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COMMUNICATION
ChemComm
Ramana, Chem. Commun., 2013, 49, 6376.
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simultaneously activate cyclic C-acylimine and enolized ketone
through the hydrogen bonding interaction, therefore creating
a chiral environment wherein the enol attacks the Si face of
the C=N group preferentially. Further studies are required to
fully elucidate the detailed mechanism of this direct Mannich
reaction.
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Figure 2 Proposed transition state for the reaction.
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In summary, we have developed a chiral Brønsted acid-
catalyzed direct asymmetric Mannich reaction of cyclic C-
acylimines with unmodified methyl ketones. This method
tolerates a series of 2-aryl-substituted 3H-indol-3-ones,
affording the C2-quaternary indolin-3-ones in good to high
yields (up to 98%) and enantioselectivities (up to 99% ee).
Moreover, the adducts obtained can be readily converted into
various interesting compounds such as gem-disubstituted
indolines, tricyclic indolin-3-one fused aziridines, and
tetracyclic tetrahydro-indolo[1,2-a]quinolines by simple
modifications. Further applications of this strategy to other
substrate classes are ongoing in our laboratory.
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Notes and references
‡
This work was supported by the National Natural Science
Foundation of China (No. 21472137, 21532008, and 21772142),
the National Basic Research Program of China (973 Program,
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0. Preparation of N-tosylated 1'H,3H-[2,3'-biindol]-3-ones 5 see the
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