A novel strategy for the functionalization and design of 4-methylene-4H-pyran merocyanines via enamination and 1,8-conjugate addition

Abstract

4-Methylene-4H-pyrans are popular merocyanine dyes, but their functionalization is limited by the Knoevenagel condensation with aromatic aldehydes. In this work, we developed a novel approach for the construction of a new class of pyran fluorophores based on enamination and subsequent nucleophilic substitution of the dimethylamino group via 1,8-conjugate addition/elimination. This methodology includes selective transformations leading to previously unknown symmetrical and asymmetrical structures. The dimethylaminovinyl-substituted pyrans are reactive intermediates and can be considered as a convenient synthetic tool for the construction of new merocyanines with tunable fluorescence (417–628 nm). The main strategies for the modification of the pyran moiety have been determined for the construction and targeted design of fluorophores. Pyrans bearing two enamine moieties demonstrate significant light extinction coefficients (up to 116 000 M⁻¹ cm⁻¹), high quantum yields (up to 69%) and large Stokes shifts (up to 152 nm) because of their strong push–pull nature. Density Functional Theory (DFT) calculations were performed for the explanation of the structural and photophysical features of the prepared merocyanines. The developed approach can be considered as a useful platform for further application of 4-methylene-4H-pyrans as promising fluorophores for sensors and solar cells, and in bioimaging.