Facile Synthesis of 2-Bromo-3-fluorobenzonitrile:  An Application and Study of the Halodeboronation of Aryl Boronic Acids

• Published in: Journal of organic chemistry Vol. 69; no. 2; pp. 566 - 569
• Main Authors: Szumigala, Ronald H, Devine, Paul N, Gauthier, Donald R, Volante, R. P
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 23.01.2004; Amer Chemical Soc
• Subjects: Chemistry; Chemistry, Organic; Exact sciences and technology; Noncondensed benzenic compounds; Organic chemistry; Physical Sciences; Preparations and properties; Science & Technology; ELECTROPHILIC DISPLACEMENT REACTIONS; HALIDES; PALLADIUM; MILD CONDITIONS; DIRECTED ORTHO-METALATION; IPSO-SUBSTITUTION; CHLORIDES; CATALYST; BROMIDES; ARYLBORONIC ACIDS; Catalytic reaction; Nitrile; Halogenation; Benzonitrile derivatives; Boronic acid derivatives; Organic bromine compounds; Aromatic compound; Fluorine Organic compounds; Sodium methanolate; Chemical synthesis; Organic chlorine compounds
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/jo035184p

A scaleable synthesis of 2-bromo-3-fluorobenzonitrile via the NaOMe-catalyzed bromodeboronation of 2-cyano-6-fluorophenylboronic acid was developed. The generality of this transformation was demonstrated through the halodeboronation of a series of aryl boronic acids. Both aryl bromides and aryl chlorides were formed in good to excellent yields when the corresponding aryl boronic acid was treated with 1,3-dihalo-5,5-dimethylhydantoin and 5 mol % NaOMe.