Edge Article
Chemical Science
short synthesis of the highly useful chiral BHA ligand 9F in high
yield with retention of conguration. The spectroscopic data
were in good accordance with the data reported previously by
our group.11b
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Conclusions
In summary, we have developed for the rst time a general and
efficient method for N–O bond synthesis from 1,2-diamines by
eliminating undesirable amide (C–N bond) formation in most
cases. The oxidation of 1,2-diamines using commercially avail-
able 75% BPO and Cs2CO3 furnished the challenging bis-
(benzoyloxy)-1,2-diamines with a good yield (up to 85%). The
presence of a small amount of water and Cs2CO3 plays a crucial
role in achieving high selectivity. The method was successfully
explored in the efficient synthesis of bis-(benzoyloxy)hydroxa-
mic acids and bis-hydroxamic acids. Further, this method was
extended to the efficient synthesis of bis-(benzoyloxy)-1,2-
disubstituted-1,2-diamines and a new type of bis-hydroxyl
amine ligand. Excitingly, all of these products can be trans-
formed to a variety of building blocks and chiral ligands, some
of them are shown. The reaction proceeds stereoselectively
without any racemization. The synthetic utility of this meth-
odology was further demonstrated in the efficient synthesis of
a chiral BHA ligand. Currently, a detailed mechanistic study and
synthetic application to biologically active molecules is under
progress in our laboratory. We believe that the present method
will be able to provide the direct synthesis of chiral bis-hydroxyl
amines and bis-hydroxamic acids for future use.
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Conflicts of interest
There are no conicts to declare.
Acknowledgements
This work was supported by Grant-in-Aid for Scientic Research
(No. 17H06142).
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