Journal of the American Chemical Society
Page 4 of 5
4. (a) Shin, K.; Kim, H.; Chang, S. Acc. Chem. Res. 2015, 48, 1040; (b)
Romero, N. A.; Margrey, K. A.; Tay, N. E.; Nicewicz, D. A. Science 2015,
349, 1326.
5. Kurti, L.; Czakó, B., Strategic applications of named reactions in or-
ganic synthesis. Elsevier: 2005.
1
2
3
6. (a) Hartwig, J. F.; Collman, J. P., Organotransition metal chemistry:
from bonding to catalysis. University Science Books Sausalito, CA: 2010;
(b) Luo, Y.-R., Handbook of bond dissociation energies in organic com-
pounds. CRC press: 2002; (c) Crabtree, R. H., The organometallic chemis-
try of the transition metals. John Wiley & Sons: 2009.
4
5
6
7
8
9
7. Hall, D. G., Boronic acids: preparation, applications in organic syn-
thesis and medicine. John Wiley & Sons: 2006.
8. (a) Miyaura, N.; Suzuki, A. Chem. Rev. 1995, 95, 2457; (b) Su, B.;
Cao, Z.-C.; Shi, Z.-J. Acc. Chem. Res. 2015, 48, 886; (c) Zarate, C.; van
Gemmeren, M.; Somerville, R. J.; Martin, R. Adv. Organomet. Chem. 2016,
66, 143; (d) Rosen, B. M.; Quasdorf, K. W.; Wilson, D. A.; Zhang, N.;
Resmerita, A.-M.; Garg, N. K.; Percec, V. Chem. Rev. 2011, 111, 1346; (e)
Tobisu, M.; Chatani, N. Acc. Chem. Res. 2015, 48, 1717; (f) Kakiuchi, F.;
Usui, M.; Ueno, S.; Chatani, N.; Murai, S. J. Am. Chem. Soc. 2004, 126,
2706; (g) Tollefson, E. J.; Hanna, L. E.; Jarvo, E. R. Acc. Chem. Res. 2015,
48, 2344; (h) Guo, L.; Liu, X.; Baumann, C.; Rueping, M. Angew. Chem.
Int. Ed. 2016, 55, 15415.
9. (a) Ouyang, K.; Hao, W.; Zhang, W.-X.; Xi, Z. Chem. Rev. 2015, 115,
12045; (b) Wang, Q.; Su, Y.; Li, L.; Huang, H. Chem. Soc. Rev. 2016, 45,
1257.
10. (a) Blakey, S. B.; MacMillan, D. W. J. Am. Chem. Soc. 2003, 125,
6046; (b) Wenkert, E.; Han, A.-L.; Jenny, C.-J. J. Chem. Soc., Chem. Com-
mun. 1988, 975; (c) Reeves, J. T.; Fandrick, D. R.; Tan, Z.; Song, J. J.; Lee,
H.; Yee, N. K.; Senanayake, C. H. Org. Lett. 2010, 12, 4388; (d) Xie, L.-
G.; Wang, Z.-X. Angew. Chem. Int. Ed. 2011, 50, 4901.
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
Scheme 3. Plausible mechanism for the SMC reaction
In summary, we demonstrated the first Suzuki-Miyaura coupling
reaction of N,N-dialkyl aryl amines via nickel catalysis under re-
ductive conditions in the absence of any directing groups and pre-
activation. Magnesium was proved to play dual roles to facilitate
the reported cross-coupling reaction. Further experiments demon-
strated that the reaction was delivered via Ni(I)/Ni(III) catalytic cy-
cle. Efforts to investigate the detailed mechanism, to extend the
substrate scope and to improve the efficiency of this transformation
are undergoing.
ASSOCIATED CONTENT
Supporting Information
11. (a) Ueno, S.; Chatani, N.; Kakiuchi, F. J. Am. Chem. Soc. 2007, 129,
6098; (b) Koreeda, T.; Kochi, T.; Kakiuchi, F. J. Am. Chem. Soc. 2009, 131,
7238.
The Supporting Information is available free of charge on the ACS
Publications website.
12. (a) Tobisu, M.; Nakamura, K.; Chatani, N. J. Am. Chem. Soc. 2014,
136, 5587; (b) Cao, Z.-C.; Li, X.-L.; Luo, Q.-Y.; Fang, H.; Shi, Z.-J. Org.
Lett. 2018, 20, 1995.
Supporting Information (PDF);
Cif files of Ni(IMesMe)2Br2, Ni(IMesMe)2, and Ni(IMesMe)2Br
13. Compared to other ligands, such as IMes, IMesMe was more electron-
rich: Huynh, H. V. Chem. Rev. 2018.
AUTHOR INFORMATION
Corresponding Author
14. Jun, C.-H. Chem. Soc. Rev. 2004, 33, 610.
15. (a) Everson, D. A.; Weix, D. J. The Journal of Organic Chemistry
2014, 79, 4793; (b) Weix, D. J. Acc. Chem. Res. 2015, 48, 1767; (c) I., K.
C. E.; Sabine, G.; Dominik, G.; Martin, C.; Corinne, G.; Axel, J. v. W.
Chemistry – A European Journal 2014, 20, 6828; (d) Cao, Z.-C.; Luo, Q.-
Y.; Shi, Z.-J. Org. Lett. 2016, 18, 5978; (e) Cao, Z.-C.; Shi, Z.-J. J. Am.
Chem. Soc. 2017, 139, 6546.
Z.J.S.: zshi@pku.edu.cn, zjshi@fudan.edu.cn
H.F.: hfang@fudan.edu.cn
Notes
The authors declare no competing financial interests.
16. Chan, C. K.; Amy, F.; Zhang, Q.; Barlow, S.; Marder, S.; Kahn, A.
Chem. Phys. Lett. 2006, 431, 67.
ACKNOWLEDGMENT
17. (a) Cornella, J.; Zarate, C.; Martin, R. Chem. Soc. Rev. 2014, 43,
8081; (b) Yu, D.-G.; Li, B.-J.; Shi, Z.-J. Acc. Chem. Res. 2010, 43, 1486.
18. (a) Jun, T.; Hirohisa, T.; Hideyuki, W.; Aki, I.; Nobuaki, K. Angew.
Chem. Int. Ed. 2004, 43, 6180; (b) Hatakeyama, T.; Hashimoto, T.; Kondo,
Y.; Fujiwara, Y.; Seike, H.; Takaya, H.; Tamada, Y.; Ono, T.; Nakamura,
M. J. Am. Chem. Soc. 2010, 132, 10674; (c) Ito, S.; Fujiwara, Y.-i.; Naka-
mura, E.; Nakamura, M. Org. Lett. 2009, 11, 4306.
19. Stoll, S.; Schweiger, A. J. magn. reson. 2006, 178, 42.
20. (a) Macgregor, S. A.; Neave, G. W.; Smith, C. Faraday Discuss.
2003, 124, 111; (b) Lim, C.-H.; Kudisch, M.; Liu, B.; Miyake, G. M. J. Am.
Chem. Soc. 2018, 140, 7667; (c) Lin, B. L.; Clough, C. R.; Hillhouse, G. L.
J. Am. Chem. Soc. 2002, 124, 2890; (d) Corcoran, E. B.; Pirnot, M. T.; Lin,
S.; Dreher, S. D.; DiRocco, D. A.; Davies, I. W.; Buchwald, S. L.; MacMil-
lan, D. W. C. Science 2016, 353, 279.
Support of this work by the “973” Project from the MOST
(2015CB856600),
NSFC
(Nos.
21332001,
21431008,
21761132027, and 91645111), Shanghai city (18YF1401800 and
18JC1411300), and Fudan-SIMM Joint Research Fund are grate-
fully acknowledged. Kai Wang (Fudan University), Ying Liu (Fu-
dan University), and Zhen Wang (Fudan University) were
acknowledged for the purification and analysis of partial substrates.
REFERENCES
1. Ricci, A., Amino group chemistry: from synthesis to the life sciences.
John Wiley & Sons: 2008.
2. Monnier, F.; Taillefer, M. Angew. Chem. Int. Ed. 2009, 48, 6954.
3. (a) Hartwig, J. F. Handbook of organopalladium chemistry for organic
synthesis 2002, 1051; (b) Yang, B. H.; Buchwald, S. L. J. Organomet. Chem.
1999, 576, 125.
SYNOPSIS TOC
Insert Table of Contents artwork here
ACS Paragon Plus Environment