Novel Reactions of Aromatic Compounds Enabled by π-Coordination

November 12, 2025

Nucleophilic Borylation of Benzene Derivatives

Researchers at the RIKEN CSRS have developed a method that directly functionalizes aromatic hydrocarbons, important natural resources, by leveraging π-coordination to chromium (Cr).

Direct functionalization of hydrocarbon resources is an important approach for the efficient synthesis of complex molecules. For example, borylation reactions using metal catalysts such as iridium (Ir) or cobalt (Co) have been extensively studied. However, in metal-catalyzed borylation, the low reactivity of electron-rich arenes has required the use of complex catalytic systems to drive the reaction. Because organoboron compounds are key intermediates in the synthesis of pharmaceuticals, agrochemicals, and functional molecules, developing methods that enable their efficient synthesis is of significant importance.

In this study, the research team succeeded in developing an efficient borylation of simple arenes, including electron-rich substrates, enabled by π-coordination to a metal. This result demonstrates the feasibility of a strategy in which inert arenes are transiently activated for functionalization. Theoretical calculations and mechanistic experiments support a mechanism where nucleophilic attack by a boron compound proceeds on a benzene ring activated through π-coordination.

These findings are expected to contribute to the development of rapid and efficient synthesis methods for pharmaceuticals, agrochemicals, and functional molecules.

 

Original article

Chemical Science　doi: 10.1039/D5SC08107F

Y. Mutoh, R. Khalaf, S. Asako, L. Ilies,

"Transient π-Coordination Enables Nucleophilic Borylation of Simple Arenes".

Contact

Laurean Ilies; Team Director
Yuichiro Mutoh; Senior Research Scientist
Advanced Organic Synthesis Research Team