6-vinylbicyclo[3.1.0]hexan-2-one | 73522-96-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 6-vinylbicyclo[3.1.0]hexan-2-one
• 英文别名: (+/-)-exo-6-vinyl-bicyclo[3.1.0]hexane-2-one；(1S,5S,6S)-6-ethenylbicyclo[3.1.0]hexan-2-one
• CAS: 73522-96-0
• 化学式: C₈H₁₀O
• 分子量: 122.167
• InChiKey: IJGPTRGYEZQWQS-VMHSAVOQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  9.0
• 可旋转键数：
  1.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  17.07
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  6-vinylbicyclo[3.1.0]hexan-2-one 在 碳酸铅(II) 作用下， 生成 cis-bicyclo<3.3.0>oct-6-en-2-one
  参考文献：
  名称：

  分子内类胡萝卜素除1,3二烯。环戊烯环环体系的合成。

  摘要：

  含有1，3-二烯部分的重氮酮被分解以立体定向地产生相应的乙烯基环丙烷。描述了乙烯基环丙烷到环戊烯的转化，并讨论了反应的范围。

  DOI：

  10.1016/s0040-4039(01)86741-1
• 作为产物：
  描述：

  1-diazoocta-5,7-dien-2-one 在 copper acetylacetonate 作用下， 以 苯 为溶剂， 生成 6-vinylbicyclo[3.1.0]hexan-2-one
  参考文献：
  名称：

  分子内类胡萝卜素除1,3二烯。环戊烯环环体系的合成。

  摘要：

  含有1，3-二烯部分的重氮酮被分解以立体定向地产生相应的乙烯基环丙烷。描述了乙烯基环丙烷到环戊烯的转化，并讨论了反应的范围。

  DOI：

  10.1016/s0040-4039(01)86741-1

文献信息

• Synthesis of 1-Acyl-2-vinylcyclopropanes: Utilizing Copper-Carbenoid versus Sulfur Ylide Methodology
  作者：Sabine Laschat、Anna Zens、Philipp Seubert、Benedikt Kolb、Marius Wurster、Marcel Holzwarth、Fabian Mannchen、Robert Forschner、Birgit Claasen、Doris Kunz

  DOI：10.1055/s-0036-1591554

  日期：2018.6

  Abstract The synthesis of a range of racemic 1-acyl-2-vinylcyclo­propanes by using two different methodologies is studied. We have developed a copper-catalyzed process for converting diazoketones into 1-acyl-2-vinylcyclopropanes and a sulfur-ylide-mediated procedure which allows, in only two steps, a simplified access to 1-acyl-2-vinyl­cyclopropanes with alkyl or aryl substituents on the alkene moiety

  摘要 研究了使用两种不同方法合成一系列外消旋1-酰基-2-乙烯基环丙烷的方法。我们已经开发出了一种铜催化的方法，用于将重氮酮转化为1-酰基-2-乙烯基环丙烷，以及由硫代叶酸介导的方法，该方法仅需两个步骤即可简化烷基或芳基生成1-酰基-2-乙烯基环丙烷的过程。烯烃部分上的取代基。 研究了使用两种不同方法合成一系列外消旋1-酰基-2-乙烯基环丙烷的方法。我们已经开发出了一种铜催化的方法，用于将重氮酮转化为1-酰基-2-乙烯基环丙烷，以及由硫代叶酸介导的方法，该方法仅需两个步骤即可简化烷基或芳基生成1-酰基-2-乙烯基环丙烷的过程。烯烃部分上的取代基。
• Potent tricyclic pyrazole tetrazole agonists of the nicotinic acid receptor (GPR109a)
  作者：P. Douglas Boatman、Thomas O. Schrader、Michelle Kasem、Benjamin R. Johnson、Philip J. Skinner、Jae-Kyu Jung、Jerry Xu、Martin C. Cherrier、Peter J. Webb、Graeme Semple、Carleton R. Sage、Jens Knudsen、Ruoping Chen、Andrew K. Taggart、Ester Carballo-Jane、Jeremy G. Richman

  DOI：10.1016/j.bmcl.2010.03.062

  日期：2010.5

  Tricyclic pyrazole tetrazoles which are potent partial agonists of the high affinity niacin receptor, GPR109a, have been discovered and optimized. One of these compounds has proven to be effective at lowering free fatty acids in vitro and in vivo.

  已经发现并优化了作为高亲和力烟酸受体GPR109a的部分激动剂的三环吡唑四唑。这些化合物中的一种已被证明可有效降低体内和体外的游离脂肪酸。
• Thermal rearrangement of divinylcyclopropane systems. Preparation of functionalized, stereochemically defined bicyclic and tricyclic products containing the bicyclo[3.2.1]octane skeleton
  作者：Edward Piers、Grace L. Jung、Neil Moss

  DOI：10.1016/0040-4039(84)80040-4

  日期：——

  A study involving the preparation and thermolysis of substituted 6--(1-alkenyl)bicyclo[3.1.0]hex-2-ene systems (14, 15, 23, 29, 40) shows (a) that C-8 functionalized bicyclo[3.2.1]octa-2,6-dienes can be prepared readily this methodology (14 → 16; 15 → 17), (b) that the rearrangement reaction is stereospecific even when the 6-(1-alkenyl) group is substituted with a sterically bulky isopropyl group (23

  一项涉及制备和热取代取代的6 --（1-烯基）双环[3.1.0]己-2-烯体系（14，15，23，29，40）的研究表明（a）C-8功能化的双环[3.2.1] octa-2,6-dienes可以很容易地用这种方法制备（14→16； 15→17），（b）即使6-（1-烯基）基团被取代，重排反应也是立体有序的（23→24； 29→30），并且（c）该方法可以扩展到包括三环系统的制备（40→41）。
• Piers, Edward; Jung, Grace L.; Ruediger, Edward H., Canadian Journal of Chemistry, 1987, vol. 65, p. 670 - 682
  作者：Piers, Edward、Jung, Grace L.、Ruediger, Edward H.

  DOI：——

  日期：——
• Generation of [5.5.<i>n</i>] Tricyclic Ring Systems by Radical-Promoted Inter- and Intramolecular [3 + 2] Cycloadditions
  作者：Michael E. Jung、Heather L. Rayle

  DOI：10.1021/jo9706133

  日期：1997.7.1

  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.