10.1002/anie.201914864
Angewandte Chemie International Edition
COMMUNICATION
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Scheme 7. Reaction of (S)-2 in the presence of phenol. The yield and
enantiospecificity in the absence of phenol are shown in the bracket.
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Miyaura-type
coupling
of
-[(o-
bromobenzoyl)amino]benzylboronates, which affords highly
enantioenriched isoindolinone derivatives in high yields. The
reaction yield and stereospecificity were contradictorily and
sharply affected by the steric effect at the substituents at the 6-
and 6′-positions of the bipyridyl ligands. Employing 6-
monosubstituted bipyridine ligands allowed finer tuning of the
steric effect than using 6,6′-disubstituted bipyridines. The
stereochemical course of the coupling was determined to be
invertive, relying on the stereoinvertive transmetalation step,
which becomes more preferable by using phenol as a Brønsted
acid additive. The reaction protocol was applicable to -
aminobenzylboronates of which boron-bound stereogenic
carbon center is fully substituted. These results reveal that the
stereoinvertive transmetalation with organoboron compounds is
not limited to palladium-catalyzed cross-couplings, but has more
generality in boron-based transition-metal-catalyzed reactions.
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Acknowledgements
This work was supported by JSPS KAKENHI (M.S., Precisely
Designed Catalysts with Customized Scaffolding, JP15H05811)
and CREST, JST (M.S., Establishment of Molecular Technology
towards the Creation of New Function, JPMJCR14L1). We thank
Dr. T. Ohmura (Kyoto University) for his kind advice and help.
Synchrotron X-ray diffraction measurements were performed at
the BL40XU beam line in SPring-8 with the approval of JASRI
(2018A1114). We are grateful to Dr. N. Yasuda (JASRI) and
Prof. T. Hatakeyama (Kwansei Gakuin University) for their
supports in X-ray diffraction measurements.
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Keywords: stereospecific reaction • bipyridine ligand • carbon
stereocenter • copper catalysis • enantiospecificity
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