4-((4-(benzyloxy)but-2-yn-1-yl)oxy)-4-methylcyclohexa-2,5-dienone | 1448451-09-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 4-((4-(benzyloxy)but-2-yn-1-yl)oxy)-4-methylcyclohexa-2,5-dienone
• CAS: 1448451-09-9
• 化学式: C₁₈H₁₈O₃
• 分子量: 282.339
• InChiKey: MBNNCILDTHRJQT-UHFFFAOYSA-N

物化性质

• 沸点：
  439.5±45.0 °C(Predicted)
• 密度：
  1.13±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.68
• 重原子数：
  21.0
• 可旋转键数：
  5.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.28
• 拓扑面积：
  35.53
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  4-((4-(benzyloxy)but-2-yn-1-yl)oxy)-4-methylcyclohexa-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54 %的产率得到(3aS,4R,7aS,3Z)-rel-3-(2-(benzyloxy)-1-bromoethylidene)-4-bromo-7a-methyl-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：

  对甲酚 在 phenyliodine(III) diacetate 、 sodium hydride 作用下， 以 四氢呋喃 、 mineral oil 为溶剂， 反应 2.0h， 生成 4-((4-(benzyloxy)but-2-yn-1-yl)oxy)-4-methylcyclohexa-2,5-dienone
  参考文献：
  名称：

  Tunable Arylative Cyclization of 1,6-Enynes Triggered by Rhodium(III)-Catalyzed C–H Activation

  摘要：

  Two tunable arylative cyclizations of cyclohexadienone-containing 1,6-enynes are reported via rhodium(III)-catalyzed C-H activation of O-substituted N-hydroxybenzamides. The use of different O substituents, i.e. O-Piv and O-Me, on the directing group allows the formation of either tetracyclic isoquinolones through an (c)-Michael addition process or hydrobenzofurans through a (N)Michael addition process. Mechanistic investigations of these two cascade reactions clearly indicated that the C-H bond cleavage process was involved in the turnover-limiting step. Furthermore, the cyclization products could be subjected to various transformations for elaborating the pharmaceutically and synthetically valuable potential. This is the first example of a rhodium(III)-catalyzed arylative cyclization reaction of 1,6-enynes, and the results extend the application realm of Cp*Rh-III-catalyzed C-H activation cascade reactions.

  DOI：

  10.1021/ja5072702

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。
• 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。
• 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。
• Rhodium-Catalyzed Enantioselective and Desymmetrizative Pauson–Khand Reaction: Access to Tricyclo[6.2.1.0^4,11]undecenes
  作者：Pengfei Yang、Yaodu Zhang、Ming Chen、Qingyang Zhao、Zhi-Hui Ren、Zheng-Hui Guan

  DOI：10.1021/acs.orglett.1c03589

  日期：2021.12.3

  Rhodium-catalyzed asymmetric desymmetrization Pauson–Khand reaction of C4-alkynyl-tethered cyclohexadienones has been developed as a novel strategy for access to fused 6–5–5 tricycles bearing three consecutive stereogenic centers. An array of chiral tricyclo[6.2.1.04,11]undecenes have been synthesized in high yields and enantioselectivities in a single step under mild conditions. This strategy employs

  铑催化的不对称去对称化 C4-炔基连接的环己二烯酮的 Pauson-Khand 反应已被开发为一种获得具有三个连续立体中心的稠合 6-5-5 三环化合物的新策略。一系列手性三环[6.2.1.0 4,11 ]十一碳烯已在温和条件下以高产率和对映选择性在一个步骤中合成。该策略采用容易获得的含内烯烃的 1,6-烯炔，为构建含有环戊烯酮和环己烯酮的复杂分子的手性多环支架提供了潜在的强大工具。