Organic Letters
Letter
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The mechanism and the role of TMSCl are not clear at this
time. We propose that Ni(0) was generated by manganese and
added to the C−N bond of amide through oxidative addition
to give an acyl amino nickel(II) complex, followed by the
coordination of a primary amine to the nickel complex to
provide a transaminated nickel(II) complex. We suggest that
TMSCl might accelerate oxidative addition and/or trans-
amination steps. Finally, the reductive elimination provides the
transamidated secondary amide and Ni(0) catalyst.
In summary, we developed a direct transamidation of
secondary amides using a catalytic combination of nickel and a
Briphos ligand. Preactivation of the secondary amide is not
necessary because TMSCl activates the aniline derivatives via
the formation of the corresponding bis(trimethylsilyl)anilines.
The reaction of secondary amides and anilines proceeded
efficiently to afford the transamidation products in moderate to
good yields. Aniline derivatives having electron-donating
groups showed higher yields than those having electron-
withdrawing groups. Secondary amines participated in this
reaction, but the product yields were low. Further studies on
the reaction mechanism are underway in our laboratory.
ASSOCIATED CONTENT
* Supporting Information
■
S
The Supporting Information is available free of charge on the
Experimental procedures, NMR spectroscopic and MS
data for all new compounds (PDF)
(7) Hoerter, J. M.; Otte, K. M.; Gellman, S. H.; Cui, Q.; Stahl, S. S. J.
Am. Chem. Soc. 2008, 130, 647.
AUTHOR INFORMATION
Corresponding Authors
■
(8) (a) Bon, E.; Bigg, D. C. H.; Bertrand, G. J. J. Org. Chem. 1994,
59, 4035. (b) Eldred, S. E.; Stone, D. A.; Gellman, S. H.; Stahl, S. S. J.
Am. Chem. Soc. 2003, 125, 3422. (c) Hoerter, J. M.; Otte, K. M.;
Gellman, S. H.; Stahl, S. S. J. Am. Chem. Soc. 2006, 128, 5177.
(d) Stephenson, N. A.; Zhu, J.; Gellman, S. H.; Stahl, S. S. J. Am.
Chem. Soc. 2009, 131, 10003.
ORCID
(9) (a) Baker, E. L.; Yamano, M. M.; Zhou, Y.; Anthony, S. M.;
Garg, N. K. Nat. Commun. 2016, 7, 11554. (b) Hu, J.; Zhao, Y.; Liu,
J.; Zhang, Y.; Shi, Z. Angew. Chem., Int. Ed. 2016, 55, 8718.
(c) Dander, J. E.; Baker, E. L.; Garg, N. K. Chem. Sci. 2017, 8, 6433.
(d) Meng, G.; Lei, P.; Szostak, M. Org. Lett. 2017, 19, 2158. (e) Shi,
S.; Szostak, M. Chem. Commun. 2017, 53, 10584.
Notes
The authors declare no competing financial interest.
(10) Cheung, C. W.; Ploeger, M. L.; Hu, X. ACS Catal. 2017, 7,
7092.
ACKNOWLEDGMENTS
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(11) (a) Lee, A.; Ahn, S.; Kang, K.; Seo, M.-S.; Kim, Y.; Kim, W. Y.;
Kim, H. Org. Lett. 2014, 16, 5490−5493. (b) Lee, A.; Kim, H. J. Am.
Chem. Soc. 2015, 137, 11250−11253. (c) Kang, K.; Kim, J.; Lee, A.;
Kim, W. Y.; Kim, H. Org. Lett. 2016, 18, 616−619. (d) Lee, A.; Kim,
H. J. Org. Chem. 2016, 81, 3520.
(12) Heinz, C.; Lutz, J. P.; Simmons, E. M.; Miller, M. M.; Ewing,
W. R.; Doyle, A. G. J. Am. Chem. Soc. 2018, 140, 2292.
(13) The effect of the amount of p-toluidine and TMSCl was studied
(14) Lee, S.; Jorgensen, M.; Hartwig, J. F. Org. Lett. 2001, 3, 2729.
This research was supported by the National Research
Foundation of Korea (NRF) grant funded by the Korean
government (MSIP) (NRF-2015R1A4A1041036, NRF-
2017R1A2B4002650, and NRF-2017R1A2B2002929). The
spectral and HRMS data were obtained from the Korea
Basic Science Institute, Gwangju Center and Daegu Center.
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