An endohedrally functionalized self‐assembled Fe4L6cage complex can catalyze oxa‐Pictet—Spengler cyclizations of tryptophols and various aldehyde derivatives, showing strong rate accelerations and size‐selectivity. Selective molecular recognition of substrates controls the reactivity, and the cage is capable of binding and activating multiple different species along the multistep reaction pathway. The combination of a functionalized active site, size‐selective reactivity, and multistep activation, all from a single host molecule, illustrates the biomimetic nature of the catalysis.
Selective, cofactor-mediated catalytic oxidation of alkanethiols in a self-assembled cage host
A spacious Fe( ii )-iminopyridine self-assembled cage complex can catalyze the oxidative dimerization of alkanethiols, with air as stoichiometric oxidant. The reaction is aided by selective molecular recognition of the reactants, and the active catalyst is derived from the Fe( ii ) centers that provide the structural vertices of the host. The host is even capable of size-selective oxidation and can discriminate between alkanethiols of identical reactivity, based solely on size.
- Publication Date:
- NSF-PAR ID:
- 10284044
- Journal Name:
- Chemical Communications
- Volume:
- 56
- Issue:
- 91
- Page Range or eLocation-ID:
- 14263 to 14266
- ISSN:
- 1359-7345
- Sponsoring Org:
- National Science Foundation
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Abstract -
Abstract An endohedrally functionalized self‐assembled Fe4L6cage complex can catalyze oxa‐Pictet—Spengler cyclizations of tryptophols and various aldehyde derivatives, showing strong rate accelerations and size‐selectivity. Selective molecular recognition of substrates controls the reactivity, and the cage is capable of binding and activating multiple different species along the multistep reaction pathway. The combination of a functionalized active site, size‐selective reactivity, and multistep activation, all from a single host molecule, illustrates the biomimetic nature of the catalysis.
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