4,5-Dimethylen-cyclohexen | 54290-41-4

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: 4,5-Dimethylen-cyclohexen
• 英文别名: 1,2-Dimethylen-4-cyclohexen；Cyclohexene, 4,5-bis(methylene)-；4,5-dimethylidenecyclohexene
• CAS: 54290-41-4
• 化学式: C₈H₁₀
• 分子量: 106.167
• InChiKey: AYDXFMFJWWTQQK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  8
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  4,5-Dimethylen-cyclohexen 生成 (3aR,4aS,4a1s,8aR,9aS)-3a1,4a1-dimethyl-3a1,4a1,5,8-tetrahydro-1H,3H,4H,9H-benzo[1'',2'']cyclopropa[3',4']pentaleno[1',6':2,3,1]cyclopropa[1,2-c]furan-1,3-dione
  参考文献：
  名称：

  Neue wege zum elassovalensystem

  摘要：

  DOI：

  10.1016/s0040-4039(00)92794-1
• 作为产物：
  描述：

  cis-1,2,3,6-tetrahydrophthalic anhydride 在 咪唑 、 lithium aluminium tetrahydride 、 碘 、 三苯基膦 、 potassium hydroxide 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 4.5h， 生成 4,5-Dimethylen-cyclohexen
  参考文献：
  名称：

  Trisequential Photooxygenation Reaction: Application to the Synthesis of Carbasugars

  摘要：

  4,5-Dimethylenecyclohex-1-ene was subjected to a photooxygenation reaction to introduce oxygen functionalities. The endoperoxide obtained underwent an ene-reaction to form hydroperoxides with 1,3-diene structures. Further addition of singlet oxygen to the diene units resulted in the formation of tricyclic hydroperoxides having three oxygens in the molecule. Cleavage of the oxygen-oxygen bonds followed by epoxidation of the remaining C-C double bond and concomitant ring-opening reaction furnished the isomeric carbasugars.

  DOI：

  10.1021/ol401823m

文献信息

• 3‐(Methoxycarbonyl)Cyclobutenone as a Reactive Dienophile in Enantioselective Diels–Alder Reactions Catalyzed by Chiral Oxazaborolidinium Ions
  作者：Peng Yan、Changxu Zhong、Jie Zhang、Yu Liu、Huayi Fang、Ping Lu

  DOI：10.1002/anie.202014308

  日期：2021.2.23

  Cyclobutenone has been used as a highly reactive dienophile in Diels–Alder reactions, however, no enantioselective example has been reported. We disclose herein a chiral oxazaborolidine‐aluminum bromide catalyzed enantioselective Diels–Alder reaction of 3‐alkoxycarbonyl cyclobutenone with a variety of dienes. Furthermore, a total synthesis of (−)‐kingianin F was completed for the first time via enantioenriched

  环丁烯酮已被用作Diels-Alder反应中的高反应性亲二烯体，但是，没有报道对映体选择性的例子。我们在此公开了3-烷氧基羰基环丁烯酮与各种二烯的手性恶唑硼烷-溴化铝催化的对映选择性Diels-Alder反应。此外，通过对映体富集的环加合物双环[4.2.0]辛烷衍生物首次完成了（-）-kingianin F的全合成。
• General Synthetic Entry to Linearly-Fused Dihydrobenzocyclobutene-1,2-diones and Benzocyclobutene-1,2-diones via Annulation of 1,2-Bis(methylene)carbocycles with 3-Chloro-3-cyclobutene-1,2-dione¹
  作者：Arthur H. Schmidt、Gunnar Kircher、Markus Willems

  DOI：10.1021/jo9915877

  日期：2000.4.1

  The tandem Diels-Alder/dehydrochlorination reaction of semisquaric chloride (1) with the 1,2-bis(methylene)cycloalkanes 2a-c and 1,2-bis(methylene)-4-cyclohexene (9) affords the linearly-fused cycloalkanodihydrobenzocyclobutene-1,2-diones 3a-c and 3,4,7,8-tetrahydrocyclobuta[b]-naphthalene-1,2-dione (10), respectively. On treatment with MnO2, 3a-c are dehydrogenated to the respective carbocycle-fused

  半方氯化物（1）与1,2-双（亚甲基）环烷烃2a-c和1,2-双（亚甲基）-4-环己烯（9）的串联Diels-Alder /脱氯化氢反应可得到线性稠合的环烷二氢苯并环丁烯-1,2-二酮3a-c和3,4,7,8-四氢环丁[b]-萘-1,2-二酮（10）。在用MnO 2处理时，以良好的产率将3a-c脱氢为各自的碳环稠合的苯并环丁烯-1，2-二酮4a-c。3a和3b与溴反应得到加成产物5a，b，用三氟乙酸银处理后，得到苯并环丁烯-1，2-二酮4a，b。为了制备目的，序列3-> 5-> 4可以有利地作为“一锅法”进行。4a，b与alpha，alpha'的双缩合反应 -双氰基-邻-二甲苯和邻-苯二胺分别提供了五环联苯撑7a，b和环丁烯撑戊烯8a，b。这些环丁烯二酮表明它们本身是构建具有新颖环序列的延伸的线性稠合多环化合物的基础。通过热分解相应的1,4-二氢-2,3-苯并氧杂i-3-氧化物（阿魏酸）1
• The photochemical reaction of 9-cyanoanthracene with s-cisoid 2,3-disubstituted butadienes and the molecular structures of their photochemical [4+4]adducts
  作者：Yoshimasa Fukazawa、Tomiyoshi Fujihara、Shuji Usui、Yoshinori Shiobara、Mitsuaki Kodama

  DOI：10.1016/s0040-4039(00)85283-1

  日期：1986.1

  The photochemical cycloaddition of 9-cyanoanthracene with s-cisold 1,3-dienes (2–4) gave predominantly [4+4]cycloadducts (5.6a and 9a). The conformational study of the adducts by the spectral and X-ray analysis confirmed that 4- or 5-membered ring condensed derivatives (5 and 6a) have symmetric C2v type structure and those with 6-membered ring (9a and 10a) are rapidly equilibrating between two equivalent

  9-氰基蒽与s-顺式1,3-二烯（2-4）的光化学环加成反应主要产生[4 + 4]环加合物（5.6a和9a）。通过光谱和X射线分析对加合物进行构象研究，证实4或5元环稠合衍生物（5和6a）具有对称的C 2v型结构，而具有6元环的衍生物（9a和10a）迅速在两个等效的折叠结构之间平衡。
• 1,1-Dihalogenonaphtho[b]cyclopropenes
  作者：Paul Müller、Huong-Can Nguyen-Thi

  DOI：10.1016/s0040-4039(00)78981-7

  日期：1980.1

  The synthesis of 1,1-dichloro- and 1,1-difluoronaphtho[b]cyclopropene is described, starting from 4,5-dimethylenecyclohexene and the respective tetrahalogenocyclopropenes.

  描述了从4，5-二亚甲基环己烯和相应的四卤代环丙烯开始的1，1-二氯-和1，1-二氟萘[b]环丙烯的合成。
• A Convenient Diels-Alder Approach toward Potential Polyketide-like Antibiotics Using α-Activated α,β-Unsaturated 4,4-Dimethyl-1-tetralones as Dienophiles
  作者：Chia-Jui Lee、Manickavasakam Ramasamy、Hsuan-Hao Kuan、Chien-Huang Wu、Chein-Chung Lee、Jinq-Chyi Lee、Kak-Shan Shia

  DOI：10.3390/molecules28062739

  日期：——

  Making use of a Diels–Alder approach based on various α,β-unsaturated 2-carbomethoxy-4,4-dimethyl-1-tetralones as novel dienophiles, the corresponding polycyclic adducts could be efficiently synthesized in good to high yields (74~99%) in the presence of Lewis acid (e.g., SnCl4). Accordingly, a synthetically useful platform is established to provide a focused aromatic polyketide-like library for screening of potential natural and non-natural antimicrobial agents.

  利用基于各种α,β-不饱和 2-羰基甲氧基-4,4-二甲基-1-四氢萘酮作为新型二亲体的 Diels-Alder 方法，在路易斯酸（如 SnCl4）存在下，可以高效合成相应的多环加合物，产率高达 74%~99%。因此，我们建立了一个有用的合成平台，为筛选潜在的天然和非天然抗菌剂提供了一个有针对性的芳香族多酮类化合物库。

表征谱图