4.6 Article

Regioselective Synthesis of 1,2,3,4-Tetrasubstituted Arenes by Vicinal Functionalization of Arynes Derived from Aryl(Mes)iodonium Salts**

期刊

CHEMISTRY-A EUROPEAN JOURNAL
卷 27, 期 24, 页码 7168-7175

出版社

WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.202100201

关键词

arylation; aryne; deprotonation; diaryliodonium salt; hypervalent iodine

资金

  1. Portland State University
  2. National Science Foundation [MRI 0604188, MRI 1828573]
  3. Vicki & Patrick F. Stone family
  4. National Science Foundation (NSF) [CHE 1352663]

向作者/读者索取更多资源

This study describes a method for synthesizing 1,2,3,4-tetrasubstituted benzenoid rings, addressing previous challenges in regioselective synthesis of these compounds. By using substituted arynes derived from aryl(Mes)iodonium salts, a range of densely functionalized 1,2,3,4-tetrasubstituted benzenoid rings can be accessed. The study demonstrates improved conditions for generating arynes at room temperature and in shorter reaction times, allowing for post-synthetic elaboration via palladium-catalyzed coupling.
Herein, the synthesis of 1,2,3,4-tetrasubstituted benzenoid rings, motifs found in pharmaceutical, agrochemical, and natural products, is described.([1]) In the past, the regioselective syntheses of such compounds have been a significant challenge. This work reports a method using substituted arynes derived from aryl(Mes)iodonium salts to access a range of densely functionalized 1,2,3,4-tetrasubstituted benzenoid rings. Significantly, it was found that halide substituents are compatible under these conditions, enabling post-synthetic elaboration via palladium-catalyzed coupling. This concise strategy is predicated on two regioselective events: 1) ortho- deprotonation of aryl(Mes)iodonium salts to generate a substituted aryne intermediate, and 2) regioselective trapping of said arynes, thereby improving previously reported reaction conditions to generate arynes at room temperature and in shorter reaction times. Density functional theory (DFT) computations and linear free energy relationship (LFER) analysis suggest the regioselectivity of deprotonation is influenced by both proximal and distal ring substituents on the aryne precursor. A competition experiment further reveals the role of arene substituents on relative reactivity of aryl(Mes)iodoniums as aryne precursors.

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