endo-bicyclo[3.1.0]hex-2-ene-6-carbaldehyde | 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: endo-bicyclo[3.1.0]hex-2-ene-6-carbaldehyde
• 英文别名: bicyclo[3.1.0]hex-2-ene-6-carbaldehyde；(1α,5α,6β)-bicyclo[3.1.0]hex-2-ene-6-carbaldehyde；(1R,5S,6S)-bicyclo[3.1.0]hex-2-ene-6-carbaldehyde
• CAS: 4729-05-9
• 化学式: C₇H₈O
• 分子量: 108.14
• InChiKey: DVZTVIVLAFIUFZ-DSYKOEDSSA-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：

  endo-bicyclo[3.1.0]hex-2-ene-6-carbaldehyde 在 silver nitrate 作用下， 生成 Bicyclo<3.1.0>hex-2-en-6-endo-carbonsaeure
  参考文献：
  名称：

  Luebbe,F.; Sustmann,R., Chemische Berichte, 1979, vol. 112, p. 57 - 70

  摘要：

  DOI：
• 作为产物：
  描述：

  2,5-降冰片二烯 在 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 生成 endo-bicyclo[3.1.0]hex-2-ene-6-carbaldehyde
  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

文献信息

• Synthesis of 2-heterobicyclo[3.2.1]octanes and the corresponding monoenes and dienes
  作者：Paul Barraclough、Sevim Bilgic、Douglas W. Young

  DOI：10.1016/0040-4020(79)85013-9

  日期：1979.1

  Synthesis of the theoretically interesting 2-heterobicyclo[3.2.1.]octa-3,6-dienes and their dihydro-and tetrahydro-derivatives has been achieved in the oxygen, nitrogen and sulphur series. The parent compound of the nitrogen series appears to exist as 2-azabicyclo[3.2.1]octa-2,6-diene rather than as the enamine (3, R=H). The Cope rearrangement equilibrium (2, X=NR)⇌(3) lies more to the side of the

  在氧，氮和硫系列中，已经实现了理论上令人感兴趣的2-杂双环[3.2.1。]八-3,6-二烯及其二氢和四氢衍生物的合成。氮系列的母体化合物似乎以2-氮杂双环[3.2.1]八-2,6-二烯形式存在，而不是以烯胺形式存在（3，R = H）。当氮被吸电子基团取代时，与存在烷基取代基时相比，Cope重排平衡（2，X = NR）⇌（3）更位于二烯3的侧面。这些效果似乎表明二烯3中没有特殊的双糖共轭稳定作用。
• Further studies on metal-promoted vinylcyclopropane to cyclopentene rearrangements. Structure and thermolysis of rhodium complexes of exo-6-vinylbicyclo[3.1.0]hex-2-ene and the crystal structure of the 1,6–8-η⁴-5-allylcyclopent-2-enyl(hexafluoroacetylacetonato)rhodium(<scp>III</scp>) tetramer
  作者：Nathaniel W. Alcock、John M. Brown、John A. Conneely、David H. Williamson

  DOI：10.1039/p29790000962

  日期：——

  The reactions of exo-6-vinylbicyclo[3.1.0]hex-2-ene with bis(ethylene)rhodium(I) complexes lead to displacement of ethylene and formation of ring-opened σπ-bis-allylrhodium derivatives. The hexafluoroacetylacetonate (11) is tetrameric in the solid state and its structure has been determined by X-ray methods. Crystals of [C13H11F6RhO2]4 are monoclinic, space group P21/c, a= 19.641(7), b= 14.353(7),

  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。
• Blocking Fluorine Substitution in Biotransformation of Nortricyclanyl N-Phenylcarbamates with Beauveria bassiana
  作者：Günter Haufe、Dörthe Wölker

  DOI：10.1002/ejoc.200200647

  日期：2003.6

  The biotransformation of tricyclo[2.2.1.02,6]hept-3-yl N-phenylcarbamate (8) by a standard procedure using Beauveria bassiana gave a 7:1 mixture of optically active exo,exo- and exo,endo-5-hydroxytricyclo[2.2.1.02,6]hept-3-yl N-phenylcarbamates 15 and 16 in 19% isolated yield. No ring opening of the three-membered ring was observed. Substitution with a fluorine atom at the 5-endo- or 5-exo-position

  三环 [2.2.1.02,6]hept-3-yl N-phenylcarbamate (8) 通过标准程序使用白僵菌进行生物转化，得到 7:1 的旋光外型、外型和外型、内型 5-羟基三环混合物[2.2.1.02,6]庚-3-基N-苯基氨基甲酸酯15和16，分离产率为19%。没有观察到三元环的开环。在 5-内-或 5-外-位用氟原子取代可防止分子的任何脂环位置发生羟基化，而在较小程度上发生芳环的对羟基化。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
• A facile synthesis of an aminal of bicyclo[3.1.0]hexan-6-one and of endo-6-piperidinobicyclo[3.1.0]hexane
  作者：J. Szmuszkovicz、E. Cerda、M.F. Grostic、J.F. Zieserl

  DOI：10.1016/s0040-4039(01)89762-8

  日期：1967.1
• Aliphatic semidiones. XV. 2,3-Semidiones derived from the bicyclo[n.1.0]alkanes
  作者：Glen Allan Russell、John J. McDonnell、Philip R. Whittle、Richard S. Givens、Robert G. Keske

  DOI：10.1021/ja00735a022

  日期：1971.3