2,4,6-trimethyl-4-(prop-2-yn-1-yloxy)cyclohexa-2,5-dien-1-one

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2,4,6-trimethyl-4-(prop-2-yn-1-yloxy)cyclohexa-2,5-dien-1-one
• 英文别名: 2,4,6-Trimethyl-4-prop-2-ynoxycyclohexa-2,5-dien-1-one；2,4,6-trimethyl-4-prop-2-ynoxycyclohexa-2,5-dien-1-one
• 化学式: C₁₂H₁₄O₂
• 分子量: 190.242
• InChiKey: RQNBAOLVXZHFTL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.87
• 重原子数：
  14.0
• 可旋转键数：
  2.0
• 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：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  2,4,6-trimethyl-4-(prop-2-yn-1-yloxy)cyclohexa-2,5-dien-1-one 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,7aR,3Z)-rel-4-bromo-3-(bromomethylene)-4,6,7a-trimethyl-2,3,3a,7a-tetrahydro-benzofuran-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：

  (2,4,6-trimethylphenoxy)trimethylsilane 在 碘苯二乙酸 、 水 、 sodium hydride 作用下， 以 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 0.5h， 生成 2,4,6-trimethyl-4-(prop-2-yn-1-yloxy)cyclohexa-2,5-dien-1-one
  参考文献：
  名称：

  Tandem Dienone Photorearrangement–Cycloaddition for the Rapid Generation of Molecular Complexity

  摘要：

  A tandem dienone photorearrangement-cycloaddition (DPC) reaction of novel cyclohexadienone substrates tethered with various 2 pi and 4 pi reaction partners resulted in the formation of polycyclic, bridged frameworks. In particular, use of alkynyl ether-tethered substrates led to (3 + 2) cycloaddition to afford strained alkenes which could be further elaborated by intra- and intermolecular cycloaddition chemistry to produce complex, polycyclic chemotypes.

  DOI：

  10.1021/ja409992m

文献信息

• Catalyst-Controlled Regiodivergent Alkyne Insertion in the Context of C−H Activation and Diels-Alder Reactions: Synthesis of Fused and Bridged Cycles
  作者：Xukai Zhou、Yupeng Pan、Xingwei Li

  DOI：10.1002/anie.201704036

  日期：2017.7.3

  Rhodium(III)- and cobalt(III)-catalyzed C−H activation of indoles and coupling with 1,6-enynes is discussed. Under rhodium(III) catalysis, the alkyne insertion follows 2,1-regioselectivity with a subsequent type-I intramolecular Diels–Alder reaction (IMDA) to afford [6,5]-fused cycles. When catalyzed by the cobalt(III) congener, 1,2-insertion of the alkyne is preferred, and followed by a rare type-II

  讨论了铑（III）和钴（III）催化吲哚的CH活化以及与1,6-炔烃的偶联。在铑（III）催化下，炔烃的插入遵循2,1-区域选择性，随后发生I型分子内Diels-Alder反应（IMDA），从而得到[6,5]稠合的循环。当被钴（III）同源物催化时，优选炔烃的1,2-插入，然后是稀有的II型IMDA，从而导致桥连的[3,3,1]循环。炔烃插入的选择性主要通过催化剂的空间敏感性来调节。
• Silver(I)-Catalyzed Enyne Cyclization/Aromatization of Alkyne-Tethered Cyclohexadienones to Access Meta-Substituted Phenols
  作者：Anandarao Munakala、Rambabu Chegondi

  DOI：10.1021/acs.orglett.0c03819

  日期：2021.1.15

  Herein we report a highly regioselective silver(I)-catalyzed intramolecular annulation of alkyne-tethered cyclohexadienones to access meta-substituted phenols with enone functionality, which are difficult to synthesize from conventional methods. The reaction proceeds via intramolecular 1,6-enyne cyclization followed by aromatization and subsequent oxetene ring rearrangement. This strategy has also

  在本文中，我们报道了炔键连接的环己二酮的高度区域选择性的银（I）催化的分子内环化反应，以得到具有烯酮官能团的间位取代的苯酚，这很难通过常规方法合成。该反应通过分子内的1，6-烯炔环化，随后的芳构化和随后的氧杂环丁烯环重排进行。该策略还与广泛的C系环己二烯酮兼容，从而可以高产率生产茚满。产品的独特功能允许进行进一步的转换以扩展多样性。
• Divergent Annulative C–C Coupling of Indoles Initiated by Manganese-Catalyzed C–H Activation
  作者：Bingxian Liu、Jie Li、Panjie Hu、Xukai Zhou、Dachang Bai、Xingwei Li

  DOI：10.1021/acscatal.8b02560

  日期：2018.10.5

  Manganese(I)-catalyzed C–H activation of indoles and divergent annulative coupling with alkyne-tethered cyclohexadienones has been realized under operationally simple conditions. These annulation systems are under condition control. The coupling in the presence of BPh3 additive followed a C–H activation-alkyne insertion-Michael addition pathway, affording an exocyclic olefin attached to a tetrahydrofuran

  在操作简单的条件下，已经实现了锰（I）催化的吲哚的CH活化和与炔烃系环己二酮的不同的环状偶联。这些环形系统处于状态控制之下。在存在BPh 3添加剂的情况下，偶联反应遵循C–H活化-炔烃插入-迈克尔加成途径，从而提供连接到四氢呋喃环上的环外烯烃。相反，当Zn（OAc）2引入了/ PivOH添加剂，在分子内Diels–Alder反应的过程中进行了初始烯烃化反应，随后消除了醇，从而生成了稠合的六元环。选择性与使用铑（III）和钴（III）催化剂报道的那些相反，突出了锰催化剂的独特反应性和选择性。
• CuH-Catalyzed Asymmetric Intramolecular Reductive Coupling of Allenes to Enones
  作者：Yun-Xuan Tan、Xiao-Qi Tang、Ping Liu、De-Shen Kong、Ya-Li Chen、Ping Tian、Guo-Qiang Lin

  DOI：10.1021/acs.orglett.7b03608

  日期：2018.1.5

  The CuH-catalyzed asymmetric intramolecular reductive coupling of allenes to enones is successfully realized, providing cis-hydrobenzofurans with promising yields and excellent enantioselectivities. Such brilliant enantioselectivities are partially contributed by CuH-catalyzed favorable kinetic resolution of the cyclization products. This protocol tolerates a broad range of functional groups, allowing

  成功实现了CuH催化的烯丙基与烯酮的不对称分子内还原性偶联，为顺式-氢苯并呋喃提供了有希望的收率和出色的对映选择性。此类出色的对映选择性是由CuH催化的环化产物的良好动力学拆分而部分贡献的。该协议容许广泛的官能团，从而允许进一步构建三环和桥环结构。此外，还描述了4-取代的苯酚的间手性官能化和含酚的生物活性分子的不对称脱芳香化修饰。
• Enantioselective Synthesis of Tetrahydropyrano[3,4-<i>b</i> ]indoles: Palladium(II)-Catalyzed Aminopalladation/1,4-Addition Sequence
  作者：Junjie Chen、Xiuling Han、Xiyan Lu

  DOI：10.1002/anie.201708900

  日期：2017.11.13

  At the end of a tether: Palladium(II)-catalyzed asymmetric cyclization of aniline-tethered alkynyl cyclohexadienones leads to functionalized tetrahydropyrano-[3,4-b]indoles in good yields and excellent enantioselectivities. The process involves a novel intramolecular aminopalladation/1,4 addition sequence.

  在束缚的末端：钯（II）催化的苯胺束缚的炔基环己二烯酮的不对称环化反应以高收率和出色的对映选择性导致官能化的四氢吡喃基-[3,4- b ]吲哚。该过程涉及新的分子内氨基palpalation / 1,4加成序列。