The development of synthetic methods for elaborate π-conjugated molecules is crucial for the creation of new functional organic materials. The annulative two-fold C(sp2)-C(sp2) cross-coupling reaction between organodimetallic reagents and dihalides represents a powerful method for this purpose. Among the organodimetallic reagents reported to date, cyclic diarylborinic acid is particularly useful, because of its stability towards air and moisture, and the low toxicity and easily removable nature of the boron-based residue generated after the cross-coupling. However, the utility of cyclic diarylborinic acid remains limited, because all of the reported syntheses of cyclic diarylborinic acid require the use of organolithium reagents, thus rendering the introduction of many common functional groups impossible. Herein, we report the development of catalytic synthesis of cyclic diarylborinic acids via two-fold borylation of dihalides using dihydroaminoborane. This reaction allows for the synthesis of cyclic diarylborinic acids containing a series of functional groups. Furthermore, these cyclic diarylborinic acids enabled the synthesis of functionalized six- to nine-membered π-extended heteroarenes through annulative two-fold cross-coupling reactions.

Catalytic double carbon-boron bond formation for the synthesis of cyclic diarylborinic acids as versatile building blocks for π-extended heteroarenes

254th National Meeting (2017)

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