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Journal of the American Chemical Society
B. M.; Thaisrivongs, D. A.; Hartwig, J. Palladium-Catalyzed
ORCID
David Huang: 0000-00027179-0738
Timothy R. Newhouse: 0000-0001-8741-7236
Asymmetric Allylic Alkylations of Polynitrogen-Containing
Aromatic Heterocycles. J. Am. Chem. Soc. 2011, 133, 12439–
12441. (c) Sha, S.-C.; Zhang, J.; Carroll, P. J.; Walsh, P. J. Raising
the pKa Limit of “Soft” Nucleophiles in Palladium-Catalyzed
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Allylic
Substitutions:
Application
of
Diarylmethane
Author Contributions
Pronucleophiles. J. Am. Chem. Soc. 2013, 135, 17602−17609. (d)
Sha, S.-C.; Jiang, H.; Mao, J.; Bellomo, A.; Jeong, S. A.; Walsh, P.
†P.Z. and D.H. contributed equally.
J. Nickel ‐ Catalyzed Allylic Alkylation with Diarylmethane
Notes
Pronucleophiles: Reaction Development and Mechanistic Insights.
Angew. Chem. Int. Ed. 2016, 55, 1070–1074. (e) Murakami, R.;
Sano, K.; Iwai, T.; Taniguchi, T.; Monde, K.; Sawamura, M.
Palladium-Catalyzed Asymmetric C(sp3)-H Allylation of 2-
Alkylpyridines. Angew. Chem. Int. Ed. 2018, 57, 9465–9469.
(10) For recently reported benzylic arylation reactions: (a) Hlavinka, M.
L.; Hagadorn, J. R. Zn(tmp)2: A Versatile Base for the Selective
Functionalization of C-H Bonds. Organometallics 2007, 26, 4105–
4108. (b) Niwa, T.; Yorimitsu, H.; Oshima, K. Palladium-Catalyzed
Direct Arylation of Aryl(azaaryl)methanes with Aryl Halides
Providing Triarylmethanes. Org. Lett. 2007, 9, 2373–2375. (c) Cao,
X.; Sha, S.-C.; Kim, B.-S.; Morgan, C.; Huang, R.; Yang, X.;
Walsh, P. J. Nickel-Catalyzed Arylation of Heteroaryl-Containing
Diarylmethanes: Exceptional Reactivity of the Ni(NIXANTPHOS)-
Based Catalyst. Chem. Sci. 2016, 7, 611–618. (d) Moo, P. J.; Wei,
Z.; Lundgren, R. J. Direct Catalytic Enantioselective Benzylation
from Aryl Acetic Acids. J. Am. Chem. Soc. 2018, 140, 17418–
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(11) Huang, D.; Szewczyk, S. M.; Zhang, P.; Newhouse, T. R. Allyl-
Nickel Catalysis Enables Carbonyl Dehydrogenation and Oxidative
Cycloalkenylation of Ketones. J. Am. Chem. Soc. 2019, 141, 5669–
5674.
(12) Best, D.; Lam, H. W. C=N-Containing Azaarenes as Activating
Groups in Enantioselective Catalysis. J. Org. Chem. 2014, 79, 831–
845.
(13) (a) Hartwig, J. F. Electronic Effects on Reductive Elimination to
Form Carbon-Carbon and Carbon-Heteroatom Bonds from
Palladium(II)-Complexes. Inorg. Chem. 2007, 46, 1936–1947. (b)
Huang, D.; Olivieri, D.; Sun, Y.; Zhang, P.; Newhouse, T. R.
Nickel-Catalyzed Difunctionalization of Unactivated Alkenes
Initiated by Unstabilized Enolates. J. Am. Chem. Soc. 2019, 141,
16249–16254.
(14) Alexanian, E. J.; Hartwig, J. F. Mechanistic Study of -Hydrogen
Elimination from Organoplatinum(II) Enolate Complexes. J. Am.
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The authors declare no competing financial interests.
ACKNOWLEDGMENT
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We are grateful for financial support from Yale University,
Amgen, the Sloan Foundation, the Anderson Foundation (post-
doctoral fellowship to P.Z.) and Bristol Myers Squibb (Graduate
Student Fellowship to D.H.). We gratefully acknowledge Yannan
Liu for a procedural check with substrate 1q.
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