4-benzyl-4-(but-2-yn-1-yloxy)cyclohexa-2,5-dienone | 1448450-96-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 4-benzyl-4-(but-2-yn-1-yloxy)cyclohexa-2,5-dienone
• 英文别名: 4-Benzyl-4-but-2-ynoxycyclohexa-2,5-dien-1-one
• CAS: 1448450-96-1
• 化学式: C₁₇H₁₆O₂
• 分子量: 252.313
• InChiKey: PJDNHZNZSXQXAQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  19
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.24
• 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-benzyl-4-(but-2-yn-1-yloxy)cyclohexa-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58%的产率得到(3aS,7aS,Z)-7a-benzyl-3-(1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)ethylidene)-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：

  4-Benzyl-4-hydroxy-2,5-cyclohexadienone 、 1-溴-2-丁炔 在 sodium hydride 、 盐酸 作用下， 以 四氢呋喃 、 mineral oil 、 水 为溶剂， 反应 2.0h， 以47.9 mg的产率得到4-benzyl-4-(but-2-yn-1-yloxy)cyclohexa-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。
• 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。
• 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。
• Enantioselective Reductive Cyclization of Alkynyl-Tethered Cyclohexadienones Catalyzed by Rhodium Complexes
  作者：Yi-Fan Wang、Feng Wang、Dan-Dan Yang、Prasat Kittakoop、Yun-Xuan Tan、Ping Tian

  DOI：10.1021/acs.orglett.4c01276

  日期：2024.7.12

  of asymmetric cyclization reactions of 1,6-enynes have been established, simple asymmetric reductive cyclization remains underdeveloped. In this study, the enantioselective reductive cyclization of alkynyl-tethered cyclohexadienones (1,6-enynes) has been developed via a chiral pincer rhodium catalyst, affording cis-hydrobenzofurans and cis-hydroindoles with high enantioselectivities (90–99% ee). Furthermore

  尽管已经建立了各种类型的1,6-烯炔的不对称环化反应，但简单的不对称还原环化反应仍然不发达。在这项研究中，通过手性钳铑催化剂开发了炔基束缚的环己二酮（1,6-烯炔）的对映选择性还原环化，得到具有高对映选择性（90-99% ee）的顺式氢苯并呋喃和顺式氢吲哚。此外，还介绍了针对 SARS-CoV-2 3CL pro 的几种合成应用和初步抑制活性研究。