10.1002/chem.201900715
Chemistry - A European Journal
COMMUNICATION
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peripheral scaffold. The new route provides access to various
Pym-DATB derivatives, including markedly soluble DATB
derivatives, revealing the dynamic nature of the B3NO2 ring
system in solution phase under alcohol-rich conditions. Pym-
DATBs are bench-stable solids endowed with catalytic
competency in the dehydrative amidation of carboxylic acids and
amines. While the catalytic performance was attenuated by
substituents on the peripheral scaffold, the most accessible
derivative without any substituent exhibited sufficiently high
catalytic performance for a range of substrate sets. The tolerance
toward steric hindrance, Lewis basic and acid-labile functionalities,
and α-chirality is notable, and supports the broad utility of Pym-
DATB catalysts in forging amide bonds to offer a catalytic
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Acknowledgements
This work was financially supported by KAKENHI (17H03025 and
18H04276 in Precisely Designed Catalysts with Customized
Scaffolding) from JSPS and MEXT. NK thanks the Shorai
Foundation for financial support. Dr. Tomoyuki Kimura is
gratefully acknowledged for the X-ray crystallographic analysis of
5e. We are grateful to Dr. Ryuichi Sawa, Ms. Yumiko Kubota, Dr.
Kiyoko Iijima, and Ms. Yuko Takahashi for the NMR and HRMS
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Keywords: amidation • boron heterocycles • catalysis •
triborinane • DATB
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Pym-DATB 5a will be commercially available from Merck-Sigma-Aldrich
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