globucat · 2019-04-05 · dramatically reduce pd leaching in suzuki coupling . efficient and...
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+O O
O
O
Sc(OTf)3, 10 mol%
Ligand 0.11to 10 mol%
OO
CH3CN,reflux, 16h
100806040200
Yie l
d %
TPy TPy-G1 TPy-G2 TPy-G3 TPy-G4
4755 59 66
80
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60
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0
Yie l
d %
Run number1 2 3 4 5 6 7 8 9 10
95 90 87 85 86 85 86 8684 85
6068
74809195
PN
PN
PN
on CoNPon Co NP
GLOBUCAT Towards sustainable chemical processes: immobilization of molecular organo- and metal catalysts and their applications for fine chemical synthesis.
EFC 2008
Jean-Pierre MAJORAL,a Anne-Marie CAMINADE,a Armelle OUALI,a Michel KELLER,a Arnaud PERRIER,a Laurie TRAVERS,a Oliver REISERb a Laboratoire de Chimie de Coordination du CNRS, 205 route de Narbonne, 31077 Toulouse Cedex 4, France. b Institut fur Organische Chemie, Universität Regensburg, Universitätsstr. 31, 93053 Regensburg, Germany.
Catalytic entities immobilized as terminal groups of dendrimers and dendrons
Efficient and recyclable dendritic catalysts to dramatically reduce Pd leaching in Suzuki coupling
Efficient and recyclable pyrene-dendron catalyst non covalently grafted onto magnetic nanoparticles
CONTACT : Anne-Marie CAMINADE, Laboratoire de Chimie de Coordination, UPR CNRS 8241, 205 route de Narbonne, 31077 Toulouse Cedex 4, France [email protected]
Coupling of 4-bromoacetophenone and PhB(OH)2 in water/THFa
Ligand mol % Yield b Pd leaching PPh3 0.5 74 2227 ppm
Mono-thia 0.5 95 1400 ppm PPh3-G1 0.04 78 173 ppm Thia-G1 0.04 80 < 0.55 ppm PPh3-G3 0.01 75 Thia-G3 0.01 80
a Pd(OAc)2 (0.005 mmol), phosphine moieties (0.5 mol%), PhBr (1 mmol), PhB(OH)2 (1.1 mmol), Na2CO3 (3 mmol), H2O/THF (7 mL). b GC yields determined with 1,3-dimethoxybenzene as standard.
Ligand Yield run 1
Yield run 2
Yield run 3
Yield run 4
Yield run 5
PPh3-G1 95 80 50 - - Thia-G1 94 95 96 94 95
met the requirements of EU pharmaceutical industry Recycling and reuse
* An efficient and recyclable dendritic catalyst able to dramatically reduce palladium leaching in Suzuki couplings. Keller M., Hameau A., Spataro G., Ladeira S., Caminade A.M., Majoral J.P., Ouali A. Green Chemistry, in press, DOI: 10.1039/C2GC35832H
Positive dendritic effect in Friedel-Crafts acylation with terpyridine-Rare earths complexes
Organocatalyzed Michael additions (no metal, no base)
LCC
10 times reused: same efficiency
graphene layerscobalt nanoparticle
5N3P3OPh2P O
HN
O
Co
Magnetic recovery of the catalyst
Positive dendritic effect
P P
PP
P
Dendrimer Dendron: catalytic entity
P
N
N NN
NN
Positive dendritic effects on the efficiency and the recovery
N NMe
P
S
ON N
Me
P
S
ON N
Me
P
S
6
2 2
N3P3 O2
TPy-G3
O N
N
N
N NMe
P
S
ON N
Me
P
S
ON N
Me
P
S
62 2
N3P3 O
2O
NH
O
SN
N
P
N NMe
P
S
ON N
Me
P
S
ON N
Me
P
S
6
2 2N3P3 O
2PO
Thia-G3
PPh3-G3
N NMe
P
S
ON N
Me
P
S
O
6
2 2N3P3 O
N
NNO
NH O
SiMe3
G2
BrMeOC (HO)2B+ MeOC
Pd(OAc)2 (0.5 mol%)Ligand (0.01 to 0.5 mol%)
Na2CO3, H2O, THF, 25°C, 14h
Br (HO)2B+Na2CO3 (3 eq.)
THF/H2O (25), 60°C, 14h
Pd(OAc)2 0.5 mol% Ligand onto NPs
0.5 to 0.01 mol%
+
O
H
Dendritic catalyst
0.21-10 mol%CH2Cl2,0°C, 14h
Ph
NO2
O
H
PhNO2
ee 93%
100
80
60
40
20
0
Yie l
d %
Run number1 2 3 4 5 6 7
100 100 98 98
8072
5240
70100
80
64
33
53
G2
G3
G1
mono-mer