10.1002/anie.201911742
Angewandte Chemie International Edition
COMMUNICATION
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In conclusion, we have developed a Cu(I)/CPA-catalyzed
asymmetric intramolecular radical-involved C−H amination of
allylic and benzylic substrates, giving facile access to chiral α-
alkenyl/α-aryl
pyrrolidines
with
excellent
levels
of
enantioselectivity, moderate to high efficiency, broad substrate
scope and good functional group tolerance. This is the first
example to construct C−N bond with excellent enantiocontrol
through asymmetric radical oxidative C−H bond amination.
Critical to the success of this protocol is the application of 4-OMe-
PINO as a stable and chemoselective HAT mediator to selectively
abstract H atom of allylic and benzylic positions. The fulfillment of
this asymmetric radical-involved CH amination might provide
useful insight for radical-involved enantioselective oxidative
C(sp3)−H bond functionalization.
Acknowledgements
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Financial support from the National Natural Science Foundation
of China (nos 21722203, 21831002, and 21702093), Shenzhen
special funds for the development of biomedicine, Internet, new
energy, and new material industries (JCYJ20180302174416591 )
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and Shenzhen Nobel Prize
(C17783101).
Scientists
Laboratory
Project
Conflict of Interest
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The authors declare no conflict of interest.
Chemical Bond Energies, CRC Press, Boca Raton, 2007.
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Keywords: copper • chiral phosphoric acid • radical asymmetric
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