Synthesis and Photophysical Properties of β‑Alkenyl-Substituted BODIPY Dyes by Indium(III)-Catalyzed Intermolecular Alkyne Hydroarylation

• Published in: Journal of organic chemistry Vol. 89; no. 7; pp. 4702 - 4711
• Main Authors: Da Lama, Ana, Pérez Sestelo, José, Sarandeses, Luis A., Martínez, M. Montserrat
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 05.04.2024; Amer Chemical Soc
• Subjects: Chemistry; Chemistry, Organic; Physical Sciences; Science & Technology; FUNCTIONALIZATION; MILD; ARENES; IONIC LIQUID; DERIVATIVES; FRIEDEL-CRAFTS ALKENYLATION; C-H BONDS; PROBES
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/acs.joc.3c02951

A new atom-economical synthesis of β-alkenyl-substituted BODIPYs via indium­(III)-catalyzed intermolecular alkyne hydroarylation with meso-substituted BODIPYs is described. While catalysis with InI3 allows the double β-functionalization of BODIPY, resulting in regioselectively branched β,β′-disubstituted alkenyl BODIPYs, catalytic InCl3 enables the formation of linear β-substituted alkenyl BODIPYs. Subsequent In­(III)-catalyzed intermolecular alkyne hydroarylation allows the synthesis of unsymmetrical push–pull BODIPY derivatives. Therefore, indium catalysis offers complementary regioselectivity in good chemical yields and functional group tolerance. The resulting BODIPY dyes displayed bathochromically shifted absorption and emission according to the electron-nature of the substituents in the alkenyl moiety with high molar extinction coefficients (ε up to 88,200 M–1 cm–1) and quantum yields (0.14–0.96).