Synthesis, Structure, and Properties of β-Vinyl Ketone/Ester Functionalized AzaBODIPYs from FormylazaBODIPYs

Postfunctionalization of azaBODIPY (the BF2 complex of azadipyrromethene) is highly desirable due to the strong tunable absorption bands at wavelengths above 650 nm and the wide-ranging applications of this class of dyes in biomedicine and materials science. Currently available postfunctionalization methods for this class of dyes have been limited to the Pd-catalyzed coupling reactions on beta-halogenated (brominated or iodinated) azaBODIPY platforms. In this work, we report a new strategy for the facile postfunctionalization of the azaBODIPY chromophore with various vinyl ketone and vinyl esters based on a Wittig reaction on our previously developed beta-formylazaBODIPYs and our recently developed beta-bromo-beta'-formylazaBODIPYs. Our strategy uses easily accessible starting materials and mild reaction conditions. It is highly compatible with various common phosphonium ylides (aliphatic, aromatic, and ester substituted ones). These resultant bromo-containing beta-vinyl ketone/ester functionalized azaBODIPYs are potential photosensitizers and can be further functionalized via coupling reactions. The ester groups on some of these resultant azaBODIPYs can be further hydrolyzed to achieve the desired water solubility and conjugate with the biomolecule and solid surface.