10.1002/anie.201913388
Angewandte Chemie International Edition
COMMUNICATION
Scheme 7. Amination of aryl pinacol boronates. Reaction conditions: 1c (0.25
mmol), H2N-DABCO (0.25 mmol), KOtBu (0.6 mmol), THF (3 mL), 100 oC, 1 h,
then TFAA (0.5 mmol), 100 oC, 1 h; [a] Without TFAA quenching; Yields based
on isolated products.
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In summary, the aminoazanium of DABCO was firstly
developed as a general and practical amination reagent for the
direct amination of alkyl and aryl pinacol boronates (Alkyl-Bpin
and Ar-Bpin). Various primary, secondary and tertiary alkyl-Bpin
were well aminated to their amine derivatives. The amination is
stereospecific for alkyl pinacol boronates. The anti-Markovnikov
hydroamination of olefins was easily achieved via catalytic
hydroboration with HBpin followed by in-situ amination using our
newly developed reagent H2N-DABCO. Moreover, the
combination of 1,2-diboration of olefins using B2pin2 with this
amination process achieved the unprecedented 1,2-diamination
of olefins to synthesize various 1,2-diamine derivatives. Aryl
pinacol boronates were also successfully aminated.
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Acknowledgements
This work was supported by the National Natural Science
Foundation of China (91745110, 21673261, 21603245,
21703265, 21872156, 21802150, 21773210, and 21603190),
Natural Science Foundation of Jiangsu Province (BK20190002,
BK20181194, and BK20180247). Support from the Young Elite
Scientist Sponsorship Program by CAST (YESS20170217), the
Youth Innovation Promotion Association CAS (2018458) were
also acknowledged. We thank Prof. Guoyin Yin (Wuhan
University) for providing several pinacol boronates. We thank
Prof. Xin Xu (Soochow University) for the assistance on crystal
structure analysis.
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Keywords: Aminoazanium • Amination • Organoboron • Amine •
Synthetic methods
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