Neopentylglycolborylation of ortho-Substituted Aryl Halides Catalyzed by NiCl2-Based Mixed-Ligand Systems

• Published in: Journal of organic chemistry 2010-08, Vol.75 (16), p.5438-5452
• Main Authors: Moldoveanu, Costel, Wilson, Daniela A, Wilson, Christopher J, Leowanawat, Pawaret, Resmerita, Ana-Maria, Liu, Chi, Rosen, Brad M, Percec, Virgil
• Format: Article
• Language: English
• Subjects: Catalysis; Catalysts: preparations and properties; Chemistry; Exact sciences and technology; General and physical chemistry; Heterocyclic compounds; Miscellaneous; Organic chemistry; Preparations and properties; Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/jo101023t

NiCl2-based mixed-ligand systems were shown to be very effective catalysts for the neopentylglycolborylation of aryl iodides, bromides, and chlorides bearing electron-rich and electron-deficient ortho-substituents. Although NiCl2-based single-ligand catalytic systems were able to mediate neopentylglycolborylation of selected substrates, they were not as effective for all substrates, highlighting the value of the mixed-ligand concept. Optimization of the Ni(II)-catalyzed neopentylglycolborylation of 2-iodoanisole and methyl 2-iodobenzoate demonstrated that, while the role of ligand and coligand in the conversion of Ni(II) precatalyst to Ni(0) active catalyst cannot be ignored, a mixed-ligand complex is likely present throughout the catalytic cycle. In addition, protodeborylation and hydrodehalogenation were demonstrated to be the predominant side reactions of Ni(II)-catalyzed borylation of ortho-substituted aryl halides containing the electron-deficient carboxylate substituents. Ni(II) complexes in the presence of H2O and Ni(0) are responsible for the catalysis of these side reactions.