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Dalton Transactions
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Journal Name
ARTICLE
Notes and references
DOI: 10.1039/C8DT01852A
1
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2
a 1 mol % Pd. b 2.5 mol % Pd
For a method to be useful, it must be scalable. To test the
scalability, 4.0 mmol of 2l was utilized in the cross-coupling with 6c
to provide 95% yield of 7cl (1.0 g) (Scheme 1).
Scheme 1. Gram scale synthesis of N-(4-ethoxyphenyl)naphthalen-1-amine
with 500 ppm palladium loading
Conclusions
A reactivity comparison of the Pd(NIXANTPHOS)-based catalyst for
coupling of sterically hindered secondary anilines was made with the
analogous Xantphos system and various mono- and bidentate
phosphine ligands using unactivated aryl chloride substrates. It was
found that the NIXANTPHOS-based catalyst outperformed the parent
ligand Xantphos. The Pd(NIXANTPHOS) system exhibited excellent
reactivity in N-arylations of primary aniline derivatives with as low
as 0.05 mol % palladium loading. The data presented herein
indicate that when screening and optimizing the palladium
catalyzed Buchwald-Hartwig coupling reaction of amines with aryl
chlorides, NIXANTPHOS is likely a better choice than the commonly
used Xantphos.
3
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Conflicts of interest
There are no conflicts to declare.
Acknowledgements
The authors acknowledge the National Science Foundation
(CHE-1464744 to P.J.W.) and Nanjing Tech University
(3980001601 and 39837112) and Natural Science Foundation
of Jiangsu Province, China (BK20170965) for financial support.
We also thank the financial support by SICAM Fellowship by
Jiangsu National Synergetic Innovation Center for Advanced
Materials. Dr. Spencer Dreher (Merck) is thanked for helpful
discussions and preliminary experiments.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 5
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