Synthesis of (1-silyl)allylboronates by KOtBu-catalyzed ring-opening gem-silylborylation of cyclopropenes.

A KOtBu-catalyzed ring-opening gem-silylborylation of cyclopropenes with silylboronates has been developed for the synthesis of (1-silyl)allylboronates, a useful class of compounds in organic synthesis. The reaction proceeds with high selectivity under mild conditions, and the reaction mechanism has been theoretically investigated using DFT calculations.

The Kumada-Tamao-Corriu Coupling Reaction Catalyzed by Rhodium-Aluminum Bimetallic Complexes.

Rhodium-aluminum bimetallic complexes catalyze the Kumada-Tamao-Corriu (KTC) cross-coupling reaction using arylmagnesium compounds that are generated from the corresponding aryl fluorides or chlorides in situ by these catalysts. This method allows the challenging KTC coupling reaction to be carried out using aryl fluorides as nucleophiles, which affords various biaryls.

Magnesiation of Aryl Fluorides Catalyzed by a Rhodium-Aluminum Complex.

We report the magnesiation of aryl fluorides catalyzed by an Al-Rh heterobimetallic complex. We show that the complex is highly reactive to cleave the C-F bonds across the polarized Al-Rh bond under mild conditions. The reaction allows the use of an easy-to-handle magnesium powder to generate a range of arylmagnesium reagents from aryl fluorides, which are conventionally inert to such metalation compared with other aryl halides.