Journal of the American Chemical Society
Page 4 of 5
1
2
3
4
5
6
7
8
9
(15) Chen, Z.; Zeng, H.; Girard, S. A.; Wang, F.; Chen, N.; Li, C.-J.,
Formal Direct Cross-Coupling of Phenols with Amines. Angew. Chem.,
Int. Ed. 2015, 54, 14487-14491.
ASSOCIATED CONTENT
Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website.
Detailed experimental procedures, characterization of new com-
pounds (PDF)
(16) Mellegaard-Waetzig, S. R.; Rayabarapu, D. K.; Tunge, J. A., Allylic
Amination via Decarboxylative C-N Bond Formation. Synlett 2005, 2005,
2759-2762.
(17) The decarboxylative amination of 2-naphthyl carbamate was reported
as a side reaction pathway when 100 mol% of a nickel complex was used
in the Supporting Information of the following paper: Wang, Y.; Wu, S.-
B.; Shi, W.-J.; Shi, Z.-J., C–O/C–H Coupling of Polyfluoroarenes with
Aryl Carbamates by Cooperative Ni/Cu Catalysis. Org. Lett. 2016, 18,
2548-2551.
AUTHOR INFORMATION
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Corresponding Author
*tobisu@chem.eng.osaka-u.ac.jp;
sawamura@sci.hokudai.ac.jp; chatani@chem.eng.osaka-u.ac.jp;
(18) (a) Iwai, Y.; Harada, T.; Shimada, H.; Asano, K.; Sawamura, M., A
Polystyrene-Cross-Linking Bisphosphine: Controlled Metal Monochela-
iwai-t@sci.hokudai.ac.jp;
tion and Ligand-Enabled First-Row Transition Metal Catalysis. ACS Catal.
2017, 7, 1681-1692. (b) Yamazaki, Y.; Arima, N.; Iwai, T.; Sawamura, M.
Adv. Synth. Catal. in press, DOI: 10.1002/adsc.201801713.
(19) Maiti, D.; Fors, B. P.; Henderson, J. L.; Nakamura, Y.; Buchwald, S.
L., Palladium-catalyzed coupling of functionalized primary and secondary
amines with aryl and heteroaryl halides: two ligands suffice in most cases.
Chem. Sci. 2011, 2, 57-68.
(20) Brusoe, A. T.; Hartwig, J. F., Palladium-Catalyzed Arylation of
Fluoroalkylamines. J. Am. Chem. Soc. 2015, 137, 8460-8468.
(21) Wolfe, J. P.; Buchwald, S. L., Nickel-Catalyzed Amination of Aryl
Chlorides. J. Am. Chem. Soc. 1997, 119, 6054-6058.
ACKNOWLEDGMENT
We thank the Instrumental Analysis Center, Faculty of Engineer-
ing, Osaka University, for their assistance with HRMS. This work
was supported by JSPS KAKENHI (15H03811 to MT and
17H04877 to TI) and Scientific Research on Innovative Area
"Precisely Designed Catalysts with Customized Scaffolding"
(18H04259 to MT and 15H05801 to MS) from MEXT, Japan. MT
thanks Toray Science Foundation for financial support.
(22) p-NMe2-substituted (S1a) and o-Me-substituted (S1b) carbamates
were also applicable to form S2a and S2b, respectively. Alkenyl carba-
mate S1c was much less reactive under these conditions and the product
was formed in only 8%.
REFERENCES
(1) Ruiz-Castillo, P.; Buchwald, S. L., Applications of Palladium-
Catalyzed C–N Cross-Coupling Reactions. Chem. Rev. 2016, 116, 12564-
12649.
(2) Surry, D. S.; Buchwald, S. L., Biaryl Phosphane Ligands in Palladium-
Catalyzed Amination. Angew. Chem., Int. Ed. 2008, 47, 6338-6361.
(3) Hartwig, J. F., Evolution of a Forth Generation Catalyst for the Amina-
tion and Thioetherification of Aryl Halides. Acc. Chem. Res. 2008, 41,
1534-1544.
(4) Rosen, B. M.; Quasdorf, K. W.; Wilson, D. A.; Zhang, N.; Resmerita,
A.-M.; Garg, N. K.; Percec, V., Nickel-Catalyzed Cross-Couplings In-
volving Carbon−Oxygen Bonds. Chem. Rev. 2011, 111, 1346-1416.
(5) Li, B.-J.; Yu, D.-G.; Sun, C.-L.; Shi, Z.-J., Activation of “Inert”
Alkenyl/Aryl C–O Bond and Its Application in Cross-Coupling Reactions.
Chem.–Eur. J. 2011, 17, 1728-1759.
(6) Yamaguchi, J.; Muto, K.; Itami, K., Recent Progress in Nickel-
Catalyzed Biaryl Coupling. Eur. J. Org. Chem. 2013, 2013, 19-30 .
(7) Cornella, J.; Zarate, C.; Martin, R., Metal-catalyzed activation of
ethers via C–O bond cleavage: a new strategy for molecular diversity
Chem. Soc. Rev. 2014, 43, 8081-8097.
(23) Vitaku, E.; Smith, D. T.; Njardarson, J. T., Analysis of the Structural
Diversity, Substitution Patterns, and Frequency of Nitrogen Heterocycles
among U.S. FDA Approved Pharmaceuticals. J. Med. Chem. 2014, 57,
10257-10274.
(24) Adger, B. M.; O'Farrell, C.; Lewis, N. J.; Mitchell, M. B., Catalytic
Transfer Hydrogenolysis of N-Benzyl Protecting Groups. Synthesis 1987,
1987, 53-55.
(25) Garg reported that the oxidative addition of a C(aryl)-O bond in aryl
carbamates is a relatively facile process when a Ni/NHC catalyst is used
(ref 13). However, ligand 3g is by far a weaker -donor, thus requiring a
higher barrier for the oxidative addition.
(26) Another possible mechanism for the formation of crossover products
is the generation of a free amine, followed by amination of the aryl car-
bamate. However, we conclude that this mechanism is unlikely because
free amines were not detected during the course of the reaction. The fact
that a formyl group is compatible also supports the absence of a free
amine during the course of the reaction.
(27) Wang, X.; Kauppi, Anna M.; Olsson, R.; Almqvist, F., Efficient
Solution-Phase Parallel Synthesis of 4-Substituted N-Protected Piperidines.
Eur. J. Org. Chem. 2003, 2003, 4586.
(28) (a) Schwarz, J.; König, B., Decarboxylative reactions with and with-
out light – a comparison. Green Chem. 2018, 20, 323-361. (b) Rodríguez,
N.; Goossen, L. J., Decarboxylative coupling reactions: a modern strategy
for C–C-bond formation. Chem. Soc. Rev. 2011, 40, 5030-5048.
(8) Tobisu, M.; Chatani, N., Cross-Couplings Using Aryl Ethers via C–O
Bond Activation Enabled by Nickel Catalysts. Acc. Chem. Res. 2015, 48,
1717-1726.
(9) Zeng, H.; Qiu, Z.; Domínguez-Huerta, A.; Hearne, Z.; Chen, Z.; Li,
C.-J., An Adventure in Sustainable Cross-Coupling of Phenols and Deriv-
atives via Carbon–Oxygen Bond Cleavage. ACS Catal. 2017, 7, 510-519.
(10) Surry, D. S.; Buchwald, S. L., Dialkylbiaryl phosphines in Pd-
catalyzed amination: a user's guide. Chem. Sci. 2011, 2, 27-50.
(11) Ramgren, S. D.; Silberstein, A. L.; Yang, Y.; Garg, N. K., Nickel-
Catalyzed Amination of Aryl Sulfamates. Angew. Chem. Int. Ed. 2011, 50,
2171-2173.
(12) Shimasaki, T.; Tobisu, M.; Chatani, N., Nickel-Catalyzed Amination
of Aryl Pivalates by the Cleavage of Aryl C–O Bonds Angew. Chem. Int.
Ed. 2010, 49, 2929-2932.
(13) Mesganaw, T.; Silberstein, A. L.; Ramgren, S. D.; Nathel, N. F. F.;
Hong, X.; Liu, P.; Garg, N. K., Nickel-catalyzed amination of aryl carba-
mates and sequential site-selective cross-couplings. Chem. Sci. 2011, 2,
1766-1771.
(14) (a) Tobisu, M.; Shimasaki, T.; Chatani, N., Ni0-catalyzed Direct
Amination of Anisoles Involving the Cleavage of Carbon-Oxygen Bonds.
Chem. Lett. 2009, 38, 710-711. (b) Tobisu, M.; Yasutome, A.; Yamakawa,
K.; Shimasaki, T.; Chatani, N., Ni(0)/NHC-catalyzed amination of N-
heteroaryl methyl ethers through the cleavage of carbon‒oxygen bonds.
Tetrahedron 2012, 68, 5157-5161.
ACS Paragon Plus Environment