Catalytic transformations of aromatic thiophenes

2016 Fiscal Year Final Research Report

• Project/Area Number: 24685007
• Research Category: Grant-in-Aid for Young Scientists (A)
• Allocation Type: Partial Multi-year Fund
• Research Field: Organic chemistry
• Research Institution: Kyoto University
• Principal Investigator: Yorimitsu Hideki 京都大学, 理学(系)研究科(研究院), 教授 (00372566)
• Research Collaborator: DHANANJAYAN Vasu 京都大学, 大学院理学研究科, 博士研究員 ; BHANUCHANDRA Malli 京都大学, 大学院理学研究科, 博士研究員 ; KURATA Yuto 京都大学, 大学院理学研究科, 大学院生 ; SAITO Hayate 京都大学, 大学院理学研究科, 大学院生 ; NOGI Keisuke 京都大学, 大学院理学研究科, 助教 ; OSUKA Atsuhiro 京都大学, 大学院理学研究科, 教授
• Project Period (FY): 2012-04-01 – 2017-03-31
• Keywords: チオフェン / 芳香環メタモルフォシス / パラジウム / ニッケル

Outline of Final Research Achievements

Aromatic thiophene skeletons are usually considered as being unbreakable due to their aromatic resonance energy. Compared with exocyclic modifications of thiophene rings, little is known about substitutions of endocyclic atoms through partial disassembly of the cyclic skeletons and subsequent ring reconstruction. Our endeavours have resulted in establishing aromatic metamorphosis, where heteroaromatic compounds such as dibenzothiophenes are transformed into different ring systems using a multi-step strategy or ideally in one step. Specifically, we have developed the following transformations: 1) Aromatic metamorphosis of dibenzothiophenes into triphenylenes, 2) Transition-metal-free synthesis of carbazoles and indoles by an SNAr-based aromatic metamorphosis of thiaarenes, 3) Synthesis of spirocyclic diarylfluorenes by one-pot twofold SNAr reactions of diaryl sulfones with diarylmethanes. Additionally, nickel-catalyzed transformations of benzofurans were also developed.

Free Research Field

有機化学