title: 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.
abstract: 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.
authors: Organic Chemistry, Department of Chemistry, Lund University, P.O. Box 124, SE-221 00, Lund, Sweden.
authors: Stefán
authors: S
authors: Jónsson
authors: Fabrice G J
authors: FG
authors: Odille
authors: Per-Ola
authors: PO
authors: Norrby
authors: Kenneth
authors: K
authors: Wärnmark