Skeleton Decoration of NHCs by Amino Groups and its Sequential Booster Effect on the Palladium-Catalyzed Buchwald–Hartwig Amination†
Yin Zhang
CNRS, LCC (Laboratoire de Chimie de Coordination), 205 route de Narbonne, BP44099, 31077 Toulouse Cedex 4 (France) http://www.lcc-toulouse.fr/lcc/spip.php?article24
Université de Toulouse, UPS, INPT, 31077 Toulouse (France)
Search for more papers by this authorCorresponding Author
Dr. Vincent César
CNRS, LCC (Laboratoire de Chimie de Coordination), 205 route de Narbonne, BP44099, 31077 Toulouse Cedex 4 (France) http://www.lcc-toulouse.fr/lcc/spip.php?article24
Université de Toulouse, UPS, INPT, 31077 Toulouse (France)
CNRS, LCC (Laboratoire de Chimie de Coordination), 205 route de Narbonne, BP44099, 31077 Toulouse Cedex 4 (France) http://www.lcc-toulouse.fr/lcc/spip.php?article24Search for more papers by this authorGolo Storch
CNRS, LCC (Laboratoire de Chimie de Coordination), 205 route de Narbonne, BP44099, 31077 Toulouse Cedex 4 (France) http://www.lcc-toulouse.fr/lcc/spip.php?article24
Université de Toulouse, UPS, INPT, 31077 Toulouse (France)
Search for more papers by this authorDr. Noël Lugan
CNRS, LCC (Laboratoire de Chimie de Coordination), 205 route de Narbonne, BP44099, 31077 Toulouse Cedex 4 (France) http://www.lcc-toulouse.fr/lcc/spip.php?article24
Université de Toulouse, UPS, INPT, 31077 Toulouse (France)
Search for more papers by this authorCorresponding Author
Dr. Guy Lavigne
CNRS, LCC (Laboratoire de Chimie de Coordination), 205 route de Narbonne, BP44099, 31077 Toulouse Cedex 4 (France) http://www.lcc-toulouse.fr/lcc/spip.php?article24
Université de Toulouse, UPS, INPT, 31077 Toulouse (France)
CNRS, LCC (Laboratoire de Chimie de Coordination), 205 route de Narbonne, BP44099, 31077 Toulouse Cedex 4 (France) http://www.lcc-toulouse.fr/lcc/spip.php?article24Search for more papers by this authorYin Zhang
CNRS, LCC (Laboratoire de Chimie de Coordination), 205 route de Narbonne, BP44099, 31077 Toulouse Cedex 4 (France) http://www.lcc-toulouse.fr/lcc/spip.php?article24
Université de Toulouse, UPS, INPT, 31077 Toulouse (France)
Search for more papers by this authorCorresponding Author
Dr. Vincent César
CNRS, LCC (Laboratoire de Chimie de Coordination), 205 route de Narbonne, BP44099, 31077 Toulouse Cedex 4 (France) http://www.lcc-toulouse.fr/lcc/spip.php?article24
Université de Toulouse, UPS, INPT, 31077 Toulouse (France)
CNRS, LCC (Laboratoire de Chimie de Coordination), 205 route de Narbonne, BP44099, 31077 Toulouse Cedex 4 (France) http://www.lcc-toulouse.fr/lcc/spip.php?article24Search for more papers by this authorGolo Storch
CNRS, LCC (Laboratoire de Chimie de Coordination), 205 route de Narbonne, BP44099, 31077 Toulouse Cedex 4 (France) http://www.lcc-toulouse.fr/lcc/spip.php?article24
Université de Toulouse, UPS, INPT, 31077 Toulouse (France)
Search for more papers by this authorDr. Noël Lugan
CNRS, LCC (Laboratoire de Chimie de Coordination), 205 route de Narbonne, BP44099, 31077 Toulouse Cedex 4 (France) http://www.lcc-toulouse.fr/lcc/spip.php?article24
Université de Toulouse, UPS, INPT, 31077 Toulouse (France)
Search for more papers by this authorCorresponding Author
Dr. Guy Lavigne
CNRS, LCC (Laboratoire de Chimie de Coordination), 205 route de Narbonne, BP44099, 31077 Toulouse Cedex 4 (France) http://www.lcc-toulouse.fr/lcc/spip.php?article24
Université de Toulouse, UPS, INPT, 31077 Toulouse (France)
CNRS, LCC (Laboratoire de Chimie de Coordination), 205 route de Narbonne, BP44099, 31077 Toulouse Cedex 4 (France) http://www.lcc-toulouse.fr/lcc/spip.php?article24Search for more papers by this authorWe thank the CNRS for financial support and the Chinese Scholarship Council (CSC) for a PhD grant to Y.Z. NHCs=N-Heterocyclic Carbenes.
Graphical Abstract
Boosting the PEPPSI: A sequential enhancement of the activity of the PEPPSI NHC-based palladium pre-catalyst in the Buchwald–Hartwig amination was obtained by a rational modification of its standard N-heterocyclic carbene (IMes or IPr), consisting of a “simple” incorporation of one, and then two, dimethylamino groups as substituents. These results highlight the valuable benefits of NHC-skeleton decoration in C–N cross-coupling.
Abstract
A challenging synthetic modification of PEPPSI-type palladium pre-catalysts consisting of a stepwise incorporation of one and two amino groups onto the NHC skeleton was seen to exert a sequential enhancement of the electronic donor properties. This appears to be positively correlated with the catalytic performances of the corresponding complexes in the Buchwald–Hartwig amination. This is illustrated, for example, by the quantitative amination of 4-chloroanisole by morpholine within 2 h at 25 °C with a 2 mol % catalyst/substrate ratio or by a significant reduction of catalytic loading (down to 0.005 mol %) for the coupling of aryl chlorides with anilines (max TON: 19 600).
Supporting Information
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