3-(4-硝基苯基)二环[2.2.1]庚-5-烯-2-甲醛 | 917760-52-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 3-(4-硝基苯基)二环[2.2.1]庚-5-烯-2-甲醛
• 英文名称: 3-(4-nitrophenyl)bicyclo[2.2.1]hept-5-ene-2-carboxaldehyde
• 英文别名: 3-(4-Nitrophenyl)bicyclo[2.2.1]hept-5-ene-2-carbaldehyde；3-(4-nitrophenyl)bicyclo[2.2.1]hept-5-ene-2-carbaldehyde
• CAS: 917760-52-2
• 化学式: C₁₄H₁₃NO₃
• 分子量: 243.262
• InChiKey: YOKLCWQYGJDLHV-UHFFFAOYSA-N

物化性质

• 沸点：
  386.1±42.0 °C(Predicted)
• 密度：
  1.343±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  18
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  62.9
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  3-(4-硝基苯基)二环[2.2.1]庚-5-烯-2-甲醛 在 sodium tetrahydroborate 作用下， 以 甲醇 为溶剂， 生成
  参考文献：
  名称：

  A General Approach for Preparation of Polymer-Supported Chiral Organocatalysts via Acrylic Copolymerization

  摘要：

  Polymer-supported chiral organocatalysts, as well as most other forms of immobilized catalysts! arc traditionally prepared by a postmodification approach where modified catalyst precursors are anchored onto prefabricated polymer beads. Herein, we report an alternative and more scalable approach where polymer-supported chiral enamine and iminium organocatalysts are prepared in a bottom-up fashion where methacrylic functional monomers are prepared in an entirely nonchromatographic manner and subsequently copolymerized with suitable comonomers to give cross-linked polymer beads. All syntheses have been conducted on multigram scale for all intermediates and finished polymer products, and the catalysts have proven successful in reactions taking place in solvents spanning a wide range of solvent polarity. While polymer-supported proline and proline-amides generally demonstrated excellent results and recycling robustness in asymmetric aldol reactions or ketones and benzaldehydes, the simplest type of Jorgensen/Hayashi diarylprolinol TMS-ether showed excellent selectivity, but rather sluggish reactivity in the Enders-type asymmetric cascade. The polymer-supported version of the first-generation MacMillan imidazolidinone had a pattern of reactivity very similar to that of the monomeric catalyst, but is too unstable to allow recycling.

  DOI：

  10.1021/jo902585j
• 作为产物：
  描述：

  4-硝基肉桂醛 、 环戊二烯 在 solid phase supported (5S)-5-Benzyl-2,2-dimethyl-3-(2-hydroxyethyl)-imidazolidin-4-one 作用下， 以 水 、 乙腈 为溶剂， 反应 24.0h， 以92%的产率得到3-(4-硝基苯基)二环[2.2.1]庚-5-烯-2-甲醛
  参考文献：
  名称：

  A General Approach for Preparation of Polymer-Supported Chiral Organocatalysts via Acrylic Copolymerization

  摘要：

  Polymer-supported chiral organocatalysts, as well as most other forms of immobilized catalysts! arc traditionally prepared by a postmodification approach where modified catalyst precursors are anchored onto prefabricated polymer beads. Herein, we report an alternative and more scalable approach where polymer-supported chiral enamine and iminium organocatalysts are prepared in a bottom-up fashion where methacrylic functional monomers are prepared in an entirely nonchromatographic manner and subsequently copolymerized with suitable comonomers to give cross-linked polymer beads. All syntheses have been conducted on multigram scale for all intermediates and finished polymer products, and the catalysts have proven successful in reactions taking place in solvents spanning a wide range of solvent polarity. While polymer-supported proline and proline-amides generally demonstrated excellent results and recycling robustness in asymmetric aldol reactions or ketones and benzaldehydes, the simplest type of Jorgensen/Hayashi diarylprolinol TMS-ether showed excellent selectivity, but rather sluggish reactivity in the Enders-type asymmetric cascade. The polymer-supported version of the first-generation MacMillan imidazolidinone had a pattern of reactivity very similar to that of the monomeric catalyst, but is too unstable to allow recycling.

  DOI：

  10.1021/jo902585j

文献信息

• Immobilization of MacMillan Imidazolidinone as Mac-SILC and its Catalytic Performance on Sustainable Enantioselective Diels-Alder Cycloaddition
  作者：Hisahiro Hagiwara、Toshihiro Kuroda、Takashi Hoshi、Toshio Suzuki

  DOI：10.1002/adsc.200900865

  日期：2010.3.22

  (Mac‐SILC) in the pores of silica gel with the aid of an ionic liquid – 1‐butyl‐3‐methylimidazolium bis(trifluoromethylsulfonyl)imide. The heterogenized organocatalyst was utilized for the enantioselective Diels–Alder reaction of cyclopentadiene and cinnamaldehyde, recovered by simple filtration and subsequent evacuation, and repeatedly used up to six times in 81% average chemical yield, 87% ee for endo‐

  麦克米伦的咪唑啉酮催化剂作为负载型离子液体催化剂（Mac‐SILC）借助离子液体– 1-丁基-3-甲基咪唑双（三氟甲基磺酰基）酰亚胺固定在硅胶孔中。所述多相有机催化剂是用于环戊二烯与肉桂醛的对映选择性狄尔斯-阿尔德反应，回收通过简单过滤和随后的抽空，并重复使用多达六次在81％的平均化学产率，87％ee值用于内切-和80％ee值用于exo产品。Mac‐SILC对多种基材均有效。
• DABCO‐based chiral ionic liquids as recoverable and reusable organocatalyst for asymmetric Diels–Alder reaction
  作者：Mohd Jubair Aalam、Deepa、Pooja Chaudhary、Dhan Raj Meena、Geeta Devi Yadav、Surendra Singh

  DOI：10.1002/chir.23385

  日期：2022.1

  New DABCO-based chiral ionic liquids were synthesized and evaluated in asymmetric Diels–Alder reaction of cyclopentadiene with α,β-unsaturated aldehydes or 4-phenyl-3-buten-2-one. Chiral ionic liquid of modified MacMillan catalyst having a DABCO cation and hexafluorophosphate anion acts as organocatalyst (5 mol%) for the Diels–Alder reaction of crotonaldehyde and cyclopentadiene producing 98% of the

  在环戊二烯与α,β-不饱和醛或 4-苯基-3-丁烯-2-酮的不对称 Diels-Alder 反应中合成并评估了基于 DABCO 的新型手性离子液体。具有 DABCO 阳离子和六氟磷酸根阴离子的改性 MacMillan 催化剂的手性离子液体作为有机催化剂 (5 mol%) 用于巴豆醛和环戊二烯的 Diels-Alder 反应，在 CH 3 CN/中产生 98% 的产物和 87% ee ( endo ) H 2 O (95/5) 在 25°C 下 2 小时。还通过使用环戊二烯和α,β-不饱和醛研究了催化的范围和局限性，Diels-Alder 产物的产率为 18%–92%，ee为 68%–93%. 催化剂被再循环和重复使用多达 6 个循环，ee和产品的转化率略有下降。
• Novel binaphthyl and biphenyl α- and β-amino acids and esters: organocatalysis of asymmetric Diels–Alder reactions. A combined synthetic and computational study
  作者：Philip C. Bulman Page、Francesca S. Kinsey、Yohan Chan、Ian R. Strutt、Alexandra M. Z. Slawin、Garth A. Jones

  DOI：10.1039/c8ob01795f

  日期：——

  aid in the identification of major enantiomers. The calculated product ratios agree well with the experimental data; the transition states identified involve preferential approach of cyclopentene along a trajectory adjacent to the acid/ester group. The four lowest energy transition states display a stabilizing dipolar interaction between the carbonyl group oxygen atom and a terminal proton of the diene

  已经研究了环戊二烯与肉桂醛之间Diels-Alder反应的不对称催化，使用了一系列具有联萘和联苯骨架的新型α-和β-氨基酸和氨基酯，提供高达62％ee的对映选择性。已在联萘催化剂实例上进行了B3LYP / 6-31G *计算，包括自由能校正，以识别过渡态结构并帮助鉴定主要对映异构体。计算出的产品比例与实验数据非常吻合；所确定的过渡态涉及沿环戊烯沿酸/酯基团相邻的轨迹的优先途径。四个最低的能量跃迁状态显示出羰基氧原子与二烯单元的末端质子之间稳定的偶极相互作用。
• One-step assembly of a MacMillan catalyst-based phenolic-type polymer
  作者：Yuan Zhang、Xiaorong Yang、Liqi Li、Yansong Hu、Shutao Wang

  DOI：10.1039/d3ob00624g

  日期：——

  herein a “bottom-up” approach for the one-step assembly of a MacMillan catalyst-based phenolic-type polymer (Mac-CP). The resulting self-supported polymeric organocatalyst possesses homogeneously distributed and highly concentrated catalytic sites. Furthermore, Mac-CP is soluble in CH3CN but insoluble in hexane. This unique property can be used to employ the polymer as an efficient catalyst in homogeneous

  我们在此报告了一种“自下而上”的方法，用于一步组装基于 MacMillan 催化剂的酚类聚合物 ( Mac-CP )。由此产生的自支撑聚合物有机催化剂具有均匀分布和高度集中的催化位点。此外，Mac-CP可溶于CH 3 CN但不溶于己烷。这种独特的性质可用于将聚合物用作均相有机催化和多相回收中的有效催化剂。因此，Mac-CP在不对称 Diels-Alder 反应中具有与其均相对应物相当的催化活性和对映选择性（产率为 95%，内切为 93% 对映体过量 (ee)，外切为 92 % ee）。
• Asymmetric Diels-Alder Reactions of α,β-Unsaturated Aldehydes Catalyzed by a Diarylprolinol Silyl Ether Salt in the Presence of Water
  作者：Yujiro Hayashi、Sampak Samanta、Hiroaki Gotoh、Hayato Ishikawa

  DOI：10.1002/anie.200801408

  日期：2008.8.18