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

2023

The Chemical Record

Self Cite

Fluorinated functional groups, including trifluoromethyl group, play important roles in the development of drugs, agrochemicals, and organic functional materials. Therefore, the development of highly effective and practical reactions to introduce fluorinated functional groups into (hetero)aromatic compounds is highly desirable. We have achieved several regioselective C−H trifluoromethylation and related reactions by electrophilic and nucleophilic activation of six‐membered heteroaromatic compounds and steric protection of aromatic compounds. These reactions proceed in good to excellent yields, even on a gram scale, with high functional group tolerance, and are applicable to the regioselective trifluoromethylation of drug molecules. In this personal account, the background of the introduction reactions of fluorinated functional groups, our reaction designs to achieve regioselective C−H trifluoromethylation and the related reactions of (hetero)aromatic compounds are explained.

Section: Discussionmentioning

confidence: 99%

Regioselective C−H Trifluoromethylation and Its Related Reactions of (Hetero)aromatic Compounds

2023

The Chemical Record

Self Cite

“…In summary, we developed site-selective CÀ H transformations using non-covalent interactions such as hydrogen bonds, Lewis acid-base interactions, and electrostatic interactions between substrates and reagents, and catalysts and substrates. [26] Orthoselective C(sp 2 )À H borylation and silylation were achieved using Lewis acidÀ base interactions between the substrate and the reagent to avoid steric repulsion between the active catalytic species and the substituent(s) of the substrates. To realize site-selective CÀ H transformations by catalyst control, we designed a new catalytic system with a substrate-recognition site that recognized the substrate and brought the desired reaction site of the substrate to the catalytic active site.…”

Section: Discussionmentioning

confidence: 99%

Non‐Covalent Interaction‐Controlled Site‐Selective C−H Transformations

2023

The Chemical Record

Self Cite

Site‐selective C−H transformations are important to obtain desired compounds as single products in a highly efficient manner. However, it is generally difficult to achieve such transformations because organic substrates contain many C−H bonds with similar reactivities. Therefore, the development of practical and efficient methods for controlling site selectivity is highly desirable. The most frequently used strategy is “directing group method”. Although this method is highly effective and promotes site‐selective reactions, it has several limitations. Our group recently reported other methods to achieve site‐selective C−H transformations using non‐covalent interactions between a substrate and a reagent or a catalyst and a substrate (non‐covalent method). In this personal account, the background of site‐selective C−H transformations, our reaction design to achieve site‐selective C−H transformations, and recently reported reactions are explained.

Hydrogen Bond‐Accelerated Meta‐Selective CH Functionalization with Iridium

Handbook of CH-Functionalization

2022

This article summarizes the design of the catalytic systems and regioselective CH borylation of (hetero)aromatic compounds using the noncovalent interactions, such as hydrogen bonding and Lewis acid–base interaction, between the substrate recognition part of the ligand of catalysts and the functional group of substrates. Formal meta‐selective introduction of a variety of functional groups into (hetero)aromatic compounds based on the meta‐selective CH borylation is explained. In addition, acceleration of the reaction and expression of functional group and substrate specificities are introduced. In the summary section, recently reported reactions using the noncovalent interaction method and the several reviews and accounts are cited.