1-Isopropylbenzocyclobuten-1-ol

• 分子结构分类: 有机化合物 - 苯类化合物
• 英文名称: 1-Isopropylbenzocyclobuten-1-ol
• 英文别名: Bicyclo[4.2.0]octa-1,3,5-trien-7-ol, 7-(1-methylethyl)-(9CI)；7-propan-2-ylbicyclo[4.2.0]octa-1,3,5-trien-7-ol
• 化学式: C₁₁H₁₄O
• 分子量: 162.232
• InChiKey: JHLAHFNEPCOIHV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  12
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1-Isopropylbenzocyclobuten-1-ol 在 碘 作用下， 95.0 ℃ 、3.33 kPa 条件下， 以36%的产率得到Isopropylidenebenzocyclobutene
  参考文献：
  名称：

  Preparation and Photosensitized Oxidation of Isopropylidenecyclobutanes and -cyclobutenes

  摘要：

  Isopropylidenecyclobutanes 2-5 underwent facile ene reaction with singlet dioxygen, yielding (upon Ph(3)P reduction) the corresponding pairs of epimeric allylic alcohols 9 and 10, 11 and 12, 13 and 14, and 15 and 16, respectively. A combination of spectral evidence and molecular modeling studies were utilized in the structural assignment of the epimers. The data clearly indicate that steric considerations play an important role in determining the face of the ring which O-1(2) approaches. Isopropylidenecyclobutenes 6 and 7 reacted with singlet oxygen more slowly than their monoolefinic analogs, yielding upon reduction allylic alcohols 21b and 22, respectively. Benzo analog 7 also generated a small and solvent-dependent amount of isomeric aldehydes 23 and 24, presumably via a free-radical mechanism. n-Butyl diene 8 underwent rapid photosensitized oxygenation producing allylic alcohol 35 (as the O-1(2) ene product) and dione 37 (the Hock-cleavage product of allylic hydroperoxide 39, formed in turn via a free-radical route) in a 1:9 ratio. Ah initio (STO-3G) calculations confirm that, in their lowest energy conformations, compounds 2-8 are planar with the methylene ring hydrogens displaced ca. 36 degrees from the perpendicular. As a result, only exocyclic ene product is formed, since O-1(2) strongly prefers axial or pseudoaxial allylic hydrogens. These calculations combined with the relative rate data suggest that the initial interaction between the electrophilic O-1(2) and alkylidenecyclobutenes involves both ends of the singlet dioxygen molecule, in which the ''front'' end attacks the reactive exocyclic double bond while the ''back'' end obtains stabilization by interacting with the more electron rich but unreactive endocyclic olefin linkage. Because of this added, and presumably substantial, stabilization, the relative rates within this system are determined in part by the orbital coefficients at the latter olefinic center.

  DOI：

  10.1021/jo00083a019
• 作为产物：
  描述：

  2-碘苯乙酸 在 4-二甲氨基吡啶 、 叔丁基锂 、 盐酸-N-乙基-Nˊ-(3-二甲氨基丙基)碳二亚胺 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 为溶剂， 反应 4.0h， 生成 1-Isopropylbenzocyclobuten-1-ol
  参考文献：
  名称：

  催化剂和条件控制下钴/铑催化的 C-C 裂解苯并环丁烯醇的多样化酰胺化

  摘要：

  使用二恶唑酮作为酰胺化试剂，实现了钴(III)和铑(III)催化的苯并环丁烯醇的区域和化学选择性酰胺化，通过苯并环丁烯醇的β-碳消除得到三类C-N偶联产物。Co(III)催化的偶联最初提供了可分离的邻- ( N-酰氨基)芳基甲基酮，其可以在条件控制下进一步环化为相应的吲哚衍生物。相比之下，在 Rh(III) 催化剂控制下实现了有效的逐步二酰胺化。化学选择性由催化剂和反应条件共同控制。

  DOI：

  10.1021/acs.orglett.3c01788

文献信息

• Construction of tetralin skeletons based on rhodium-catalysed site-selective ring opening of benzocyclobutenols
  作者：Naoki Ishida、Norikazu Ishikawa、Shota Sawano、Yusuke Masuda、Masahiro Murakami

  DOI：10.1039/c4cc09327e

  日期：——

  Tetralins (tetrahydronaphthalenes) are synthesised from benzocyclobutenols based on the rhodium-catalysed site-selective ring opening followed by intermolecular/intramolecular conjugate addition of the resulting arylrhodium species to electron-deficient alkenes. The produced structures make a remarkable contrast with those available from the same compounds under thermal reaction conditions.

  在铑催化的位点选择性开环的基础上，由苯并环丁烯醇合成四氢萘（四氢萘），然后将所得的芳基铑分子间/分子内共轭加成至电子不足的烯烃中。所产生的结构与在热反应条件下可从相同化合物获得的结构形成显着对比。
• Expeditious Synthesis of Isoquinolone Derivatives by Rhodium(I)-Catalyzed Annulation Reaction through C–C Bond Cleavage
  作者：Yiyi He、Chengsha Yuan、Zeqi Jiang、Li Shuai、Qing Xiao

  DOI：10.1021/acs.orglett.8b03653

  日期：2019.1.4

  A Rh(I)-catalyzed intermolecular cyclization between isocyanates and benzocyclobutenols leading to isoquinolin-1(2H)-ones through selective cleavage of a C–C bond has been realized. Exploiting the same strategy, we developed a Rh(I)-catalyzed three-component reaction of benzocyclobutenols, isonitriles, and sulfonyl azides to access isoquinolin-1(2H)-imines. These procedures provide unique and expeditious

  通过选择性裂解CC键，Rh（I）催化的异氰酸酯和苯并环丁烯醇之间的分子间环化反应导致异喹啉-1（2 H）-ones的形成。利用相同的策略，我们开发了Rh（I）催化的苯并环丁烯醇，异腈和磺酰叠氮化物的三组分反应，以访问异喹啉-1（2 H）-亚胺。这些程序提供了异喹诺酮衍生物的独特而迅速的途径，否则在温和的反应条件下，很难以令人满意的产率制备具有优异的官能团耐受性的异喹诺酮衍生物。
• Hydrogenolysis of 1-Alkoxybenzocyclobutenes with Site-selective Cleavage of the Sterically Hindered C(sp²)–C(sp³) Bond
  作者：Shota Sawano、Naoki Ishida、Masahiro Murakami

  DOI：10.1246/cl.150719

  日期：2015.11.5

  1-Alkoxybenzocyclobutenes undergo ring-opening hydrogenolysis with site-selective cleavage of the sterically hindered C(sp2)–C(sp3) bond on Pd/C.

  1-烷氧基苯并环丁烯在Pd/C条件下经历环开氢解反应，择位选择性地断裂空间位阻的C(sp2)–C(sp3)键。
• Rh(I)-Catalyzed Insertion of Allenes into C–C Bonds of Benzocyclobutenols
  作者：Chunliang Zhao、Li-Chuan Liu、Jing Wang、Chenran Jiang、Qing-Wei Zhang、Wei He

  DOI：10.1021/acs.orglett.5b03518

  日期：2016.1.15

  Herein we report a Rh(I)-catalyzed two carbon insertion into C–C bonds of benzocyclobutenols by employing symmetrical and unsymmetrical allenes. This reaction provides rapid access to alkylidene tetralins bearing two adjacent stereogenic centers in good yields and diasteroselectivities.

  在本文中，我们报告了通过使用对称和不对称的丙二烯，Rh（I）催化两个碳插入到苯并环丁烯醇的C–C键中。该反应提供了以良好的收率和非对映选择性快速接近带有两个相邻立体异构中心的亚烷基四氢化萘。
• Pd-Catalyzed Ring-Closing/Ring-Opening Cross Coupling Reactions: Enantioselective Diarylation of Unactivated Olefins
  作者：Lantao Liu、Fangyuan Cheng、Chenxiang Meng、An-An Zhang、Mingliang Zhang、Kai Xu、Naoki Ishida、Masahiro Murakami

  DOI：10.1021/acscatal.1c02277

  日期：2021.7.16

  Pd-catalyzed chemo-, regio-, and enantioselective ring-closing/ring-opening cross coupling reaction has been developed with diverse aryl halide-tethered alkenes and benzocyclobutenols as substrates, which renders the highly enantioselective diarylation of unactivated alkenes and provides a convenient method toward chiral 2,3-dihydrobenzofurans bearing a quaternary stereocenter with excellent enantioselectivities

  Pd催化的化学-、区域-和对映选择性闭环/开环交叉偶联反应已经开发出来，以多种芳基卤化物系链烯烃和苯并环丁烯醇为​​底物，这使得未活化烯烃的高度对映选择性二芳基化并提供了一种方便的方法具有四元立体中心的手性 2,3-二氢苯并呋喃，具有出色的对映选择性（高达 98% ee）。描述了大麻素受体2激动剂类似物在简明合成中的应用。