4-(but-2-yn-1-yloxy)-4-ethylcyclohexa-2,5-dienone | 1448450-93-8

• 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-ethylcyclohexa-2,5-dienone
• 英文别名: 4-But-2-ynoxy-4-ethylcyclohexa-2,5-dien-1-one
• CAS: 1448450-93-8
• 化学式: C₁₂H₁₄O₂
• 分子量: 190.242
• InChiKey: OULQEYYEZJGYAE-UHFFFAOYSA-N

物化性质

• 沸点：
  317.3±42.0 °C(Predicted)
• 密度：
  1.04±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.42
• 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-ethylcyclohexa-2,5-dienone 在 1,3-二溴-5,5-二甲基海因 、 水 、 硫脲 作用下， 以 乙酸乙酯 为溶剂， 以60 %的产率得到(3aS,4R,7aS,3Z)-rel-4-bromo-3-(1-bromoethylidene)-7a-ethyl-2,3,3a,7a-tetrahydrobenzofuran-5(4H)-one
  参考文献：
  名称：

  Thiourea‐Promoted Cascade Dihalogenation‐Cyclization of Cyclohexadienone‐Containing 1,6‐Enynes

  摘要：

  AbstractOrganohalogens play an important role in the drug discovery and functional materials. However, the convenient preparation of organohalogens still remains a challenging task. Herein, we report a metal‐free cascade dihalogenation‐cyclization of cyclohexadienone‐containing 1,6‐enynes in a biodegradable solvent to generate the dibrominated cis‐tetrahydrobenzofuran‐5(4H)‐ones and cis‐dihydrobenzopyran‐6(5H)‐ones respectively bearing 1,4‐dibromobut‐1‐enyl subunit in trans‐trans and trans‐cis form. A subgram‐scale experiment and several downstream transformations are presented for elaborating the synthetic utility. Moreover, the potent anticancer activity is observed against MDA‐MB‐468 cells for the corresponding products.magnified image

  DOI：

  10.1002/adsc.202201185
• 作为产物：
  描述：

  4-乙基苯酚 、 2-丁炔-1-醇 在 [双(三氟乙酰氧基)碘]苯 作用下， 以30%的产率得到4-(but-2-yn-1-yloxy)-4-ethylcyclohexa-2,5-dienone
  参考文献：
  名称：

  铑催化的内消旋1,6-二烯炔的不对称芳环化反应导致对映体富集顺式苯并呋喃

  摘要：

  串联：通过串联芳基化/共轭加成序列实现了含环己二酮的内消旋-1,6-二烯酮与芳基硼酸的标题反应，并提供了一种具有优异收率和对映选择性的对映体富集的顺式-氢苯并呋喃的新颖方法。binap = 2,2'-双（二苯基膦基）-1,1'-联萘基，Boc =叔丁氧羰基。

  DOI：

  10.1002/anie.201300137

文献信息

• Palladium Enolate Umpolung: Cyclative Diacetoxylation of Alkynyl Cyclohexadienones Promoted by a Pd/SPRIX Catalyst
  作者：Kazuhiro Takenaka、Suman C. Mohanta、Hiroaki Sasai

  DOI：10.1002/anie.201311172

  日期：2014.4.25

  A novel palladium‐catalyzed reaction involving an unusual nucleophilic attack on a palladium enolate was developed using a spiro‐bis(isoxazoline) (SPRIX) ligand. Treatment of alkynyl cyclohexadienone substrates with a Pd/SPRIX catalyst in acetic acid under an oxygen atmosphere furnished diacetoxylated benzofuranone derivatives in good yields. This cyclative diacetoxylation proceeded enantioselectively

  使用螺双（异恶唑啉）（SPRIX）配体开发了一种新颖的钯催化反应，涉及对烯醇钯的不寻常亲核攻击。在氧气气氛下，在乙酸中用Pd / SPRIX催化剂在乙酸中处理炔基环己二烯酮底物，可提供高收率的二乙酰氧基化苯并呋喃酮衍生物。在光学纯的SPRIX配体的存在下，该环化二乙酰氧基化对映选择性地进行。
• 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。
• Ligand and substrate effects during Pd-catalyzed cyclizations of alkyne-tethered cyclohexadienones
  作者：Rodolfo Tello-Aburto、Kyle A. Kalstabakken、Andrew M. Harned

  DOI：10.1039/c3ob27491h

  日期：——

  The effects of ligand and substrate choice on the Pd-catalyzed cyclization of alkyne-tethered cyclohexadienones were examined. In the presence of a chiral ligand, the enantioselectivity of the desymmetrization is remarkably sensitive to structural changes in both the ligand and the substrate. Additionally, the regioselectivity of the reaction (5- vs. 6-membered ring formation) is dependent on the proximity

  考察了配体和底物选择对Pd催化的炔烃系环己二酮环化反应的影响。在手性配体的存在下，去对称化的对映选择性对配体和底物的结构变化都非常敏感。此外，反应的区域选择性（5元对6元环形成）取决于杂原子与炔烃的接近程度。
• Arylation/Intramolecular Conjugate Addition of 1,6-Enynes Enabled by Manganese(I)-Catalyzed C–H Bond Activation
  作者：Yun-Xuan Tan、Xing-Yu Liu、Yi-Shuang Zhao、Ping Tian、Guo-Qiang Lin

  DOI：10.1021/acs.orglett.8b03288

  日期：2019.1.4

  established through initiation by manganese(I)-catalyzed C–H bond activation. This tandem reaction involved unusual E/Z-isomerized alkenyl-Mn intermediates and proceeded smoothly with high chemoselectivities and perfect atom economy. The cyclization products could be further transformed to various structures. Mechanistic studies suggested that cleavage of the C–H bond was involved in the turnover-limiting

  含环己二烯酮的1，6-烯炔的芳基化/分子内共轭加成反应是通过锰（I）催化的CH键活化而引发的。该串联反应涉及不寻常的E / Z异构化的烯基-Mn中间体，并以高化学选择性和完美的原子经济性顺利进行。环化产物可以进一步转化为各种结构。机理研究表明，C–H键的断裂参与了周转限制步骤，并提出了锰卡宾阴离子中间体来解释这种E / Z异构化过程。
• Asymmetric Synthesis of a Fused Tricyclic Hydronaphthofuran Scaffold by Desymmetric [2+2+2] Cycloaddition
  作者：Qi Teng、Wenxiu Mao、Dong Chen、Zhen Wang、Chen‐Ho Tung、Zhenghu Xu

  DOI：10.1002/anie.201911071

  日期：2020.2.3

  rhodium(I)-BINAP-catalyzed highly enantioselective [2+2+2] cycloaddition of enynes with alkynes has been developed. Diverse fused tricyclic hydronaphthofuran scaffolds with three consecutive stereogenic centers were constructed in one step from easily available materials with excellent chemo-, regio-, diastereo-, and enantioselectivity. Notable features of these reactions include 100 % atom economy

  已经开发了铑（I）-BINAP催化的炔烃与炔烃的高对映选择性[2 + 2 + 2]环加成反应。一步一步从容易获得的材料中，以优异的化学，区域，非对映和对映体选择性构建了具有三个连续立体异构中心的多元稠合三环萘并呋喃骨架。这些反应的显着特征包括100％的原子经济性，非常宽的范围和温和的反应条件。