Bitransition Metal Catalyzed C-H Acitvation

• Applicant: Professor Dr. A. Stephen K. Hashmi
• Subject Area: Organic Molecular Chemistry - Synthesis and Characterisation
• Term: from 2008 to 2013
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 54801797

• Final Report Year: 2014

Final Report Abstract

The project provided fundamental insights into the combination of gold catalysis and palladium catalysis. One important point was to avoid ligand exchange between the two metal centres, another point was the efficient transmetalation from gold to palladium in the presence of halide ions, a process going along with a high functional group tolerance. This need of halide ions prevents reactions catalytic in both gold and palladium, for reactions avoiding halides by using activated allylic fragments it could be shown that in most cases the reactions published for a gold/palladium mixture needs only one of the two metals. All of this was supported by a computational study of the transmetalation step and the overall catalytic cycle. Finally, a step-wise one-pot procedure for the combination of gold and palladium catalysis could be achieved.

Publications

• "Gold und Palladium treffen sich bei Kreuzkupplungen", Angew. Chem. 2009, 121, 8392-8395. "Gold meets Palladium for Cross-Coupling", Angew. Chem. Int. Ed. 2009, 48, 8243-8246
  A. Stephen K. Hashmi, Christian Lothschütz, René Döpp, Matthias Rudolph, Tanuja Dondeti Ramamurthi, Frank Rominger
  
• "Scope and Limitations of Palladium-Catalyzed Cross-Coupling Reactions with Organogold Compounds", Adv. Synth. Catal. 2010, 352, 1307-1314
  A. Stephen K. Hashmi, René Döpp, Christian Lothschütz, Matthias Rudolph, Dominic Riedel, Frank Rominger
  
• "Combining Gold and Palladium Catalysis: One-Pot Access to Pentasubstituted Arenes from Furan–Yne and En–Diyne Substrates", Chem. Eur. J. 2012, 18, 8113-8119
  A. Stephen K. Hashmi, Mohammad Ghanbari, Matthias Rudolph, Frank Rominger
  
• "On Homogeneous Gold/Palladium Catalytic Systems", Adv. Synth. Catal. 2012, 354, 133-147
  A. Stephen K. Hashmi, Christian Lothschütz, René Döpp, Martin Ackermann, Janosc De Buck, Matthias Rudolph, Christian Scholz, Frank Rominger
  (See online at https://doi.org/10.1002/adsc.201000044)
• "A Theoretical DFT-based and an Experimental Study of the Transmetalation Step in Au/Pd Mediated Cross-Coupling Reactions", Chem. Eur. J. 2013, 19, 15290-15303
  Max M. Hansmann, Markus Pernpointner, Rene Döpp, A. Stephen K. Hashmi
  (See online at https://doi.org/10.1002/chem.201301840)