+ O O O O S c ( OTf ) 3, 10 mo l % Li g an d 0 . 11 t o 10 mo l % O O CH 3 CN , re fl ux , 16h 100 80 60 40 20 0 Yi e l d % TP y TP y - G 1 TP y - G 2 TP y - G 3 TP y - G 4 47 55 59 66 80 100 80 60 40 20 0 Yi e l d % R un num b er 1 2 3 4 5 6 7 8 9 10 95 90 87 85 86 85 86 86 84 85 60 68 74 80 91 95 P N P N P N on C o NP on C o 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 REISER b 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/THF a Ligand mol % Yield b Pd leaching PPh 3 0.5 74 2227 ppm Mono-thia 0.5 95 1400 ppm PPh 3 -G 1 0.04 78 173 ppm Thia-G 1 0.04 80 < 0.55 ppm PPh 3 -G 3 0.01 75 Thia-G 3 0.01 80 a Pd(OAc) 2 (0.005 mmol), phosphine moieties (0.5 mol%), PhBr (1 mmol), PhB(OH) 2 (1.1 mmol), Na 2 CO 3 (3 mmol), H 2 O/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 PPh 3 -G 1 95 80 50 - - Thia-G 1 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 g ra p h ene l a y ers co b a lt nano p ar ti c l e 5 N 3 P 3 O Ph 2 P O H N O C o Magnetic recovery of the catalyst Positive dendritic effect P P P P P D en d r i mer D en d ron : ca t a l y ti c en tit y P N N N N N N Positive dendritic effects on the efficiency and the recovery N N M e P S O N N M e P S O N N M e P S 6 2 2 N 3 P 3 O 2 TP y - G 3 O N N N N N M e P S O N N M e P S O N N M e P S 6 2 2 N 3 P 3 O 2 O NH O S N N P N N M e P S O N N M e P S O N N M e P S 6 2 2 N 3 P 3 O 2 P O Thi a- G 3 PPh 3 - G 3 N N M e P S O N N M e P S O 6 2 2 N 3 P 3 O N N N O N H O SiM e 3 G 2 B r M e OC ( HO )2 B + M e OC Pd ( OA c )2 ( 0 . 5 mo l % ) Li g an d ( 0 . 01 t o 0 . 5 mo l % ) N a 2 CO 3, H 2 O , THF , 25°C , 14h B r ( HO ) 2 B + N a 2 CO 3 ( 3 e q . ) THF/H 2 O ( 25 ) , 60°C , 14h Pd ( OA c ) 2 0 . 5 mo l % Li g an d on t o NP s 0 . 5 t o 0 . 01 mo l % + O H D en d r iti c ca t a l y s t 0 . 21 - 10 mo l % CH 2 Cl 2 , 0°C , 14h Ph NO 2 O H Ph NO 2 ee 93% 100 80 60 40 20 0 Yi e l d % R un num b er 1 2 3 4 5 6 7 100 100 98 98 80 72 52 40 70 100 80 64 33 53 G 2 G 3 G 1 mono -mer