Journal of the American Chemical Society
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Aponick, A. Acc. Chem. Res. 2006, 39, 747. (f) Rios, I. G.;
In summary, we have found that the cooperative catalysis of
palladium complexes of chiral phosphoramidite ligands and
Brønsted acids is able to render highly enantioselective allylic
C−H alkylation reactions of terminal alkenes with
RosasꢀHernandez, A.; Martin, E. Molecules 2011, 16, 970.
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pyrazolꢀ5ꢀones under mild conditions.
A
significant
synergistic effect between the chiral ligand and the chiral
counterion was observed in the stereochemical control of the
allylic C−H alkylation of allylarenes and pyrazolꢀ5ꢀones. The
palladiumꢀcatalyzed asymmetric allylic C−H alkylation of
1,4ꢀpentadienes with pyrazolꢀ5ꢀones has been established by
cooperative catalysis of chiral palladium complexes and
2ꢀfluorobenzoic acid. Both transformations show a broad
substrate scope in terms of both the pyrazolꢀ5ꢀones and olefins
to afford a wide scope of functionalized chiral Nꢀheterocycles
with an allꢀcarbon quaternary stereogenic center in high yields
and with high levels of enantioselectivity. More importantly, a
family of new chiral phosphoramidite ligands have been found
to show great potential in asymmetric allylic C−H
functionalization reactions and would allow their palladium
complexes combined with Brønsted acids to offer a generally
applicable strategy for the creation of asymmetric allylic C−H
alkylation reactions with other nucleophiles bearing
functionalities that can form hydrogenꢀbonding interaction
with conjugate bases in situ generated from Brønsted acid
coꢀcatalysts.
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ASSOCIATED CONTENT
Supporting Information. Complete experimental procedures and
characterization data for the prepared compounds. This material is
Experimental procedures; compound characterization data (PDF)
Crystallographic data for 3ao (CIF)
7 (CIF)
8 (CIF)
AUTHOR INFORMATION
Corresponding Author
ACKNOWLEDGMENT
We are grateful for financial support from MOST (973 project
2015CB856600), NSFC (21232007, 21302177 and 21502183),
Chinese Academy of Science (Grant No. XDB20020000) and the
China Postdoctoral Science Foundation (No. 2015M580534).
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