Organic Letters
Letter
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hydrogenation by HEH tend to occurred on aldimine D1 rather
than ketone imine A1 due to the fast transformation through α-
amino aldehyde intermediate C1. The chirality obtained
probably arose from asymmetric protonation (B1 to C1 or
E1 to D1) rather than asymmetric transfer hydrogenation of
ketone imine F1 (Figure 4).
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̈
In summary, amphoteric α-amino aldehyde could be
generated in situ with readily available starting materials via
the Heyns rearrangement. This transient intermediate was
proven to be available through several domino reactions. For
the traditional Heyns rearrangement, the in situ formed α-
amino aldehyde was captured by the intramolecular hydroxyl.
However, we succeeded in capturing this reactive intermediate
through intermolecular or intramolecular carbon nucleophiles
and nitrogen nucleophiles. Different types of pyrroles,
especially all-substituted pyrroles, 2-arylindoles, and quinoxa-
lines, were smoothly obtained with this efficient domino
reaction. Interestingly, the methods developed herein allowed
for the fast synthesis of four types of N-heterocycles based on
one in situ formed amphoteric α-amino aldehyde. Meanwhile,
the only byproduct formed in these domino reactions was
water. These results may pave the way for using simple α-
hydroxy ketone as the precursor of α-amino aldehyde, which
would be used as important synthon in synthetic chemistry in
the future.
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ASSOCIATED CONTENT
* Supporting Information
■
S
The Supporting Information is available free of charge on the
Experimental procedures; characterization of selected
AUTHOR INFORMATION
Corresponding Authors
■
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
We acknowledge financial support from the National Science
Foundation of China (Grant No. 21402188).
■
(13) (a) Wen, W.; Zeng, Y.; Peng, L.-Y.; Fu, L.-N.; Guo, Q.-X. Org.
Lett. 2015, 17, 3922. (b) Rueping, M.; Parmar, D.; Sugiono,
E.Asymmetric Brønsted Acid Catalysis; Wiley−VCH: Weinheim, 2015.
(c) Yang, J. W.; Hechavarria Fonseca, M. T.; List, B. Angew. Chem., Int.
Ed. 2004, 43, 6660.
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