methyl 2-(6-(6,7,8,9-tetrahydro-5-oxo-5H-benzocycloheptenyl))acetate | 115033-88-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 2-(6-(6,7,8,9-tetrahydro-5-oxo-5H-benzocycloheptenyl))acetate
• 英文别名: methyl 2-(5-oxo-6,7,8,9-tetrahydro-5H-benzo[7]annulen-6-yl)acetate；6-(2-(methylperoxy)-2l2-ethyl)-6,7,8,9-tetrahydro-5H-benzo[7]annulen-5-one；(5-oxo-6,7,8,9-tetrahydro-5H-benzocyclohepten-6-yl)-acetic acid methyl ester；(5-Oxo-6,7,8,9-tetrahydro-5H-benzocyclohepten-6-yl)-essigsaeure-methylester；Methyl 2-(9-oxo-5,6,7,8-tetrahydrobenzo[7]annulen-8-yl)acetate；methyl 2-(5-oxo-6,7,8,9-tetrahydrobenzo[7]annulen-6-yl)acetate
• CAS: 115033-88-0
• 化学式: C₁₄H₁₆O₃
• 分子量: 232.279
• InChiKey: RDBVHMKODLYEKQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  methyl 2-(6-(6,7,8,9-tetrahydro-5-oxo-5H-benzocycloheptenyl))acetate 生成 3,4,5,6-tetrahydro-benzo[6,7]cyclohepta[1,2-b]furan-2-one
  参考文献：
  名称：

  Seven-membered Ring Compounds. VIII.¹ The Cyclization of Benzosuberane-5,6-diacetic Acid

  摘要：

  DOI：

  10.1021/ja01647a024
• 作为产物：
  描述：

  methyl 6-<2-<(phenylseleno)carbonyl>phenyl>-2-hexenoate 在 偶氮二异丁腈 、 三正丁基氢锡 作用下， 以 苯 为溶剂， 反应 0.5h， 以92%的产率得到methyl 2-(6-(6,7,8,9-tetrahydro-5-oxo-5H-benzocycloheptenyl))acetate
  参考文献：
  名称：

  Acyl radicals: intermolecular and intramolecular alkene addition reactions

  摘要：

  A full study of the use of phenyl selenoesters as precursors to acyl radicals and their subsequent participation in intermolecular and intramolecular alkene addition reactions is detailed. Primary alkyl-, vinyl-, and aryl-substituted acyl radicals generated by Bu3SnH treatment of the corresponding phenyl selenoesters participate cleanly in intermolecular addition reactions with alkenes bearing electron-withdrawing or radical-stabilizing substituents at rates that exceed those of the potentially competitive decarbonylation or reduction. Similarly, their intramolecular addition to activated or unactivated alkenes proceeds without significant competitive reduction or decarbonylation and at rates generally greater-than-or-equal-to 1 x 10(6) s-1 with some occurring at rates greater-than-or-equal-to 3 x 10(7) s-1. Consistent with their behavior in intermolecular addition reactions, the 5-exo-trig cyclizations of secondary and tertiary alkyl-substituted acyl radicals to an unactivated olefin acceptor may be accompanied by varying degrees of decarbonylation, even under low-temperature free-radical reaction conditions. Studies are presented which suggest that the intramolecular additions of acyl radicals to alkenes under the conditions detailed herein may be regarded as irreversible, kinetically controlled processes which exhibit regioselectivity that is predictable based on well-established empirical rules set forth for the analogous free-radical cyclization reactions of alkyl radicals.

  DOI：

  10.1021/jo00031a021

文献信息

• Concise Synthesis of Chiral Tricyclic Lactams by Tandem Dynamic Kinetic Asymmetric Reductive Amination/Lactamization Using Ammonium Salts
  作者：Jingxin Wang、Yongjie Shi、Fangyuan Wang、Fanping Huang、Shao‐Tao Bai、Yu Zhao、Xumu Zhang

  DOI：10.1002/anie.202303868

  日期：2023.6.19

  and economical one-pot approach to chiral fused tricyclic lactams from readily available ketoesters was developed by using cheap ammonium salts as the nitrogen source through ruthenium-catalyzed tandem dynamic kinetic asymmetric reductive amination/lactamization. This protocol provides highly efficient access to drug intermediates and organocatalysts containing chiral polycyclic N-heterocycles.

  通过使用廉价的铵盐作为氮源，通过钌催化的串联动力学不对称还原胺化/内酰胺化，开发了一种从现成的酮酯中制备手性稠合三环内酰胺的有效且经济的一锅法。该协议提供了对含有手性多环 N-杂环的药物中间体和有机催化剂的高效访问。
• Electrochemical Synthesis of Spirolactones from α-Tetralone Derivatives with Methanol as a C1 Source
  作者：Wei Xiao、Jianyan Wang、Jiamin Ye、Hongyan Wang、Jie Wu、Shengqing Ye

  DOI：10.1021/acs.orglett.4c01678

  日期：2024.6.14

  natural products. However, efficient and environmentally friendly approaches to accessing spirolactones are still highly desirable. Herein, a novel electrochemical synthesis of spirolactones from α-tetralone derivatives with methanol as a C1 source is described. This electrochemical reaction exhibits a high efficiency and good functional group tolerance.

  螺内酯广泛存在于药物和生物活性天然产物中。然而，仍然非常需要有效且环境友好的方法来获取螺内酯。本文描述了一种以甲醇为 C1 源，从 α-四氢萘酮衍生物电化学合成螺内酯的新方法。该电化学反应表现出高效率和良好的官能团耐受性。
• Acyl radicals: functionalized free radicals for intramolecular cyclization reactions
  作者：Dale L. Boger、Robert J. Mathvink

  DOI：10.1021/jo00249a053

  日期：1988.7
• BOGER, D. L.;MATHVINK, R. J., J. ORG. CHEM., 53,(1988) N 14, 3377-3379
  作者：BOGER, D. L.、MATHVINK, R. J.

  DOI：——

  日期：——