Direct Observation of Triplet States in the Isomerization of Alkenylboronates by Energy Transfer Catalysis.

Abstract

Alkenylboronates are versatile building blocks for stereocontrolled synthesis owing to the traceless nature of the boron group that can be leveraged to achieve highly selective geometric isomerization. Using thioxanthone as an inexpensive photocatalyst, the photoisomerization of these species continues to provide an expansive platform for stereodivergent synthesis, particularly in the construction of bioactive polyenes. Although mechanistic investigations are consistent with light-driven energy transfer, direct experimental evidence remains conspicuously absent. Herein, we report a rigorous mechanistic investigation using two widely used alkenylboronates alongside relevant reference compounds. Through the combination of irradiation experiments, transient absorption spectroscopic studies, kinetic modeling, and DFT calculations with all isomers of the model compounds, it has been possible to unequivocally detect and characterize the perpendicular triplet generated by energy transfer. Our results serve not only as a blueprint for mechanistic studies that are challenging with organic sensitizers, but these guidelines delineated have also enabled the development of more sustainable reaction conditions: for the first time, efficient organocatalytic isomerization under sunlight irradiation has become feasible.