ACS Catalysis
Letter
In summary, we have developed an efficient biomimetic
alloxan-catalyzed oxidation method for a variety of sulfides and
amines with H O or O . This method successfully simulates
the functions of FMO and requires no original complicated
flavin skeleton but can afford the target products quickly and
cleanly under mild conditions by using the simple alloxan. As
the most efficient simple alloxan, 5a has shown us its significant
catalytic activity, better than the best-reported alloxazinium
M. M. E.; Montersino, S.; Westphal, A. H.; Tischler, D.; van Berkel,
W. J. H. Flavin dependent monooxygenases. Arch. Biochem. Biophys.
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catalysts and pyrazinium salts in sulfoxidation with H O . After
2
2
mechanism studies, the whole catalytic cycle has been proved
to be a biomimetic way with a shared highly reactive
intermediate alloxan hydroperoxide 8c in both H O and O
2
2
2
(6) Murahashi, S. I.; Oda, T.; Masui, Y. Flavin-Catalyzed Oxidation
systems, which is slightly different from the reported catalytic
mechanism of flavinium-like catalyst. Because of the simple
nonionic structure, alloxan is easy to prepare and introduce
chiral substituents to construct chiral catalysts for the
investigations of biomimetic asymmetric oxidation. Because
of the above obvious advantages, this alloxan-based catalytic
system has great potential in the biomimetic oxidation. Further
studies to expand the reaction scope of the novel catalyst and
its application in asymmetric catalysis are currently underway
in our lab.
of Amines and Sulfur-Compounds with Hydrogen-Peroxide. J. Am.
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(
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va, H.; Strnadova, I.; Kovandova, M.; Chudoba, J.;
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Dvora ova, H.; Cibulka, R. Biomimetic aerobic oxidative hydrox-
ylation of arylboronic acids to phenols catalysed by a flavin derivative.
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k
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(9) (a) Imada, Y.; Kitagawa, T.; Wang, H. K.; Komiya, N.; Naota, T.
Flavin-catalyzed aerobic oxidation of sulfides in aqueous media.
Tetrahedron Lett. 2013, 54, 621−624. (b) Murahashi, S.; Zhang, D.;
Iida, H.; Miyawaki, T.; Uenaka, M.; Murano, K.; Meguro, K. Flavin-
catalyzed aerobic oxidation of sulfides and thiols with formic acid/
ASSOCIATED CONTENT
Supporting Information
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*
S
triethylamine. Chem. Commun. 2014, 50, 10295−10298. (c) Linden
́
,
A. A.; Kruger, L.; Backvall, J.-E. Highly Selective Sulfoxidation of
̈
̈
Allylic and Vinylic Sulfides by Hydrogen Peroxide Using a Flavin as
Catalyst. J. Org. Chem. 2003, 68, 5890−5896.
(10) (a) Imada, Y.; Iida, H.; Ono, S.; Masui, Y.; Murahashi, S.-I.
Flavin-Catalyzed Oxidation of Amines and Sulfides with Molecular
AUTHOR INFORMATION
ORCID
Oxygen: Biomimetic Green Oxidation. Chem. - Asian J. 2006, 1, 136−
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147. (b) Bergstad, K.; Backvall, J. E. Mild and efficient flavin-catalyzed
H2O2 oxidation of tertiary amines to amine N-oxides. J. Org. Chem.
998, 63, 6650−6655.
11) (a) Mazzini, C.; Lebreton, J.; Furstoss, R. Flavin-catalyzed
*
1
(
*
Baeyer-Villiger reaction of ketones: Oxidation of cyclobutanones to
gamma lactones using hydrogen peroxide. J. Org. Chem. 1996, 61, 8−
9. (b) Imada, Y.; Iida, H.; Murahashi, S.; Naota, T. An aerobic,
organocatalytic, and chemoselective method for Baeyer-Villiger
oxidation. Angew. Chem., Int. Ed. 2005, 44, 1704−1706. (c) Pouy,
M. J.; Milczek, E. M.; Figg, T. M.; Otten, B. M.; Prince, B. M.;
Gunnoe, T. B.; Cundari, T. R.; Groves, J. T. Flavin-Catalyzed
Insertion of Oxygen into Rhenium−Methyl Bonds. J. Am. Chem. Soc.
2012, 134, 12920−12923. (d) Murray, A. T.; Matton, P.; Fairhurst,
N. W. G.; John, M. P.; Carbery, D. R. Biomimetic Flavin-Catalyzed
Aldehyde Oxidation. Org. Lett. 2012, 14, 3656−3659. (e) Chen, S.;
Hossain, M. S.; Foss, F. W. Organocatalytic Dakin Oxidation by
Nucleophilic Flavin Catalysts. Org. Lett. 2012, 14, 2806−2809.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
We are grateful for financial support from the Youth
Innovation Promotion Association CAS (No. 2018402); the
Natural Science Foundation of Sichuan province, China (No.
017JY0055); the Innovative Team of Sichuan Province
Grant No. 2017TD0021).
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(f) Menova, P.; Dvorakova, H.; Eigner, V.; Ludvík, J.; Cibulka, R.
́ ́ ̌ ́ ́
Electron-Deficient Alloxazinium Salts: Efficient Organocatalysts of
Mild and Chemoselective Sulfoxidations with Hydrogen Peroxide.
Adv. Synth. Catal. 2013, 355, 3451−3462.
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ACS Catal. 2020, 10, 245−252