Catalytic Undirected Meta-Selective C-H Borylation of Metallocenes

Metallocenes are privileged backbones in the fields of synthetic chemistry, catalysis, polymer science, etc. Direct C-H functionalization is undoubtedly the simplest approach for tuning the properties of metallocenes. However, owing to the presence of multiple identical C(sp2)-H sites, this protocol often suffers from low reactivity and selectivity issues, especially for the regioselective synthesis of 1,3-difunctionalized metallocenes. Herein, an efficient iridium-catalyzed meta-selective C-H borylation of metallocenes is reported. With no need of preinstalled directing groups, this approach enables a rapid synthesis of various boronic esters based on benzoferrocenes, ferrocenes, ruthenocene, and related half sandwich complex. A broad range of electron-deficient and -rich functional groups are all compatible with the process. Notably, C-H borylation of benzoferrocenes takes place exclusively at the benzene ring, which is likely ascribed to the shielding effect of pentamethylcyclopentadiene. The synthetic utility is further demonstrated by easy scalability to gram quantities, the conversion of boron to heteroatoms including N3, SePh, and OAc, as well as diverse cross-coupling reactions. With Ir(I) catalyst and dinitrogen ligands, a meta-selective C-H borylation of metallocenes enabled by steric control strategy is herein realized. With no need of directing groups, this practical method allows for a rapid synthesis of various useful boronic esters based on benzoferrocenes, ferrocenes, ruthenocene, and related half sandwich complex.image

Automated summary

This article reports an efficient iridium-catalyzed meta-selective C-H borylation reaction that allows for the rapid synthesis of various boronic esters based on benzoferrocenes, ferrocenes, ruthenocene, and related half sandwich complexes. This method does not require preinstalled directing groups and is compatible with a wide range of electron-deficient and -rich functional groups. The scalability and diverse applications of this reaction, including the conversion of boron to heteroatoms and cross-coupling reactions, are also demonstrated.