3,3-difluoro-1nitropropene | 879125-91-4

• 分子结构分类: 有机化合物 - 有机1,3-偶极化合物 - 烯丙基型1,3-偶极有机化合物
• 英文名称: 3,3-difluoro-1nitropropene
• 英文别名: (E)-3,3-Difluoro-1-nitro-1-propene；3,3-difluoro-1-nitroprop-1-ene
• CAS: 879125-91-4
• 化学式: C₃H₃F₂NO₂
• 分子量: 123.059
• InChiKey: ZTGYBIKFESHPMQ-UHFFFAOYSA-N

物化性质

• 沸点：
  183.8±40.0 °C(Predicted)
• 密度：
  1.285±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  8
• 可旋转键数：
  1
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  45.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  3,3-difluoro-1nitropropene 、 L-苯丙氨酸叔丁酯盐酸盐 在 N,N-二异丙基乙胺 作用下， 以 甲苯 为溶剂， 以68%的产率得到
  参考文献：
  名称：

  Synthesis of Ψ[CH(RF)NH]Gly-peptides: The dramatic effect of a single fluorine atom on the diastereocontrol of the key aza-Michael reaction

  摘要：

  We describe in full-detail the synthesis of new Psi[CH(R-F)NH]-peptidomimetics, having different fluoroalkyl groups RF, as peptide bond surrogates. A key step in the synthesis is a stereoselective aza-Michael addition of chiral alpha-amino acid esters to beta-fluoroalkyl-alpha-nitroethenes. The diastereoselection of the process was influenced by the electronegativity, rather than by the steric bulk, of the fluorinated residue R-F in the beta-position of the nitroalkene acceptors. Replacement of a single F atom of R-F by a hydrogen or methyl group brings about a dramatic drop of stereocontrol, whereas Br, Cl and CF3, albeit bulkier than F, provide inferior results in terms of stereocontrol. A mechanistic hypothesis is provided. (c) 2008 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jfluchem.2008.06.018
• 作为产物：
  描述：

  1,1-difluoro-3-nitro-2-propanol 在 四磷十氧化物 作用下， 生成 3,3-difluoro-1nitropropene
  参考文献：
  名称：

  The Influence of Fluoroalkyl-Group Electronegativity on Stereocontrol in the Synthesis of Ψ[CH(R_F)NH]Gly Peptides

  摘要：

  新型肽类仿生物分子已合成，这些分子具有不同氟化程度的CH(RF)NH单元，作为肽键的替代物。合成的关键步骤是选择性地将手性α-氨基酸酯与β-氟烷基-α-硝基乙烯进行氮的迈克尔加成。该过程的反式选择性受到氟化基团RF在β位的电负性影响，而非空间位阻的影响。当将RF的单个氟原子替换为氢或甲基时，立体控制能力急剧下降，而Br、Cl和CF3虽然比F体积更大，但在立体控制方面的结果更差。

  DOI：

  10.1055/s-2008-1072653

文献信息

• H-bond donor-directed switching of diastereoselectivity in the Michael addition of α-azido ketones to nitroolefins
  作者：Pei-Gang Ding、Feng Zhou、Xin Wang、Qiu-Hua Zhao、Jin-Sheng Yu、Jian Zhou

  DOI：10.1039/d0sc00475h

  日期：——

  on the control of diastereoselectivity by H-bond donors. While the squaramide-catalyzed reaction proceeded with a transition state with both squaramide N–H bonds binding to an enolate intermediate, an unprecedented model was proposed for the phosphoramide-mediated reaction wherein an amide N–H bond and an alkylammonium ion formed in situ interact with nitroolefins, with the enolate stabilized by nonclassical

  催化剂控制的立体发散性不对称催化的发展对于从同一起始原料容易获得具有多个立体中心的手性产物的所有立体异构体至关重要。尽管取得了进展，但仍非常需要用于非对映异构性不对称催化的新设计策略。在这里，我们报告了H键供体的效能，作为调节α-叠氮基酮向硝基烯烃的高度非对映选择性可转换对映选择性迈克尔加成反应中非对映选择性的控制因素。而新开发的双官能叔胺，磷酰胺，优先得到顺式-adducts，类似squaramide催化剂选择性地得到防-加合物。可以通过一锅操作将生成的多功能叔叠氮化物转化为具有四个连续立体中心的螺吡咯烷。机理研究为氢键供体控制非对映选择性提供了依据。虽然方酰胺催化的反应以过渡状态进行，且两个方酰胺N–H键均与烯醇酸酯中间体结合，但对于磷酰胺介导的反应提出了前所未有的模型，其中酰胺N–H键与原位形成的烷基铵离子相互作用与硝基烯烃结合，通过非经典的C–H⋯O氢键相互作用稳定了烯醇盐。
• The Influence of Fluoroalkyl-Group Electronegativity on Stereocontrol in the Synthesis of <i>Ψ</i>[CH(R_F)NH]Gly Peptides
  作者：Alessandro Volonterio、Matteo Zanda、Serena Bigotti

  DOI：10.1055/s-2008-1072653

  日期：——

  New peptidomimetics featuring CH(RF)NH units, having different degree of fluorination, as peptide-bond surrogates have been synthesized. The key step in the synthesis consists of a stereoselective aza-Michael addition of chiral α-amino acid esters to β-fluoroalkyl-α-nitroethenes. The diastereoselection of the process was influenced by the electronegativity, rather than by the steric bulk, of the fluorinated residue RF in β-position of the nitroalkene acceptors. Replacement of a single F atom of RF by a hydrogen or methyl group brings about a dramatic drop of stereocontrol, whereas Br, Cl, and CF3, albeit bulkier than F, provide poorer results in terms of stereocontrol.

  新型肽类仿生物分子已合成，这些分子具有不同氟化程度的CH(RF)NH单元，作为肽键的替代物。合成的关键步骤是选择性地将手性α-氨基酸酯与β-氟烷基-α-硝基乙烯进行氮的迈克尔加成。该过程的反式选择性受到氟化基团RF在β位的电负性影响，而非空间位阻的影响。当将RF的单个氟原子替换为氢或甲基时，立体控制能力急剧下降，而Br、Cl和CF3虽然比F体积更大，但在立体控制方面的结果更差。
• Highly enantioselective direct Michael addition of 1,3-dicarbonyl compounds to β-fluoroalkyl-α-nitroalkenes
  作者：Yan Zhao、Xiao-Jin Wang、Yun Lin、Chen-Xin Cai、Jin-Tao Liu

  DOI：10.1016/j.tet.2014.02.062

  日期：2014.4

  Cinchona alkaloid catalysts were used in the Michael addition reaction of 1,3-dicarbonyl compounds to β-fluoroalkyl-α-nitroalkenes for the first time. The catalytic system performed well over a broad scope of substrates including β-keto esters and 1,3-diketones with high diastereoselectivities and excellent enantioselectivities (up to 99% ee) under mild conditions. A wide range of useful fluorinated

  金鸡纳生物碱催化剂首次用于1,3-二羰基化合物与β-氟代烷基-α-硝基烯烃的迈克尔加成反应。在温和条件下，该催化体系在包括β-酮酸酯和1,3-二酮在内的各种底物上均具有良好的非对映选择性和出色的对映选择性（最高99％ee），表现良好。合成了多种有用的氟化手性结构单元。
• Synthesis of Ψ[CH(RF)NH]Gly-peptides: The dramatic effect of a single fluorine atom on the diastereocontrol of the key aza-Michael reaction
  作者：Serena Bigotti、Stefano V. Meille、Alessandro Volonterio、Matteo Zanda

  DOI：10.1016/j.jfluchem.2008.06.018

  日期：2008.9

  We describe in full-detail the synthesis of new Psi[CH(R-F)NH]-peptidomimetics, having different fluoroalkyl groups RF, as peptide bond surrogates. A key step in the synthesis is a stereoselective aza-Michael addition of chiral alpha-amino acid esters to beta-fluoroalkyl-alpha-nitroethenes. The diastereoselection of the process was influenced by the electronegativity, rather than by the steric bulk, of the fluorinated residue R-F in the beta-position of the nitroalkene acceptors. Replacement of a single F atom of R-F by a hydrogen or methyl group brings about a dramatic drop of stereocontrol, whereas Br, Cl and CF3, albeit bulkier than F, provide inferior results in terms of stereocontrol. A mechanistic hypothesis is provided. (c) 2008 Elsevier B.V. All rights reserved.