Pd-catalyzed synthesis of C-C (Sonogashira, Suzuki, Heck, Stille), C-P and C-S linked products using gem -dibromovinyl BODIPY

Abstract

The chemistry of gem-dibromovinyl derivatives has undergone a renaissance through the application of palladium catalysis and has been applied to pyrrole substituted gem-dibromovinyl BODIPY. gem-Dibromovinyl BODIPYs (substituted at either the [Formula: see text]-position of 8-phenyl or the [Formula: see text]-position of the pyrrole rings) were studied for cross-coupling reactions using Sonogashira, Suzuki, Heck and Stille conditions, and with phosphonates and thiols. The assigned structures were supported by MS and 1H NMR, [Formula: see text]C NMR, X-ray diffraction analysis as well as optical spectroscopy. The conjugates were investigated for their absorption, fluorescence and solvatochromic properties in different solvents. Substitution at the [Formula: see text]-position of 8-phenyl derivatives of gem-diethynyl BODIPYs did not induce any shift in the absorption maximum, while the [Formula: see text]-position pyrrole substituted derivatives showed a red shift. Aromatic compounds gave larger red shifts as compared to the aliphatic substituted analogs.

gem-Dibromovinyl phthalonitriles: synthesis, structure elucidation, Hirshfeld surface analysis and energy framework calculations

“…Previously, we developed the chemistry of photosensitizers through the Pd-catalyzed coupling reaction of porphyrins, 34 Pcs 35 and gem -dibromo BODIPY derivatives 36 using Sonogashira and Stille Pd-catalyzed cross-coupling reactions. 37 In this study, we report the synthesis of a series of gem -dibromovinyl phthalonitriles. These new derivatives have the potential to provide a variety of Pc precursors using different catalysts.…”