Phosphines and Catalysis

Phosphines are amongst the most important ligands in homogeneous catalysis and applied in various transformations including industrial processes. Electron-rich phosphines represent a particularly valuable subclass, which enables many difficult reactions such as in gold catalysis or palladium-catalyzed coupling reactions. 

To overcome limitations in the traditional design of phosphine ligands, we have developed the platform of ylide-substituted phosphines (YPhos). They surpass the donor ability of simple alkyl phosphines and therefore enabled the generation of highly active catalysts which have set new standards in various transformations. The flexibility of their molecular design furthermore allows the tailoring of the ligand properties to the requirements of different reactions. Thus, we were able to develop effective catalyst for various palladium-catalyzed cross-coupling reactions, gold-catalyzed hydroaminations and cyclizations as well as platinum catalyzed hydrosilylations. Further research endeavors focus on the design of anionic phosphines for the generation of zwitterionic catalysts. 

Selected publications:

J. F. Goebel, J. Löffler, Z. Zeng, J. Handelmann, A. Hermann, I. Rodstein, T. Gensch, V. H. Gessner,* L. J. Gooßen*
Computer-Driven Development of Ylide functionalized Phosphines for Palladium-Catalyzed Hiyama Couplings
Angew. Chem. Int. Ed. 2023, 62, e202216160 (https://doi.org/10.1002/anie.202216160).

J.-A. Zur+, M. Schmidt+, K.-S. Feichtner, P. Duari, J. Löffler, T. Scherpf, V. H. Gessner*
From Stable PH-Ylides to α-Carbanionic Phosphines as Ligands for Zwitterionic Catalysts

Angew. Chem. Int. Ed. 2022, e202203950. https://doi.org/10.1002/anie.202203950 
 

S. Lapointe, A. Sarbajna, V. H. Gessner*
Ylide-Substituted Phosphines: A Platform of Strong Donor Ligands for Gold Catalysis and Palladium-Catalyzed Coupling Reactions 

Acc. Chem. Res. 2022, 55, 770-782. (https://doi.org/10.1021/acs.accounts.1c00797) 

H. Darmandeh, J. Löffler, N. V. Tzouras, B. Dereli, T. Scherpf, K.-S. Feichtner, S. V. Broeck, K. Van Hecke, M. Saab, C. S. J. Cazin, L. Cavallo, S. P. Nolan*, V. H. Gessner* 

Au···H-C Hydrogen Bonds as Design Principle in Gold(I) Catalysis 

Angew. Chem. Int. Ed. 2021, 60, 21014-21024. https://doi.org/10.1002/anie.202108581

T. Scherpf, H. Steinert, A. Großjohann, K. Dilchert, J. Tappen, R. Rodstein, V. H. Gessner*
Efficient Pd-Catalyzed Direct Coupling of Aryl Chlorides with Alkyllithium Reagents
Angew. Chem. Int. Ed. 2020, 59, 20596-20603. DOI: 10.1002/anie.202008866