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Although lower-yielding than the efficient system reported by
Molander, we have avoided the use of a second catalyst and DMF
to keep our system in line with industrial requirements.12,14b
In conclusion, we devised a nickel(0) catalytic system capable
of cross-coupling normally unreactive aryl chlorides containing
electron-donating substituents. This nickel-phosphite Ni[P(Op-
tolyl)3]4 and xantphos catalytic system can also be applied to a
plethora of other aryl/heterocyclic chlorides. Importantly, the
system can also be made milder by substituting KOt-Bu for
Cs2CO3. This novel thioetherification protocol is also well suited
to a range of electronic and sterically congested thiophenols and
can be carried out in toluene, making it amenable to industrial
applications.
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ASSOCIATED CONTENT
* Supporting Information
■
S
TheSupportingInformationisavailablefreeofchargeontheACS
Experimental procedures and spectra of new compounds
(10) Xu, X.-B.; Liu, J.; Zhang, J.-J.; Wang, Y.-W.; Peng, Y. Org. Lett.
2013, 15, 550.
(11) Oderinde, M. S.; Frenette, M.; Robbins, D. W.; Aquila, B.;
Johannes, J. W. J. Am. Chem. Soc. 2016, 138, 1760.
AUTHOR INFORMATION
■
(12) (a) Jouffroy, M.; Kelly, C. B.; Molander, G. A. Org. Lett. 2016, 18,
876. (b) Vara, B. A.; Li, X.; Berritt, S.; Walters, C. R.; Petersson, E. J.;
(13) (a) Kalvet, I.; Guo, Q.; Tizzard, G. J.; Schoenebeck, F. ACS Catal.
2017, 7, 2126. (b) Yin, G.; Kalvet, I.; Englert, U.; Schoenebeck, F. J. Am.
Chem. Soc. 2015, 137, 4164.
(14) (a) Gogoi, P.; Hazarika, S.; Sarma, M. J.; Sarma, K.; Barman, P.
Tetrahedron2014, 70,7484. (b)Øpstad, C. L.;Melø, T.-B.;Sliwka, H.-R.;
Partali, V. Tetrahedron 2009, 65, 7616.
Corresponding Author
ORCID
Notes
The authors declare no competing financial interest.
(15) Jiang, M.; Li, H.; Yang, H.; Fu, H. Angew. Chem., Int. Ed. 2017, 56,
874.
ACKNOWLEDGMENTS
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The authors acknowledge the CMCA Research Facility at UWA.
The authors would like to thank Prof. Reto Dorta and A/Prof.
Keith Stubbs (UWA) for helpful discussion and several thiols.
Further NMR assistance from Dr. Mark Howard and Dr. Gareth
Nealon (UWA) is gratefully acknowledged. K.D.J. and D.J.P. are
recipients of an APA and UWA, respectively.
(16) (a) Kampmann, S. S.; Skelton, B. W.; Wild, D. A.; Koutsantonis, G.
A.; Stewart, S. G. Acta Crystallogr., Sect. C: Struct. Chem. 2015, 71, 188.
(b)Kampmann, S. S.;Man, N. Y. T.;McKinley, A. J.;Koutsantonis, G. A.;
Stewart, S. G. Aust. J. Chem. 2015, 68, 1842. (c) Tolman, C. A.; Seidel, W.
C.;Druliner, J. D.;Domaille, P. J. Organometallics 1984,3, 33. (d)Arai, S.;
Amako, Y.; Yang, X.; Nishida, A. Angew. Chem., Int. Ed. 2013, 52, 8147.
(e) Baker, M. J.; Harrison, K. N.; Orpen, A. G.; Pringle, P. G.; Shaw, G. J.
Chem. Soc., Chem. Commun. 1991, 803. (f) Wilting, J.; Janssen, M.;
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