyl (6SR,5RS)-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；verongidoic acid methyl ester；(5SR,10RS)-methyl 7,9-dibromo-10-hydroxy-8-methoxy-1-oxa-2-azaspiro[4.5]deca-2,6,8-triene-3-carboxylate；methyl (5S,6R)-7,9-dibromo-6-hydroxy-8-methoxy-1-oxa-2-azaspiro[4.5]deca-2,7,9-triene-3-carboxylate
• 化学式: C₁₁H₁₁Br₂NO₅
• 分子量: 397.02
• InChiKey: BWARHGMOCWYQHN-GXSJLCMTSA-N

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：

  (5S*,6R*)-methyl 7,9-dibromo-8-methoxy-6-oxo-1-oxa-2-azaspiro<4.5>deca-2,7,9-triene-3-carboxylate 在 吡啶 、 potassium carbonate 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 生成 Aerothionin
  参考文献：
  名称：

  Asymmetric synthesis of aerothionin, a marine dimeric spiroisoxazoline natural product, employing optically active spiroisoxazoline derivative

  摘要：

  Successful first synthesis of optically pure (+)- and (-)-aerothionins (1) from the racemic spiroisoxazoline derivative 8 has been accomplished. The absolute configuration of natural (+)-1 was determined by comparison of (+)- and (-)-8 with related derivatives. (c) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2005.11.097
• 作为产物：
  描述：

  Methyl 7,9-dibromo-6-hydroxy-8-methoxy-1-oxa-2-azaspiro[4.5]deca-2,7,9-triene-3-carboxylate 在 吡啶 、 caesium carbonate 作用下， 以 甲醇 为溶剂， 生成 (5S*,6R*)-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：

  （+）-hemifistularin 3的绝对立体化学的合成与归属

  摘要：

  对映体纯形式的海洋天然产物（+）-hemististularin 3的第一个全合成是通过使用（+）-螺杂恶唑啉酯与（+）-章鱼胺衍生物的酰胺形成反应完成的。在这项工作中采用的立体发散策略使得能够在（+）-hemifistularin 3的三个立体发生中心分配绝对构型。

  DOI：

  10.1016/j.tet.2014.07.049

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。
• Bromo-spiroisoxazoline Alkaloids, Including an Isoserine Peptide, from the Caribbean Marine Sponge <i>Aplysina lacunosa</i>
  作者：Mariam N. Salib、Matthew T. Jamison、Tadeusz F. Molinski

  DOI：10.1021/acs.jnatprod.9b01286

  日期：2020.5.22

  Three new bromotyrosine spiroisoxazoline alkaloids, lacunosins A and B (1 and 2) and desaminopurealin (3), were isolated from a MeOH extract of the marine sponge Aplysina lacunosa that showed modest α-chymotrypsin inhibitory activity. The structures of 1-3 share the spirocyclohexadienyl-isoxazoline ring system found in purealidin-R and several other Verongid sponge secondary metabolites. Compounds 1 and

  三种新的溴酪氨酸螺异恶唑啉生物碱，lacunosins A 和 B（1 和 2）以及去氨基嘌呤（3），是从海海绵 Aplysina lacunosa 的 MeOH 提取物中分离出来的，该提取物显示出适度的 α-糜蛋白酶抑制活性。1-3 的结构共享在 purealidin-R 和其他几种 Verongid 海绵次生代谢物中发现的螺环己二烯基-异恶唑啉环系统。化合物 1 和 2 分别与甘氨酸和异丝氨酸甲酯偶联。生物碱 3 与 O-1-氨基丙基 3,5-二溴酪氨酰醚相连，最后通过酰胺键与组胺相连。所有三种化合物的平面结构均通过对 MS 和 1D 和 2D NMR 数据的分析获得。SIO 单元 1-3 的绝对配置由电子圆二色性 (ECD) 分配。使用源自 Trp-NH2 的新型 Marfey 型试剂发现 2 中的异丝氨酸氨基酸残基是差向异构体的 1:1 混合物。SIO 亚基的烯丙基 O-萘酰化增强了
• 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。