exo-7-oxabicyclo[2.2.1]hept-5-ene-2-carbonitrile

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧唑烯
• 英文名称: exo-7-oxabicyclo[2.2.1]hept-5-ene-2-carbonitrile
• 英文别名: (1S,2S,4S)-7-oxabicyclo[2.2.1]hept-5-ene-2-carbonitrile
• 化学式: C₇H₇NO
• 分子量: 121.139
• InChiKey: AHQSHUPQQYFVER-XVMARJQXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.2
• 重原子数：
  9
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  33
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  exo-7-oxabicyclo[2.2.1]hept-5-ene-2-carbonitrile 在 硫氯五氟化物 、 三乙基硼 、 lithium hydroxide 作用下， 以 二氯甲烷 、 二甲基亚砜 为溶剂， 反应 1.5h， 以1.40 g的产率得到(3-呋喃基)五氟化硫
  参考文献：
  名称：

  Synthesis of Novel Pentafluorosulfanylfurans. Two Retro-Diels−Alder Approaches

  摘要：

  The first examples of furan substituted with an SF5 group are reported. 3-Pentafluorosulfanylfurans were prepared from their respective 2-pentafluorosulfanyl-5-cyano-7-oxabicyclo[ 2.2.1] hept-2-ene precursors via retro-Diels -Alder reactions. Also, a tandem cycloaddition/ retrocycloaddition reaction between 4-phenyloxazole and 1-pentafluorosulfanylhex-1-yne was used to prepare 3-pentafluorosulfanyl-4-butylfuran.

  DOI：

  10.1021/ol0622662
• 作为产物：
  描述：

  呋喃 、 丙烯腈 在 bismuth(lll) trifluoromethanesulfonate 作用下， 以 二氯甲烷 为溶剂， 反应 5.0h， 以76%的产率得到exo-7-oxabicyclo[2.2.1]hept-5-ene-2-carbonitrile
  参考文献：
  名称：

  狄尔斯-阿尔德催化反应报铋（III）

  摘要：

  我们研究了由三氟甲磺酸铋和氯化铋催化的二烯（1-3）和亲二烯体（4-6）的狄尔斯-阿尔德反应。我们将这两种催化剂分别与SnCl 4，ZnI 2，AlCl 3和Cu（BF 4）2进行了比较。对于铋衍生物，我们注意到没有聚合，在环加成反应中具有更好的产率和良好的选择性。

  DOI：

  10.1016/s0022-328x(99)00230-2

文献信息

• Synthetic studies related to diketopyrrolopyrrole (DPP) pigments. Part 1: The search for alkenyl-DPPs. Unsaturated nitriles in standard DPP syntheses: a novel cyclopenta[c]pyrrolone chromophore
  作者：Colin J.H Morton、Ryan Gilmour、David M Smith、Philip Lightfoot、Alexandra M.Z Slawin、Elizabeth J MacLean

  DOI：10.1016/s0040-4020(02)00443-x

  日期：2002.7

  methacrylonitrile give 4,4-bis(cyanoethyl) and 4,4-bis(2-cyanopropyl) derivatives, and cinnamonitrile, substituted cinnamonitriles and 3-(2-thienyl)acrylonitrile give deep red 3-aryl-5-cyano-4-hydroxy-2H-cyclopenta[c]pyrrol-1-ones. These ambident nucleophiles may undergo N- and either O- or C-alkylation according to the alkylating agent used.

  4,5-二氢-5-氧代-2-苯基吡咯-3-羧酸乙酯的阴离子与丙烯腈和各种二烯的狄尔斯-阿尔德加合物的反应很少产生预期的DPP衍生物。与环己-3-烯腈的反应提供了一个值得注意的例外：所生成的环己烯基-DPP的热解产生了丁二烯和不纯的3-乙烯基-6-苯基-DPP，后者是热不稳定的。当上述阴离子与α，β-不饱和腈反应时，迈克尔加成反应占主导：丙烯腈和甲基丙烯腈产生4,4-双（氰基乙基）和4,4-双（2-氰基丙基）衍生物，以及肉桂腈，取代的肉桂腈和3-（ 2-噻吩基）丙烯腈得到深红色的3-芳基-5-氰基-4-羟基-2 H-环戊[ c ]吡咯-1-酮。这些亲核试剂两可可经历Ñ-和根据所用烷基化剂的O-或C-烷基化。
• Tandem Diels−Alder Aromatization Reactions of Furans under Unconventional Reaction Conditions − Experimental and Theoretical Studies
  作者：José M. Fraile、José I. García、María A. Gómez、Antonio de la Hoz、José A. Mayoral、Andrés Moreno、Pilar Prieto、Luis Salvatella、Ester Vázquez

  DOI：10.1002/1099-0690(200108)2001:15<2891::aid-ejoc2891>3.0.co;2-m

  日期：2001.8

  acids are good catalysts for Diels−Alder reactions between furan and acrylonitrile and methyl acrylate at room temperature. When 2,5-dimethylfuran is used as the diene, yields of the Diels−Alder adducts with methyl acrylate are lower, due in part to the appearance of aromatization products. The use of microwave activation results in some cases in good yields of aromatic products and, as such, constitutes

  二氧化硅负载的路易斯酸是室温下呋喃与丙烯腈和丙烯酸甲酯之间的 Diels-Alder 反应的良好催化剂。当使用 2,5-二甲基呋喃作为二烯时，Diels-Alder 加合物与丙烯酸甲酯的产率较低，部分原因是芳构化产物的出现。在某些情况下，微波活化的使用导致芳族产品的高产率，因此，构成了多取代芳族化合物的良好合成途径。对反应机理和催化剂对产物分布作用的计算研究表明，“硬”路易斯酸，如铝衍生物，使加合物的开环更容易，得到芳香族产物。
• The Demjanov and Tiffeneau-Demjanov one-carbon ring enlargements of 2-aminomethyl-7-oxabicyclo[2.2.1]heptane derivatives. The stereo- and regioselective additions of 8-oxabicyclo[3.2.1]oct-6-en-2-one to soft electrophiles.
  作者：Daniela Fattori、Sylvie Henry、Pierre Vogel

  DOI：10.1016/s0040-4020(01)80352-5

  日期：——

  Nitrosation of 7-oxabicyclo[2.2.1]hept-5-en-2-exo-ylmethyl amine (20) gave 7-oxabicyclo[2.2.1]hept-5-en-2-exo-methanol (22) whereas 7-oxabicyclo[2.2.1]hept-5-en-2-endo-ylmethylamine (21) afforded a 1:1 mixture of 7-oxabicyclo[3.2.1]oct-6-en-2-ols (23) and 8-oxabicyclo[3.2.1]oct-3-en-2-ols (24). Nitrosations of 2-exo- (28) and 2-endo-aminomethyl-7-oxabicyclo[2.2.1]hept-5-en-2-ol (29) gave mixtures of 8-oxabicyclo[3

  将7-氧杂双环[2.2.1]庚-5-en-2- exo - yl甲基胺（20）亚硝化得到7-氧杂双环[2.2.1] hept-5-en-2 -exo-甲醇（22），-氧杂双环[2.2.1]庚-5-烯-2-内基甲胺（21）提供了7-氧杂双环[3.2.1] oct-6-en-2-ols（23）和8的1：1混合物-氧杂双环[3.2.1] oct-3-en-2-ols（24）。的Nitrosations 2 -exo- （28）和2 -内氨基甲基-7-氧杂双环[2.2.1]庚-5-烯-2-醇（29）得到8-氧杂双环[3.2.1] oct-6-en-2-one（25）和8-氧杂双环[3.2.1] oct-6-en-3-one（37）的混合物。对于C-（3）亚甲基迁移给25的偏好是最好的（12：1）在2- endo-氨基甲醇29的情况下。与双环[2.2.1]庚烷类似物的亚硝化作用相比，在28和29中的
• Stereochemistry of ring-opening/cross metathesis reactions of <i>exo</i>- and <i>endo</i>-7-oxabicyclo[2.2.1]hept-5-ene-2-carbonitriles with allyl alcohol and allyl acetate
  作者：Piotr Wałejko、Michał Dąbrowski、Lech Szczepaniak、Jacek W Morzycki、Stanisław Witkowski

  DOI：10.3762/bjoc.11.204

  日期：——

  ROCM reactions of exo- and endo-2-cyano-7-oxanorbornenes with allyl alcohol or allyl acetate promoted by different ruthenium alkylidene catalysts were studied. The stereochemical outcome of the reactions was established. The issues concerning chemo- (ROCM vs ROMP), regio- (1-2- vs 1-3-product formation), and stereo- (E/Z isomerism) selectivity of reactions under various conditions are discussed. Surprisingly

  研究了不同的烷基亚烷基钌催化剂促进的exo-和endo-2-cyano-7-oxanorbornebornenes与烯丙醇或乙酸烯丙酯的ROCM反应。确定了反应的立体化学结果。讨论了在各种条件下反应的化学反应（ROCM与ROMP），区域反应（1-2与1-3-产物形成）和立体反应（E / Z异构）的问题。在纯净条件下，ROCM产品的收率出乎意料地好。
• Niobium(V) Chloride as Catalyst in Diels-Alder Reaction of Furan Ring
  作者：Deborah A. dos Santos、Ludmila R. Rodrigues、Bruno H. Arpini、Valdemar Lacerda Junior、Sandro J. Greco、Reginaldo B. dos Santos、Álvaro Cunha Neto、Wanderson Romão、Eustaquio V. R. de Castro

  DOI：10.5935/0103-5053.20140052

  日期：——

  According to the relevant literature, the Diels-Alder reaction of furan without a catalyst can last several weeks and shows a low yield due to the diene's low reactivity. The use of Lewis acid catalysts or high pressures is described as an effective method for improving the reaction yields. This paper describes our recent study on the use of niobium pentachloride as the catalyst in Diels-Alder reactions between furan and several reactive dienophiles, among which methyl acrylate showed good yields, especially at lower temperatures. Other dienophiles have shown lower yields because of problems such as byproduct formation and the high reversibility of the reaction.