Synthesis of Borinic Acids and Borinate Adducts Using Diisopropylaminoborane.

In situ formation of aryl Grignard under Barbier condition and diisopropylaminoborane as boron source allows a complete control of the addition onto the boron electrophile. Analytically pure borinic acid derivatives were produced at the gram scale without column chromatography and isolated as borinates adducts, with ethanolamine or 8-hydroxyquinoline, after workup.

Borylation of unactivated aryl chlorides under mild conditions by using diisopropylaminoborane as a borylating reagent.

The synthesis of arylboronic ester derivatives from aryl chlorides by using aryl(amino)boranes is described. Palladium-catalyzed coupling between aryl chlorides and diisopropylaminoborane leads to the formation of a CB bond under mild conditions. A wide range of functional groups are tolerated, making this method particularly useful for the borylation of functionalized aromatics.

Continuous coflow synthesis of hybrid palladium nanocrystals as catalysts for borylation reaction.

The combination of highly active Pd nanocrystal (NC) types with tailored surface properties (various ligands) - e.g. organic-inorganic hybrid NCs - as catalysts opens avenues towards new synthetic pathways, implying a faster practical alternative for adjusting and screening the reaction conditions. Pd@dppf and Pd@PCy3 NCs have been successfully prepared via a continuous supercritical fluid assisted coflow route with promising results as catalysts in borylation reaction. It has been found that the ligands not only influence the catalytic properties of the systems, but also contribute to Pd metal core characteristics (size, shape and time stability).

Aminoborylation/Suzuki-Miyaura tandem cross coupling of aryl iodides as efficient and selective synthesis of unsymmetrical biaryls.

Sequential borylation of a first aryl iodide using a dialkylaminoborane followed by a Suzuki-Miyaura cross coupling of second aryl iodide ended up with an efficient, selective and practical synthesis of unsymmetrical biaryls. This tandem coupling shows a wide range of applicability.