3'-methoxy-3'-methyl-3'H-spirocyclohexa-2,5-diene-1-isobenzofuran-4-one | 120254-83-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3'-methoxy-3'-methyl-3'H-spirocyclohexa-2,5-diene-1-isobenzofuran-4-one
• 英文别名: 3′-methoxy-3′-methyl-3′H-spiro[cyclohexane-1,1′-isobenzofuran]-2,5-dien-4-one；3'-methoxy-3'-methyl-3'H-spiro[cyclohexane-1,1'-isobenzofuran]-2,5-dien-4-one；3-Methoxy-3-methylspiro[2-benzofuran-1,4'-cyclohexa-2,5-diene]-1'-one
• CAS: 120254-83-3
• 化学式: C₁₅H₁₄O₃
• 分子量: 242.274
• InChiKey: XFVSIUVZBNBUFV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.43
• 重原子数：
  18.0
• 可旋转键数：
  1.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.27
• 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：

  3'-methoxy-3'-methyl-3'H-spirocyclohexa-2,5-diene-1-isobenzofuran-4-one 在 锌铜偶 作用下， 以 四氢呋喃 为溶剂， 反应 0.5h， 以96%的产率得到4-(2-acetylphenyl)phenol
  参考文献：
  名称：

  Intramolecular Anodic Carbon−Carbon Bond Formation from Oxidized Phenol Intermediates. Effect of Oxygenated Substituents on the Yields of Spiro Dienones in Electrochemical and Iodobenzene Diacetate Oxidations

  摘要：

  The single-cell, constant-current anodic oxidation of a series of 4-(2-alkenylaryl)phenols was studied in which the aryl substituents were 2-vinyl-4,5-dimethoxy, 6a; 2-propenyl-4,5-dimethoxy, 9a; 2-vinyl-4,5-methylenedioxy, 6b; 2-propenyl-4,5-methylenedioxy, 9b; 2-vinyl-4-methoxy, 6c; 2-propenyl-4-methoxy, 9c; 2-vinyl-5-methoxy, 6d; and 2-propenyl-5-methoxy, 9d. Two compounds having methoxyl groups on the phenolic ring were also studied: 4-(2'-propenylphenyl)-2-methoxyphenol, 9e, and 4-(2'-propenylphenyl)-3-methoxyphenol, 9f. A novel synthetic route to the methoxy compounds 6c, 9c, 6d, and 9d was developed. This involved as a key step the MAD, bis(2,6-ditert-butyl-4-methylphenoxide)methylaluminum, mediated addition of organolithium and Grignard reagents to functionalize quinol ether derivatives. Anodic oxidation of compounds 6a, 9a, 9b, 6c, 9c, and 9d gave good yields of spiro dienones arising from trapping of the phenoxonium ion by the alkenyl side chain followed by reaction of the resulting cation with methanol. The products from the electrochemical oxidation of these 4-(2'-alkenylaryl)phenols were compared with those obtained from the iodobenzene diacetate oxidations. In general, the compounds that gave good yields of spiro dienones from electrochemical oxidation gave good yields from iodobenzene diacetate oxidations. However, there were two cases in which the results of the two oxidations did not parallel each other. Whereas anodic oxidation of 9f gave a low yield of spiro dienone, the iodobenzene diacetate route gave a 74% yield of this product. In the case of 9d, the opposite effect was noted: the electrochemical route gave a higher yield than did the iodobenzene diacetate oxidation.

  DOI：

  10.1021/jo951799d
• 作为产物：
  描述：

  苯硼酸 在 sodium carbonate 、 [双(三氟乙酰氧基)碘]苯 作用下， 以 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 0.08h， 生成 3'-methoxy-3'-methyl-3'H-spirocyclohexa-2,5-diene-1-isobenzofuran-4-one
  参考文献：
  名称：

  通过角酰胺催化的磺胺迈克尔去对称化反应不对称合成螺环异苯并呋喃酮

  摘要：

  通过有机催化的磺胺-迈克尔去对称反应实现了螺环己烯酮异苯并呋喃酮的对映选择性合成。金鸡纳衍生的 squaramide通过控制添加各种芳基硫醇，有效促进螺环 2,5-环己二烯酮异苯并呋喃酮的去对称化，从而产生两个具有完美非对映选择性和非常好的对映选择性的邻位立构中心。

  DOI：

  10.1039/d3ob00126a

文献信息

• Spirodienones via a thermal uncatalyzed [1,3]-oxygen-to-carbon migration
  作者：Gary W Morrow、Shaopeng Wang、John S Swenton

  DOI：10.1016/0040-4039(88)85184-0

  日期：1988.1

  Exocyclic vinyl ethers derived from -quinols, readily available from aryllithium addition to quinone monoketals, undergo high-yield thermal [1,3]-oxygen-to-carbon migration, yielding spirodienones.

  衍生自-喹诺醇的环外乙烯基醚（可从芳基锂加成醌单缩酮）容易地进行高产率的热[1,3]-氧-碳迁移，从而生成螺二烯酮。
• PIDA-Promoted/HFIP-Controlled Dearomative Spirocyclization of Phenolic Ketones via a Spirocyclohexadienone-Oxocarbenium Cation Species
  作者：Shiyong Peng、Jieyin He、Liangliang Yang、Hong Zhang、Hongguang Li、Ming Lang、Chao Chen、Jian Wang

  DOI：10.1021/acs.joc.2c00482

  日期：2022.5.6

  conditions. Control experiments unravel that the reaction proceeds through a spirocyclohexadienone-oxocarbenium cation species. In addition, an in situ-generated hypervalent iodine(III)-catalyzed version, as well as the late-stage transformation of products via conjugate additions, was also realized.

  报道了苯碘（III）二乙酸盐促进/1,1,1,3,3,3-六氟异丙醇控制的酚酮脱芳环化，提供了两个结构有趣的支架文库，螺环己二烯酮缩酮及其乙酰氧基化对应物，中等至在温和的条件下获得优异的产量。对照实验揭示了反应通过螺环己二烯酮-氧代碳鎓阳离子物种进行。此外，还实现了原位生成的高价碘 (III) 催化形式，以及通过共轭添加实现产物的后期转化。
• Spiro-fused 2,5-cyclohexadienones from the thermal 1,3-alkyl migrations of quinol vinyl ethers. A strategy for conversion of a carbonyl carbon to a quaternary carbon
  作者：Shaopeng Wang、Gary W. Morrow、John S. Swenton

  DOI：10.1021/jo00283a035

  日期：1989.10
• MORROW, GARY W.;WANG, SHAOPENG;SWENTON, JOHN S., TETRAHEDRON LETT., 29,(1988) N 28, C. 3441-3444
  作者：MORROW, GARY W.、WANG, SHAOPENG、SWENTON, JOHN S.

  DOI：——

  日期：——