New Tri(1-adamantyl)phophine Ligand for Improved Transition Metal Catalysis

Web Published:
1/27/2016
Description:

 

Princeton Docket # 16-3202-1

 

Researchers in the Department of Chemistry at Princeton University have developed a new ligand for cross-coupling reactions to use in conjunction with transition metal catalysts.

Modern palladium catalysts for cross-coupling chemistry rely predominantly on phosphine or N-heterocyclic carbene ligands to enhance their reactivity towards industrially relevant substrates. However, many established ligands can suffer from undesired side reactions during a catalytic reaction, which affects the activity, selectivity, or stability of the metal catalyst. Tri(1-adamantyl)phosphine is markedly resistant to common decomposition side reactions such as cyclometallation and P-C bond scission. Additionally, the ligand is air and moisture stable as a crystalline solid, which eliminates the need for special handling protocols common for other alkylphosphine ligands that are oxygen sensitive or even pyrophoric. The chemical stability of the new ligand also translates to a more stable metal complex during catalysis. Kinetic experiments have demonstrated that palladium catalysts with tri(1-adamantyl)phosphine are innately very reactive, which enables high turnover numbers and frequencies during cross-coupling reactions with even historically challenging substrates.

Catalytic performances of catalysts with tri(1-adamantyl)phosphine have been demonstrated as comparable or superior to existing catalysts with other ligands in important cross-coupling reactions such as Suzuki-Miyaura coupling, Kumada coupling, Buchwald-Hartwig amination, carbonyl α-arylation, and the Mizoroki-Heck Reaction. In particular, the reactivity of catalysts ligated by this new phosphine is markedly higher towards aryl chlorides than many existing state-of-the-art catalysts.

 

Applications                     

 

•       Cross-coupling reactions

•       Use with commercially attractive aryl chloride substrates for pharmaceutical  and  argrochemical synthesis

•       Optical and electronic materials synthesis

 

Advantages

•       Stable

•       High turnover frequency

•       Decomposition resistant

•       Low catalyst loading

•       High space-time yields

•       Cost effective

 

The Faculty Inventor

 

Brad Carrow is an Assistant Professor of Chemistry at Princeton University. His research interests revolve around transition metal catalysis in the context of polymer synthesis, sustainable organic synthesis, and inert bond activation. Previously he was a postdoctoral fellow and then an assistant professor at the University of Tokyo and completed his Ph.D. studies at the University of Illinois at Urbana − Champaign.

 

Intellectual Property & Development Status

 

Patent protection is pending. Princeton is seeking to identify appropriate partners for the further development and commercialization of this technology.

 

Contact:

 

Laurie Tzodikov

Princeton University Office of Technology Licensing 

• (609) 258-7256• tzodikov@princeton.edu

Xin (Shane) Peng

Princeton University Office of Technology Licensing

• (609) 258-5579• xinp@princeton.edu

 

Patent Information:
Category(s):
Chemistry
For Information, Contact:
Cortney Cavanaugh
New Ventures and licensing associate
Princeton University
ccavanaugh@princeton.edu
Inventors:
Bradley Carrow
Liye Chen
Keywords: