10.1002/anie.201901748
Angewandte Chemie International Edition
COMMUNICATION
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mol% nor-AZADO affords the corresponding phenylalanine-type
KAT 4b in 82% yield (1.5 g) without any loss of enantiopurity.
In summary, we have developed an operationally simple
protocol for the preparation of KATs in two steps from aldehydes.
This borylation/oxidation proceeds under mild conditions and
exhibits high functional-group tolerance toward e.g. halide, acetal,
sulfide, and ester moieties. The oxidation can be accomplished
with i) DMSO/Ac2O or ii) nor-AZADO catalyst, and the conditions
for either oxidation are practical as the use of expensive
stoichiometric oxidants is not required. Importantly, various α-
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amino-acid analogues containing
a KAT moiety, which is
expected to be essential for peptide-peptide conjugation, can be
prepared from naturally occurring α-amino aldehydes without
racemization. The utility of this method was demonstrated by the
synthesis of a KAT-containing carbohydrate, and a column-
chromatography-free gram-scale synthesis. This general method
is expected to broaden the range of applications of KAT not only
in the context of bioconjugation, but also in organic synthesis and
material science.
[5]
Z. He; A. K. Yudin, J. Am. Chem. Soc. 2011, 133, 13770. The preparation
of α-hydroxy MIDA boronates is shown below ([B] = MIDA boronate).
Me
Pinnick
N
BF3·Et2O
CHO
oxidation
mCPBA
R
O
B
R
O
[B]
R
[B]
Acknowledgements
O
O
O
Alkenyl MIDA boronate
Me
O
N
Barton
decarboxylation
This study was financially supported by the Institute for Chemical
Reaction Design and Discovery (WPI-ICReDD), which was
established by the World Premier International Research Initiative
(WPI), MEXT, Japan, as well as KAKENHI grants 17H06370
(JSPS) and JP18H03907. J.T. would like to thank the JSPS for a
scholarship (KAKENHI grant 16J01384).
Dess-Martin
oxidation
CO2H
OH
B
R
O
O
O
R
[B]
R
[B]
O
α-Hydroxy MIDA boronate
Acyl MIDA boronate
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Keywords: amino acid • boron • copper • oxidation • acylboron
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