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Letter
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Scheme 3 Proposed catalytic cycle
In summary, we have developed the first direct asym-
metric α-hydroxylation of α-branched ketones through
enol catalysis.19 By employing nitrosobenzene as both the
oxidant and reductant in a tandem process, various valu-
able cyclic α-hydroxy ketones were obtained in moderate to
good yields and excellent enantioselectivities. We believe
that the presented findings will further broaden the scope
of enol catalysis thus inspiring other highly enantioselec-
tive transformations.
Funding Information
The Max Planck Society, the DFG (Leibnitz award to B.L.) and the
Fonds der Chemischen Industrie (fellowship to G.P.) are acknowledged
for financial support.()
(10) (a) Felker, I.; Pupo, G.; Kraft, P.; List, B. Angew. Chem. Int. Ed.
2015, 54, 1960. (b) Monaco, M. R.; Pupo, G.; List, B. Synlett 2016,
27, 1027. For a non-enantioselective version of the reaction
reported here, see: (c) Shevchenko, G. A.; Dehn, S.; List, B.
Synlett 2018, 29, 2298.
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Acknowledgment
The authors greatly acknowledge the NMR (J. Lingnau), GC, HPLC, and
X-Ray departments of the MPI-Kohlenforschung.
Supporting Information
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(b) Yang, X.; Toste, F. D. J. Am. Chem. Soc. 2015, 137, 3205.
(13) Shevchenko, G. A.; Oppelaar, B.; List, B. Angew. Chem. Int. Ed.
2018, 57, 10756.
Supporting information for this article is available online at
S
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References and Notes
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© Georg Thieme Verlag Stuttgart · New York — Synlett 2018, 29, A–E