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Supramolecular Control of Catalyst Selectivity in the
Hydroformylation
Paweł Dydio,
Wojciech I. Dzik, M. Lutz, Bas de Bruin, Joost N.H. Reek*
Van’t Hoff Institute for Molecular Sciences University of Amsterdam,
Science Park 904, 1098 XH, Amsterdam (The Netherlands)
e-mail: p.f.dydio@uva.nl, j.n.h.reek@uva.nl
A new approach in homogeneous catalysis involves the pre-organisation of a substrate
by specific recognition, affording unusually high selectivities. 1,2
Here we present DIMPhos (1), a new bidentate phosphorus ligand with an integral anion
3
recognition site. The supramolecular interactions between the binding pocket of the
Rh(1)-catalyst and alkenes containing anionic functionalities provide an excellent
design-concept to achieve remote control of the regioselectivity in hydroformylation.
DFT calculations show that the substrate anchoring highly restricts movement of the
reactive double bond, and hence favours one reaction pathway. This gives rise to the
observed highly selective hydroformylation of a variety of unsaturated carboxylic and
phosphonic acids. 4
This provides the first example of wide-ranging remote control of
catalyst selectivity by secondary substrate-ligand interactions. In this contribution we
discuss the mechanism and the substrate range of this multifunctional catylitic system.
1
Breuil, P-A.R.; Patureau, F.W.; Reek, J.N.H. Angew. Chem. Int. Ed. 2009, 2162.
2
Smejkal, T.; Breit, B. Angew. Chem. Int. Ed. 2008, 311; Chem. Eur. J. 2010, 2470.
3
Dydio, P.; Zieliński, T.; Jurczak, J. Chem. Commun. 2009, 4560; Org. Lett. 2010, 1076.
4
Dydio, P.; Dzik, W.I; Lutz, M.; de Bruin, B; Reek, J.N.H. Angew.Chem.Int.Ed. 2011, 396.