Synlett 2018; 29(16): 2093-2107
DOI: 10.1055/s-0037-1610531
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© Georg Thieme Verlag Stuttgart · New York

Development of Novel C–H Bond Transformations and Their Application to the Synthesis of Organic Functional Molecules

Yoichiro Kuninobu*
Institute for Materials Chemistry and Engineering, Kyushu University, 6-1 Kasugakoen, Kasuga-shi, Fukuoka 816-8580, Japan   eMail: kuninobu@cm.kyushu-u.ac.jp
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I am grateful for financial support by JSPS KAKENHI Grant Numbers JP 26288014, JP 16K13946, and JP 17H03016, CREST and ERATO from Japan Science and Technology Agency (JST), Astellas Foundation for Research on Metabolic Disorders, and Yakugaku Shinkoukai.
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Publikationsverlauf

Received: 05. Juni 2018

Accepted after revision: 26. Juni 2018

Publikationsdatum:
26. Juli 2018 (online)


Abstract

This personal account summarizes our recent progress in the development of C–H transformations. We achieved ortho-selective C–H borylations and silylations by using Lewis acid–base interaction between two substrates and we achieved meta- and ortho-selective C–H borylations by using hydrogen bonding or Lewis acid–base interaction between a hydrogen donor or Lewis acid unit of a ligand and a functional group of a substrate. Regioselective C–H trifluoromethylations and related reactions of six-membered heteroaromatic compounds were realized at their 2- and 4-positions and at their benzylic positions. In addition, we developed C–H transformations directed towards the synthesis of organic functional materials, such as highly soluble polyimides or π-conjugated molecules containing either heteroatom(s) or a Lewis acid–base interaction.

1 Introduction

2 Regioselective C–H Transformations Controlled by Noncovalent Bond Interactions

2.1 Regioselective C–H Transformations Controlled by Lewis Acid–Base Interaction between Two Substrates

2.2 Regioselective C–H Transformation Controlled by Hydrogen Bonding between Ligand and Substrate

2.3 Regioselective C–H Transformations Controlled by Lewis Acid–Base Interactions between Ligands and Substrates

3 Trifluoromethylation and Related Transformations of Six-Membered Heteroaromatic Compounds

3.1 2-Position-Selective C–H Trifluoromethylation of Six-Membered Heteroaromatic Compounds

3.2 4-Position-Selective C–H Trifluoromethylation of Six-Membered Heteroaromatic Compounds

3.3 Benzyl Position-Selective C–H Trifluoromethylation of Six-Membered Heteroaromatic Compounds

4 C–H Transformations Leading to the Synthesis of Organic Functional Materials

4.1 Heteroatom-Containing π-Conjugated Molecules

4.2 π-Conjugated Molecules Containing a Lewis Acid–Base Interaction

4.3 Soluble Polyimide Derivatives

5 Conclusions