The research program in my group is aimed at the development of novel catalysis concepts.^1-5 In this talk I will shortly present our work on the Mn-catalyzed activation of H−P bonds2 allowing catalytic synthesis of chiral ligands3 and synthesis of enantiopure stereochemically defined Z-alkenes bearing a tertiary allylic stereocenter and a reactive functional group.⁴

In the final and the main part of the talk, I will move away from conventional catalytic concepts^5,6 to our recent interest in developing catalytic systems within complex reaction networks. Our group has designed a catalytically active small organic molecule oscillator.⁶ The system produces sustained oscillations in an open flow system and its product catalyzes a chemical reaction. This general design principle opens up exciting new pathways for coupling oscillatory kinetics to a wide range of reactions that require catalytic rate enhancement using the principles of catalysis and achieving unique chemoselectivities not possible by conventional catalysis. A catalytic oscillator can be considered a catalyst that switches between an ‘on’ and ‘off’ state in a periodic autonomous fashion without a need for external stimuli. The introduction of oscillating catalysis concept into organic synthesis opens the door to new methodologies beyond the current step-by-step organic synthesis paradigm.

References

1) Catalytic asymmetric addition of Grignard reagents to alkenyl-substituted aromatic N-heterocycles R. P. Jumde, F. Lanza, M. J. Veenstra, S. R. Harutyunyan, Science, 2016, 352, 433.

2) Manganese(I)-Catalyzed H–P Bond Activation via Metal–Ligand Cooperation J. M. Pérez, R. Postolache, M. Castiñeira Reis, E. G. Sinnema, D. Vargová, F. de Vries, E. Otten, L. Ge, S. R. Harutyunyan, JACS, 2021, 143, 48, 20071.

3) Manganese (I)-Catalyzed Access to 1,2-Bisphosphine Ligands L. Ge, S. R Harutyunyan, Chem. Sci., 2022, 13, 1307.

4) Enantio- and Z-selective synthesis of functionalized alkenes bearing tertiary allylic stereogenic center L. Ge, E. G. Sinnema, J. M. Pérez, R. Postolache, M. Castiñeira Reis, S. R. Harutyunyan, Science Advances, 2023, accepted.

5) Organocatalyst based cross-catalytic system M. J. Veenstra, S. R. Harutyunyan, Chem. Commun., 2022, 58, 13895.

6) A catalytically active small organic molecule oscillator M. ter Harmsel, O. Maguire, S. Runikhina, A. Wong, W. Huck, S. R. Harutyunyan, 2023, under revisions.