Green Chemistry
Paper
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Fig. 3 Recycling of TPGS-750-M. Yields were determined by 1H NMR
experiments using caffeine as an internal standard.
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Conclusions
We developed a general and high yielding method for accom-
plishing Buchwald–Hartwig coupling reactions of aryl or
heteroaryl halides under green conditions. With this versatile
catalyst system ([(cinnamyl]PdCl]2/t-BuXPhos), the cross-coup-
ling reaction was extended to several aryl and amine coupling
partners. The reaction protocols are extremely flexible and
were successfully applied to aliphatic, cyclic, acyclic, and aro-
matic amines and also to benzamide derivatives.
This is in striking contrast to the previously reported cata-
lyst system (Takasago’s cBRIDP ligand in combination with
[(allyl)PdCl]2) that shows dramatically lower activities for Buch-
wald–Hartwig reactions with aliphatic primary amines or benz-
amide derivatives. All the reactions were carried out in water at
a low temperature (50 °C), and the amides were cleanly formed
and could be isolated in good to excellent yields. Because of
the mild reaction conditions, this reaction can tolerate a wide
variety of functional groups like esters and halides and no
racemization was observed in the presence of a chiral centre.
Moreover the system allows the recycling of the aqueous micel-
lar media increasing the greenness of the method. Finally, we
hope that our new green catalytic system will allow medicinal
chemist and pharmaceutical companies to synthesize new
drugs in environment-friendly conditions.
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Acknowledgements
Financial support provided by the University of Strasbourg
(UdS), the national Center of Scientific Research (CNRS) and
the Communauté Urbaine de Strasbourg (Pharmadol) is
warmly acknowledgements with thanks.
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