Organic Letters
ORCID
Letter
Song, J. J.; Lee, H.; Yee, N. K.; Senanayake, C. H. Room Temperature
Palladium-Catalyzed Cross Coupling of Aryltrimethylammonium
Triflates with Aryl Grignard Reagents. Org. Lett. 2010, 12, 4388−
4391. (f) Xie, L.-G.; Wang, Z.-X. Nickel-Catalyzed Cross-Coupling of
Aryltrimethylammonium Iodides with Organozinc Reagents. Angew.
Chem., Int. Ed. 2011, 50, 4901−4904. (g) Wang, D.-Y.; Kawahata, M.;
Yang, Z.-K.; Miyamoto, K.; Komagawa, S.; Yamaguchi, K.; Wang, C.;
Uchiyama, M. Stille coupling via C−N bond cleavage. Nat. Commun.
2016, 7, 12937−12945.
(6) (a) Bonanno, J. B.; Henry, T. P.; Neithamer, D. R.; Wolczanski,
P. T.; Lobkovsky, E. B. Arylamine C−N Bond Oxidative Addition to
(silox)3Ta (silox = Bu3SiO). J. Am. Chem. Soc. 1996, 118, 5132−
5133. (b) Man, W.-L.; Xie, J.; Pan, Y.; Lam, W. W. Y.; Kwong, H.-K.;
Ip, K.-W.; Yiu, S.-M.; Lau, K.-C.; Lau, T.-C. C−N Bond Cleavage of
Anilines by a (Salen)ruthenium(VI) Nitrido Complex. J. Am. Chem.
Soc. 2013, 135, 5533−5536.
(7) (a) Ueno, S.; Chatani, N.; Kakiuchi, F. Ruthenium-Catalyzed
Carbon−Carbon Bond Formation via the Cleavage of an Unreactive
Aryl Carbon−Nitrogen Bond in Aniline Derivatives with Organo-
boronates. J. Am. Chem. Soc. 2007, 129, 6098−6099. (b) Koreeda, T.;
Kochi, T.; Kakiuchi, F. Cleavage of C−N Bonds in Aniline Derivatives
on a Ruthenium Center and Its Relevance to Catalytic C−C Bond
Formation. J. Am. Chem. Soc. 2009, 131, 7238−7239. (c) Zhao, Y.;
Snieckus, V. Beyond Directed Ortho Metalation: Ruthenium-
Catalyzed Amide-Directed CAr−N Activation/C−C Coupling Re-
action of Anthranilamides with Organoboronates. Org. Lett. 2014, 16,
3200−3203. (d) Cao, Z.-C.; Xie, S.-J.; Fang, H.; Shi, Z.-J. Ni-
Catalyzed Cross-Coupling of Dimethyl Aryl Amines with Arylboronic
Esters under Reductive Conditions. J. Am. Chem. Soc. 2018, 140,
13575−13579.
(8) (a) Koreeda, T.; Kochi, T.; Kakiuchi, F. Ruthenium-Catalyzed
Reductive Deamination and Tandem Alkylation of Aniline Deriva-
tives. J. Organomet. Chem. 2013, 741−742, 148−152. (b) Koreeda, T.;
Kochi, T.; Kakiuchi, F. Substituent Effects on Stoichiometric and
Catalytic Cleavage of Carbon−Nitrogen Bonds in Aniline Derivatives
by Ruthenium−Phosphine Complexes. Organometallics 2013, 32,
682−690.
(9) Kondo, H.; Akiba, N.; Kochi, T.; Kakiuchi, F. Ruthenium-
Catalyzed Monoalkenylation of Aromatic Ketones by Cleavage of
Carbon−Heteroatom Bonds with Unconventional Chemoselectivity.
Angew. Chem., Int. Ed. 2015, 54, 9293−9297.
(10) (a) Tobisu, M.; Nakamura, K.; Chatani, N. Nickel-Catalyzed
Reductive and Borylative Cleavage of Aromatic Carbon−Nitrogen
Bonds in N-Aryl Amides and Carbamates. J. Am. Chem. Soc. 2014,
136, 5587−5590. (b) Cao, Z.-C.; Li, X.-L.; Luo, Q.-Y.; Fang, H.; Shi,
Z.-J. Direct Borylation of Tertiary Anilines via C−N Bond Activation
Org. Org. Lett. 2018, 20, 1995−1998.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
We acknowledge financial support from NNSFC (J.-B. X.,
21772208; J.C., 21702212; X.H., 21702182), NSFC of Jiangsu
Province (J.-B.X., BK20161260), the Hundred-Talented
Program of the Chinese Academy of Sciences (J.-B.X.),
LICP (J.-B.X), the Chinese “Thousand Youth Talents Plan”
(X.H.), “Fundamental Research Funds for the Central
Universities” (X.H.), and Zhejiang University (X.H.). Calcu-
lations were performed on the high-performance computing
system at the Department of Chemistry, Zhejiang University.
t
REFERENCES
■
(1) The Chemistry of Anilines, Parts 1−2; Rappoport, Z., Ed.; John
Wiley & Sons: Chichester, 2007.
(2) (a) Wolfe, J. P.; Wagaw, S.; Marcoux, J.-F.; Buchwald, S. L.
Rational Development of Practical Catalysts for Aromatic Carbon−
Nitrogen Bond Formation. Acc. Chem. Res. 1998, 31, 805−818.
(b) Hartwig, J. F. Carbon−Heteroatom Bond-Forming Reductive
Eliminations of Amines, Ethers, and Sulfides. Acc. Chem. Res. 1998,
31, 852−860. (c) Ma, D.; Cai, Q. Copper/Amino Acid Catalyzed
Cross-Couplings of Aryl and Vinyl Halides with Nucleophiles. Acc.
Chem. Res. 2008, 41, 1450−1460. (d) Jiao, J.; Murakami, K.; Itami, K.
Catalytic Methods for Aromatic C−H Amination: An Ideal Strategy
for Nitrogen-Based Functional Molecules. ACS Catal. 2016, 6, 610−
633. (e) Creutz, S. E.; Lotito, K. J.; Fu, G. C.; Peters, J. C.
Photoinduced Ullmann C−N Coupling: Demonstrating the Viability
of a Radical Pathway. Science 2012, 338, 647. (f) Romero, N. A.;
Margrey, K. A.; Tay, N. E.; Nicewicz, D. A. Site-Selective Arene C-H
Amination via Photoredox Catalysis. Science 2015, 349, 1326.
(g) Paudyal, M. P.; Adebesin, A. M.; Burt, S. R.; Ess, D. H.; Ma,
Z.; Kurti, L.; Falck, J. R. Dirhodium-Catalyzed C-H Arene Amination
̈
using Hydroxylamines. Science 2016, 353, 1144. (h) Corcoran, E. B.;
Pirnot, M. T.; Lin, S.; Dreher, S. D.; DiRocco, D. A.; Davies, I. W.;
Buchwald, S. L.; MacMillan, D. W. C. Aryl Amination Using Ligand-
Free Ni(II) Salts and Photoredox Catalysis. Science 2016, 353, 279.
(i) Gao, H.; Zhou, Z.; Kwon, D.-H.; Coombs, J.; Jones, S.; Behnke, N.
E.; Ess, D. H.; Kurti, L. Rapid Heteroatom Transfer to Arylmetals
̈
Utilizing Multifunctional Reagent Scaffolds. Nat. Chem. 2016, 9, 681.
(3) (a) Ouyang, K.; Hao, W.; Zhang, W.-X.; Xi, Z. Transition-Metal-
Catalyzed Cleavage of C−N Single Bonds. Chem. Rev. 2015, 115,
12045−12090. (b) Wang, Q.; Su, Y.; Li, L.; Huang, H. Transition-
Metal Catalysed C-N Bond Activation. Chem. Soc. Rev. 2016, 45,
1257−1272. (c) Desnoyer, A. N.; Love, J. A. Recent Advances in
Well-Defined, Late Transition Metal Complexes That Make and/or
Break C−N, C−O and C−S Bonds. Chem. Soc. Rev. 2017, 46, 197−
238.
(11) Cong, X.; Fan, F.; Ma, P.; Luo, M.; Chen, H.; Zeng, X. Low-
Valent, High-Spin Chromium-Catalyzed Cleavage of Aromatic
Carbon−Nitrogen Bonds at Room Temperature: A Combined
Experimental and Theoretical Study. J. Am. Chem. Soc. 2017, 139,
15182−15190.
(12) (a) Hie, L.; Fine Nathel, N. F.; Shah, T. K.; Baker, E. L.; Hong,
X.; Yang, Y.-F.; Liu, P.; Houk, K. N.; Garg, N. K. Conversion of
Amides to Esters by the Nickel-Catalysed Activation of Amide C−N
Bonds. Nature 2015, 524, 79−83. (b) Li, X.; Zou, G. Acylative Suzuki
Coupling of Amides: Acyl-nitrogen Activation via Synergy of
Independently Modifiable Activating Groups. Chem. Commun. 2015,
51, 5089−5092. (c) Meng, G.; Szostak, M. Sterically Controlled Pd-
Catalyzed Chemoselective Ketone Synthesis via N−C Cleavage in
Twisted Amides. Org. Lett. 2015, 17, 4364−4367. (d) Meng, G.;
Szostak, M. General Olefin Synthesis by the Palladium-Catalyzed
Heck Reaction of Amides: Sterically Controlled Chemoselective
N□C Activation. Angew. Chem., Int. Ed. 2015, 54, 14518−14522.
(13) For reveiws, see: (a) Liu, C.; Szostak, M. Twisted Amides:
From Obscurity to Broadly Useful Transition-Metal-Catalyzed
Reactions by N−C Amide Bond Activation. Chem. - Eur. J. 2017,
23, 7157−7173. (b) Gao, Y.; Ji, C.-L.; Hong, X. Ni-Mediated C−N
Activation of Amides and Derived Catalytic Transformations. Sci.
(4) Blanksby, S. J.; Ellison, G. B. Bond Dissociation Energies of
Organic Molecules. Acc. Chem. Res. 2003, 36, 255−263.
(5) (a) Roglans, A.; Pla-Quintana, A.; Moreno-Manas, M.
̃
Diazonium Salts as Substrates in Palladium-Catalyzed Cross-Coupling
Reactions. Chem. Rev. 2006, 106, 4622−4643. (b) Li, G.; Chen, Y.;
Xia, J. Progress on Transition-Metal-Catalyzed Cross-coupling
Reactions of Ammonium Salts via C−N Bond Cleavage. Youji
Huaxue 2018, 38, 1949−1962. (c) Wenkert, E.; Han, A.-L.; Jenny, C.-
J. Nickel-induced conversion of carbon−nitrogen into carbon−carbon
bonds. One-step transformations of aryl, quaternary ammonium salts
into alkylarenes and biaryls. J. Chem. Soc., Chem. Commun. 1988,
975−976. (d) Blakey, S. B.; MacMillan, D. W. C. The First Suzuki
Cross-Couplings of Aryltrimethylammonium Salts. J. Am. Chem. Soc.
2003, 125, 6046−6047. (e) Reeves, J. T.; Fandrick, D. R.; Tan, Z.;
E
Org. Lett. XXXX, XXX, XXX−XXX