Exploring the Application of the Negishi Reaction of HaloBODIPYs: Generality, Regioselectivity, and Synthetic Utility in the Development of BODIPY Laser Dyes

• Published in: Journal of organic chemistry Vol. 81; no. 9; pp. 3700 - 3710
• Main Authors: Palao, Eduardo, Duran-Sampedro, Gonzalo, de la Moya, Santiago, Madrid, Miriam, García-López, Carmen, Agarrabeitia, Antonia R, Verbelen, Bram, Dehaen, Wim, Boens, Nöel, Ortiz, María J
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 06.05.2016; Amer Chemical Soc
• Subjects: Chemistry; Chemistry, Organic; Physical Sciences; Science & Technology; FUNCTIONALIZATION; SUBSTITUTION; ROUTE; DESIGN; OPTICAL-PROPERTIES; PHOTOPHYSICAL PROPERTIES; TRIPLET EXCITED-STATE; PYRROMETHENE-BF2 COMPLEXES; BORON-DIPYRROMETHENES; MODULATION
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/acs.joc.6b00350

The generality of the palladium-catalyzed C–C coupling Negishi reaction when applied to haloBODIPYs is demonstrated on the basis of selected starting BODIPYs, including polyhalogenated and/or asymmetrical systems, and organozinc reagents. This reaction is an interesting synthetic tool in BODIPY chemistry, mainly because it allows a valuable regioselective postfunctionalization of BODIPY chromophores with different functional groups. In this way, functional patterns that are difficult to obtain by other procedures (e.g., asymmetrically functionalized BODIPYs involving halogenated positions) can now be made. The regioselectivity is achieved by controlling the reaction conditions and is based on almost-general reactivity preferences, and the nature of the involved halogens and their positions. This ability is exemplified by the preparation of a series of new BODIPY dyes with unprecedented substitution patterns allowing noticeable lasing properties.