bicyclo<5.4.0>undec-5-en-2-one | 63845-03-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: bicyclo<5.4.0>undec-5-en-2-one
• 英文别名: 3,4,4a,5,7,8-hexahydro-1H-benzo[7]annulen-6(2H)-one；(Z)-1,2,3,4,4a,5,7,8-octahydrobenzo[7]annulen-6-one；1,2,3,4,4a,5,7,8-Octahydro-benzo[7]annulen-6-one；1,2,3,4,4a,5,7,8-octahydrobenzo[7]annulen-6-one
• CAS: 63845-03-4
• 化学式: C₁₁H₁₆O
• 分子量: 164.247
• InChiKey: WGNHAQDGBSMFQX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  5-(trimethylsilyl)pent-4-ynal 在 四丁基氟化铵 、 甲基锂 、 叔丁基锂 、 苯乙醚 作用下， 以 四氢呋喃 、 乙醚 、 正戊烷 为溶剂， 反应 1.5h， 生成 bicyclo<5.4.0>undec-5-en-2-one
  参考文献：
  名称：

  Synthesis of Seven-Membered Carbocyclic Rings via a Microwave-Assisted Tandem Oxyanionic 5-exo dig Cyclization−Claisen Rearrangement Process

  摘要：

  Appropriately substituted 1-alkenyl-4-pentyn-l-ol systems, readily prepared from simple starting materials, serve as useful precursors to a number of substituted cyclohept-4-enone derivatives via a microwave-assisted tandem oxyanionic 5-exo cyclization/Claisen rearrangement sequence. The reactions involving terminally substituted 4-pentyn-1-ols were found to be highly stereoselective, with the a and beta groups in the final product showing a strong preference for the trans orientation.

  DOI：

  10.1021/jo0710432

文献信息

• Carbocyclic Ring Formation by the Intramolecular Reaction between Enol Silyl Ether and Allylic Acetate Moieties
  作者：Akira Itoh、Koichiro Oshima、Hisashi Yamamoto、Hitosi Nozaki

  DOI：10.1246/bcsj.53.2050

  日期：1980.7

  yl, affording stereospecifically the cis isomer of 2,2-dimethylbicyclo[4.4.0]dec-9-en-3-one. In contrast, the cis-disubstituted cyclohexene compound reacts only sluggishly to produce a mixture of the cis- and trans-fused octalones. Similar stereospecific effect of the allylic double bond configuration on the ease of cyclization has been observed in the synthesis of karahanaenone from 3,7-dimethyl-6-trimethylsiloxy-2

  反式-3-乙酰氧基-4-(4-甲基-3-三甲基甲硅烷氧基-3-戊烯基)环己烯的标题反应在Et2AlOAr存在下进行，其中Ar=2,6-二-叔丁基-4-甲基苯基，立体特异性地提供 2,2-二甲基双环 [4.4.0]dec-9-en-3-one 的顺式异构体。相比之下，顺式二取代环己烯化合物反应缓慢，生成顺式和反式稠合辛酮的混合物。在由 3,7-二甲基-6-三甲基甲硅烷氧基-2,6-辛二烯基乙酸酯合成卡拉哈烯酮和相关反应中，观察到烯丙基双键构型对环化容易程度的类似立体定向效应。
• Seven-membered rings via silyl enol ether participation in the olefin cyclization. Anti-Markownikoff cyclization in biomimetic terpene synthesis
  作者：Shinsuke Hashimoto、Akira Itoh、Yoshizo Kitagawa、Hisashi Yamamoto、Hitosi Nozaki

  DOI：10.1021/ja00454a066

  日期：1977.6
• Gold(I)-Catalyzed Divergence in the Reactivity of 3-Silyloxy 1,6-Enynes: Pinacol-Terminated vs Claisen-Terminated Cyclization Cascades
  作者：Baburaj Baskar、Hyo J. Bae、Sang E. An、Jae Y. Cheong、Young H. Rhee、Alexander Duschek、Stefan F. Kirsch

  DOI：10.1021/ol8008733

  日期：2008.6.1

  On activation with catalytic amounts of gold(I) complexes, 3-silyloxy 1,6-enynes can react through two alternative pathways. In one, a cascade reaction consisting of carbocyclization and subsequent pinacol rearrangement takes place. In the second pathway, a heterocyclization is followed by a Claisen rearrangement. The reaction outcome differs depending on the substitution pattern of the 3-silyloxy 1,6-enynes and, more importantly, the electronic properties of the gold-bound phosphane ligand.
• Synthesis of Seven-Membered Carbocyclic Rings via a Microwave-Assisted Tandem Oxyanionic 5-<i>exo</i> <i>dig</i> Cyclization−Claisen Rearrangement Process
  作者：Xin Li、Robert E. Kyne、Timo V. Ovaska

  DOI：10.1021/jo0710432

  日期：2007.8.1

  Appropriately substituted 1-alkenyl-4-pentyn-l-ol systems, readily prepared from simple starting materials, serve as useful precursors to a number of substituted cyclohept-4-enone derivatives via a microwave-assisted tandem oxyanionic 5-exo cyclization/Claisen rearrangement sequence. The reactions involving terminally substituted 4-pentyn-1-ols were found to be highly stereoselective, with the a and beta groups in the final product showing a strong preference for the trans orientation.