(Z)-3-(furan-2-yl)-2-nitroacrylaldehyde | 1019636-31-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 杂芳族化合物
• 英文名称: (Z)-3-(furan-2-yl)-2-nitroacrylaldehyde
• 英文别名: 3-(furan-2-yl)-2-nitroacrylaldehyde；(Z)-3-(furan-2-yl)-2-nitroprop-2-enal
• CAS: 1019636-31-7
• 化学式: C₇H₅NO₄
• 分子量: 167.121
• InChiKey: VALXWELVPDCSSA-XQRVVYSFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  76
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  (E)-3-(furan-2-yl)-2-nitroprop-2-en-1-ol 在 2-碘酰基苯甲酸 作用下， 以 乙酸乙酯 为溶剂， 生成 (Z)-3-(furan-2-yl)-2-nitroacrylaldehyde 、 (E)-3-(furan-2-yl)-2-nitroacrylaldehyde
  参考文献：
  名称：

  Synthesis, Structure, and E−Z Isomerization of β-(Hetero)aryl-α-nitro-α,β-enals

  摘要：

  The first general methodology for the gram-scale preparation of previously overlooked beta-(hetero)aryl-alpha-nitro-alpha,beta-enals (3) is reported. Condensation of (hetero) aromatic aldehydes with 2-nitroethanol gave the E-isomers of uncommon beta-(hetero)aryl-alpha-hydroxymethyl-alpha,beta-unsatured-nitroalkenes (2), as determined by NOE and X-ray studies. alpha-Nitro-alpha,beta-enals 3 were subsequently obtained by hypervalent iodine oxidation of 2 as E-Z-mixtures in solid form. They showed varied stability and solvent-dependent thermal-promoted and photopromoted E-Z interconversion. Starting with furfural, experimental conditions were developed to prepare the corresponding nitroenal 3a enriched in either the E or the Z isomer: E-3a/Z-3a approximate to 90/10 and 20/80, respectively. In contrast with other structurally related compounds, nitroenals 3 have their (hetero)aryl-vinyl unit and their formyl and nitro groups all in a planar arrangement, both in solid form and in solution; accordingly, they are colored compounds with predicted high dipole moments. As deduced from solution-NMR and X-ray data, the C=C and the C=O double bonds in 3 are exclusively s-cis-oriented; this disposition corresponds in fact to the DFT-computed most stable conformer.

  DOI：

  10.1021/jo702731b

文献信息

• Chemoenzymatic Synthesis of Advanced Intermediates for Formal Total Syntheses of Tetrodotoxin
  作者：Daler Baidilov、Lukas Rycek、John F. Trant、Jordan Froese、Brennan Murphy、Tomas Hudlicky

  DOI：10.1002/anie.201804602

  日期：2018.8.20

  Advanced intermediates for the syntheses of tetrodotoxin reported by the groups of Fukuyama, Alonso, and Sato were prepared. Key steps include the toluene dioxygenase mediated dihydroxylation of either iodobenzene or benzyl acetate. The resulting diene diols were transformed into Fukuyama's intermediate in six steps, into Alonso's intermediate in nine steps, and into Sato's intermediate in ten steps

  制备了由福山，阿隆索和佐藤小组报告的河豚毒素合成的高级中间体。关键步骤包括碘代苯或乙酸苄酯的甲苯双加氧酶介导的二羟基化。所得的二烯二醇经六步转化为福山中间体，经九步转化为阿隆索的中间体，并经十步转化为佐藤的中间体。
• A Cascade Annulation Based Convergent Approach to Racemic Tetrodotoxin
  作者：Fernando Cagide-Fagín、Ricardo Alonso

  DOI：10.1002/ejoc.201001159

  日期：2010.12

  synthetic power of the recently developed cascade annulations of β-(hetero)aryl-α-nitro-α,β-enals with the pyrrolidine-derived enamine of 2,2-dimethyl-1,3-dioxan-5-one is demonstrated by the first convergent route to (±)-tetrodotoxin.

  证明了最近开发的 β-（杂）芳基-α-硝基-α,β-烯醛与吡咯烷衍生的 2,2-二甲基-1,3-二恶烷-5-one 烯胺的级联环化的合成能力通过第一个趋同途径（±）-河豚毒素。
• [EN] PROCESSES FOR THE PREPARATION OF PANCRATISTATIN AND PANCRATISTATIN ANALOGUES<br/>[FR] PROCÉDÉS DE PRÉPARATION DE PANCRATISTATINE ET D'ANALOGUES DE PANCRATISTATINE
  申请人：UNIV SANTIAGO COMPOSTELA

  公开号：WO2009026961A1

  公开（公告）日：2009-03-05

  Processes for the preparation of pancratistatin and pancratistatin analogues. The key step is the reaction of a 1,3-dioxan-5-one and a nitroolefine in the presence of an amine. The process may take place in an enantioselective way when a chiral amine is used. Reduction processes then give new and advanced intermediates that are useful for the preparation of pancratistatin or selected pancratistatin analogues. The reported process also provides a method for the efficient synthesis of nitroenals, starting materials of the synthesis. Analogues of pancratistatin are also provided.

  制备pancratistatin和pancratistatin类似物的过程。关键步骤是在胺的存在下，将1,3-二氧杂环戊酮和硝基烯烃进行反应。当使用手性胺时，该过程可能以对映选择性方式进行。然后，还可以通过还原过程得到新的和先进的中间体，这些中间体对于制备pancratistatin或选定的pancratistatin类似物非常有用。报告的过程还提供了一种高效合成硝基烯醛的方法，这是合成的起始材料。还提供了pancratistatin的类似物。
• SYNTHESIS OF POLYOXYGENATED NITROGEN SYSTEMS, COMPRISING REACTIONS BETWEEN ENAMINES OF 1,3-DIOXAN-5-ONES AND NITROOLEFINS
  申请人：UNIVERSIDADE DE SANTIAGO DE COMPOSTELA

  公开号：EP1783123B1

  公开（公告）日：2010-03-17
• Synthesis of Polyoxygenated Nitrogen Systems, Comprising Reactions Between Enamines of 1,3-Dioxan-5-Ones and Nitroolefins
  申请人：Alonso Alonso Ricardo

  公开号：US20080045523A1

  公开（公告）日：2008-02-21

  The invention relates to the synthesis of polyoxygenated nitrogen systems, comprising reactions between enamines of 1,3-dioxan-5-ones and nitroolefins. More specifically, the invention relates to the reaction between enamines having formula II which are derived from 1,3-dioxan-5-ones I and nitroolefins having formula III. In this way, novel polyoxygenated nitrogen systems are generated having formula IV and V, which, as they are or following simple transformations, constitute synthetic intermediates and/or analogues of different systems of proven biological/pharmacological interest, such as certain antibiotics, or tetrodotoxin, pancratistatin or the analogues thereof. The aforementioned reactions involve the use of enamines II in Michael-type addition reactions and in direct annealing processes with double acceptor systems at relative positions 1, 3. Said N acceptors include nitroolefins III, wherein R═CHO (alphanitroenals). The invention also relates to the preparation thereof, which is based on the oxidation of the corresponding precursor alcohols VII, and the use of same in annealing processes.