4-(but-2-yn-1-yloxy)-4-vinylcyclohexa-2,5-dienone | 1448450-97-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 4-(but-2-yn-1-yloxy)-4-vinylcyclohexa-2,5-dienone
• 英文别名: 4-But-2-ynoxy-4-ethenylcyclohexa-2,5-dien-1-one
• CAS: 1448450-97-2
• 化学式: C₁₂H₁₂O₂
• 分子量: 188.226
• InChiKey: VOAVUQHBKFUJGL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  4-(but-2-yn-1-yloxy)-4-vinylcyclohexa-2,5-dienone 、 联硼酸频那醇酯 在 copper(l) chloride 、 sodium t-butanolate 、 (3,5-Dioxa-4-phospha-cyclohepta[2,1-a;3,4-a']dinaphthalen-4-yl)-bis-((R)-1-phenyl-ethyl)-amine 、 甲醇 作用下， 以 四氢呋喃 为溶剂， 反应 48.5h， 以63%的产率得到(3aS,7aS,Z)-3-(1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)ethylidene)-7a-vinyl-2,3,3a,4-tetrahydrobenzofuran-5(7aH)-one
  参考文献：
  名称：

  Cu-Catalyzed Asymmetric Borylative Cyclization of Cyclohexadienone-Containing 1,6-Enynes

  摘要：

  The first Cu-catalyzed asymmetric borylative cyclization of cyclohexadienone-containing 1,6-enynes is achieved through a tandem process: selective beta-borylation of propargylic ether and subsequent conjugate addition to cyclohexadienone. The reaction proceeds with excellent regioselectivity and enantioselectivity to afford an optically pure cis-hydrobenzofuran framework bearing alkenylboronate and enone substructures. Furthermore, the resulting bicyclic products could be converted to bridged and tricyclic ring structures. This method extends the realm of Cu-catalyzed asymmetric tandem reactions using bis(pinacolato)diboron (B(2)pin(2)).

  DOI：

  10.1021/ja404593c
• 作为产物：
  描述：

  1,4-二氧杂螺[4.5]癸-6,9-二烯-8-酮 在 sodium hydride 作用下， 以 四氢呋喃 、 mineral oil 为溶剂， 反应 2.25h， 生成 4-(but-2-yn-1-yloxy)-4-vinylcyclohexa-2,5-dienone
  参考文献：
  名称：

  Cu-Catalyzed Asymmetric Borylative Cyclization of Cyclohexadienone-Containing 1,6-Enynes

  摘要：

  The first Cu-catalyzed asymmetric borylative cyclization of cyclohexadienone-containing 1,6-enynes is achieved through a tandem process: selective beta-borylation of propargylic ether and subsequent conjugate addition to cyclohexadienone. The reaction proceeds with excellent regioselectivity and enantioselectivity to afford an optically pure cis-hydrobenzofuran framework bearing alkenylboronate and enone substructures. Furthermore, the resulting bicyclic products could be converted to bridged and tricyclic ring structures. This method extends the realm of Cu-catalyzed asymmetric tandem reactions using bis(pinacolato)diboron (B(2)pin(2)).

  DOI：

  10.1021/ja404593c

文献信息

• Highly Enantioselective Rhodium-Catalyzed Cross-Addition of Silylacetylenes to Cyclohexadienone-Tethered Internal Alkynes
  作者：Chang-Lin Duan、Yun-Xuan Tan、Jun-Li Zhang、Shiping Yang、Han-Qing Dong、Ping Tian、Guo-Qiang Lin

  DOI：10.1021/acs.orglett.9b00249

  日期：2019.3.15

  The first highly enantioselective rhodium-catalyzed cross-addition of silylacetylenes to cyclohexadienone-tethered internal alkynes has been achieved via a tandem process: regioselective alkynylation of the internal alkynes and subsequent intramolecular conjugate addition to the cyclohexadienones, affording the cis-hydrobenzofuran frameworks with good yields (up to 88% yield) and excellent enantioselectivities

  甲硅烷基乙炔与环己二烯酮系结的内部炔烃的第一次高对映选择性铑催化的交叉加成反应是通过串联过程实现的：内部炔烃的区域选择性炔基化，随后分子内共轭添加到环己二酮中，提供了具有良好收率的顺式-氢苯并呋喃骨架（高达88％的收率）和出色的对映选择性（90％–96％ee）。这种温和的反应显示出完美的原子经济性和广泛的官能团耐受性。此外，还介绍了克级实验和环化产物的各种进一步转化。
• Palladium-catalyzed desymmetric [2+2+2] cycloaddition of 1,6-enyne and alkyne
  作者：Wei-Cheng Zhao、Xin Wang、Juhua Feng、Ping Tian、Zhi-Tao He

  DOI：10.1016/j.tet.2020.131862

  日期：2021.1

  desymmetric [2+2+2] cycloaddition reaction of alkyne-tethered cyclohexadienone and internal alkyne is established. Widely existing fused tricyclic hydronaphthofuran and hydronaphthopyrrole frameworks are prepared diastereoselectively in moderate to excellent yields. One-step aromatization process provides a new and facile access to important benzene-containing tricycles from above cycloaddition products

  建立了新颖且直接的炔烃系环己二酮与内部炔烃的钯催化不对称[2 + 2 + 2]环加成反应。非对映选择性地以中等到优异的产率制备了广泛存在的稠合三环氢萘呋喃和氢萘吡咯骨架。一步芳构化工艺提供了一种新的途径，可以轻松地从上述环加成产物中获得重要的含苯三环。