bicyclo[3.1.0]hex-2-en-6-endo-carboxaldehyde | 4729-05-9

• 分子结构分类: 有机化合物 - 有机氧化合物 - 有机氧化物
• 英文名称: bicyclo[3.1.0]hex-2-en-6-endo-carboxaldehyde
• 英文别名: 1,5α-bicyclo[3.1.0]hex-2-ene-6β-carbaldehyde；(1R,5S,6R)-bicyclo[3.1.0]hex-2-ene-6-carbaldehyde
• CAS: 4729-05-9；7176-16-1；34890-01-2；39521-41-0；39521-42-1；39643-60-2；61617-40-1；148152-96-9
• 化学式: C₇H₈O
• 分子量: 108.14
• InChiKey: DVZTVIVLAFIUFZ-VQVTYTSYSA-N

物化性质

• 沸点：
  158.5±29.0 °C(Predicted)
• 密度：
  1.238±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  8
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  bicyclo[3.1.0]hex-2-en-6-endo-carboxaldehyde 在 palladium on activated charcoal 二丁基二硫 、 Celite 、 氢气 、 对甲苯磺酰肼 、 pyridinium chlorochromate 、 儿萘酚硼烷 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 36.0h， 生成 cis-transoid-cis-tricyclo[6.3.0.0^2,6]undecane
  参考文献：
  名称：

  Generation of [5.5.n] Tricyclic Ring Systems by Radical-Promoted Inter- and Intramolecular [3 + 2] Cycloadditions

  摘要：

  A new method for the synthesis of[5.5.n] tricyclic ring systems via radical fragmentation and double cyclization is described. The general process (Scheme 1) involves addition of an alkylthio radical to an alkenylcyclopropane 1 to generate the cyclopropylcarbinyl radical which opens to the homoallylic radical; this radical then adds to an alkene or alkyne radical trap to give a new alkyl radical which then adds back to the thioalkyl allylic system to generate, after loss of the alkylthio radical, the bi- or tricyclic product, 2, thus making the process analogous to a [3 + 2] cycloaddition. Thus addition of the butylthio radical (generated by photolysis of dibutyl disulfide) to the bicyclo-[3.1.0]hex-2-en-6-yl carboxylate 3 in the presence of an alkene or alkyne-either an acyclic radical trap, e.g., ethyl vinyl ether, isopropenyl acetate, methyl acrylate, or methyl propiolate, or a cyclic one, e.g., cyclopentenone, dihydrofuran, cyclopentenyl acetate, or cyclopentene-affords the desired bi- or tricyclic products 9-16 in yields of 54-88%. One can also use 6-vinylbicyclo[3.1.0]hexan-2-one (4) as the alkenylcyclopropane unit. Trapping of the radical generated by addition of butylthio radical to 4 with ethyl vinyl ether or cyclopentene affords the bi- and tricyclic products 17 and 18 in 66-68% yields. The products are formed as diastereomeric mixtures in all cases. This cyclization process can also be carried out in an intramolecular fashion, e.g., isomerization of the ketones 25 and 27 or the esters 28-30 with butylthio radical to give the tricyclic products 31-35 and 41-43. The use of dimethyl-substituted alkenes gives reasonably good diastereoselectivity favoring the cis-syn-cis isomer over the cis-anti-cis isomer, e.g., 7.5:1 for 33 over 34 and 4.2:1 for 41 over 42. The structures of the diastereomeric products were proven by comparison of the NMR spectra of the saturated analogues, which are known for the unsubstituted series and differ in their symmetry properties for the dimethyl-substituted case. These results indicate that the cyclization of a stabilized 5-hexenyl radical, e.g., 45 in Scheme 8, is reversible and leads to the most stable final product.

  DOI：

  10.1021/jo9706133
• 作为产物：
  描述：

  endo-bicyclo[3.1.0]hex-2-ene-6-carbaldehyde 在 吡啶氢碘酸盐 作用下， 以 二甲基亚砜 为溶剂， 生成 bicyclo[3.1.0]hex-2-en-6-endo-carboxaldehyde
  参考文献：
  名称：

  金属促进的乙烯基环丙烷到环戊烯重排的进一步研究。结构和铑配合物的热解外切-6-乙烯基双环[3.1.0]己-2-烯和1,6-8-η的晶体结构4 -5- allylcyclopent -2-烯基（六氟乙酰丙酮）合铑（III ）四聚体

  摘要：

  的反应外-6-乙烯基双环[3.1.0]己-2-烯与双（乙烯）铑（我）络合物导致乙烯和形成开环σπ双- allylrhodium衍生物的位移。六氟乙酰丙酮酸酯（11）是固态的四聚体，并且其结构已经通过X射线方法确定。[C 13 H 11 F 6 RhO 2 ] 4晶体为单斜晶，空间群P 2 1 / c，a = 19.641（7），b = 14.353（7），c = 44.87（1）Å，β= 98.03（ 3），Z= 8; 用衍射仪收集了3 266个观察到的反射[ I /σ（I）> 3.0]，并细化为R 0.077。

  DOI：

  10.1039/p29790000962

文献信息

• [EN] PYRAZOLYLPYRIDINE ANTIVIRAL AGENTS<br/>[FR] AGENTS ANTIVIRAUX DE PYRAZOLYLPYRIDINE
  申请人：GLAXOSMITHKLINE LLC

  公开号：WO2011050284A1

  公开（公告）日：2011-04-28

  Provided are compounds of Formula (I) and/or Formula (II) and pharmaceutically acceptable salts thereof, their pharmaceutical compositions, their methods of preparation, and their use for treating viral infections mediated by a member of the Flaviviridae family of viruses such as hepatitis C virus (HCV).

  提供的是公式(I)和/或公式(II)的化合物以及它们的药用可接受的盐、它们的药物组合物、它们的制备方法，以及它们用于治疗由黄病毒科病毒家族成员如丙型肝炎病毒(HCV)介导的病毒感染。
• Isomerisierungen und Umlagerungen in Bicyclischen Systemenvia cyclopropan-carbaldehyd-enamine
  作者：Max Rey、Andr� S. Dreiding

  DOI：10.1002/hlca.19740570327

  日期：1974.4.27

  The pyrrolidino-aminal (4) of bicyclo[3.1.0]hex-2-ene-6-endo-carbaldehyde (3) underwent a facile (80°), mildly acid catalyzed isomerization to the corresponding exo-aminal (6), which was characterized by hydrolysis to bicyclo[3.1.0]hex-2-ene-6-exo-carbaldehyde (7).

  双环[3.1.0]己-2-烯-6-内苯甲醛（3）的吡咯烷酮-氨基（4）容易地（80°），轻度酸催化异构化为相应的外-氨基（6），其特征在于水解成双环[3.1.0]己-2-烯-6-外-甲醛（7）。
• Kim, Won; Kim, Hyangdug; Rhee, Hakjune, Heterocycles, 2000, vol. 53, # 1, p. 219 - 224
  作者：Kim, Won、Kim, Hyangdug、Rhee, Hakjune

  DOI：——

  日期：——
• Huston,R. et al., Bulletin des Societes Chimiques Belges, 1979, vol. 88, p. 911 - 921
  作者：Huston,R. et al.

  DOI：——

  日期：——
• Cytochrome P-450 catalyzed oxidation of quadricyclane. Evidence for a radical cation intermediate
  作者：Ralph A. Stearns、Paul R. Ortiz de Montellano

  DOI：10.1021/ja00299a056

  日期：1985.6