Modulation of the Reactivity, Stability and Substrate- and Enantioselectivity of an Epoxidation Catalyst by Noncovalent Dynamic Attachment of a Receptor Functionality - Aspects on the Mechanism of the Jacobsen-Katsuki Epoxidation Applied to a Supramolecular System
Jónsson, Stefán3; Odille, Fabrice G. J.3; Norrby, Per-Ola1; Wärnmark, Kenneth3
1 Department of Chemistry, Technical University of Denmark2 Lund University3 Lund University
The synthesis of the components of the dynamic supramolecular hydrogen-bonded catalytic system 2 + 3 is described. The catalytic performance and substrate- and enantioselectivity of Mn(salen) catalyst 2 were investigated in the presence and absence of the Zn(porphyrin) receptor unit 3. The effects of pyridine and pyridine N-oxide donor ligands were also studied. Some aspects on the mechanism of the Jacobsen–Katsuki epoxidation, based on literature observations, are introduced as a means to analyse the behaviour of 2 and its modulation by the formation of macrocycle 1 with 3. A complete association model of the metal-free system 4 + 5 refutes the earlier assumption that macrocycle 1 is the predominant form of catalyst 2 under the standard epoxidation reaction conditions with 2 + 3. Evidence are provided that receptor-binding substrates and nonbinding substrates, respectively, are epoxidised by two different catalytic species, or two distinct distributions of species in competitive epoxidations using catalytic system 2 + 3. The two species are assigned to the endo and exo faces of the Mn(salen) catalyst in macrocycle 1, and to equivalently folded oligomeric structures with monomers 2 and 3 in adjacent positions.
Organic and Biomolecular Chemistry, 2006, Vol 4, Issue 10, p. 1927-1948