Covalent organic frameworks (COFs) {offer|provide|supply|offer you|present|give} vast structural and chemical diversity enabling a wide and {growing|expanding|developing|increasing} {range|variety} of applications. {While|Whilst|Although|Even though|When|Though} COFs are well-established as homogeneous catalysts, so far, their {high|higher} and ordered porosity has scarcely been utilized to its {full|complete} {potential|possible|prospective} {when it comes to|with regards to|in terms of|in relation to|in regards to|on the subject of} spatially confined reactions in COF pores to alter the outcome of reactions. {Here|Right here}, we present a {highly|extremely|very|hugely} porous and crystalline, large-pore COF as catalytic {support|assistance|help} in diene ring-closing metathesis reactions, {leading|top|major} to {increased|elevated|improved|enhanced} macrocylization selectivity. COF pore-wall modification by immobilization of a Grubbs-Hoveyda-type catalyst {via|by way of|through|by means of} a mild silylation reaction {provides|offers|gives|supplies|delivers} a molecularly precise heterogeneous metathesis catalyst. An {increased|elevated|improved|enhanced} macro(mono)cyclization (MMC) selectivity {over|more than} oligomerization (O) for the heterogeneous COF-catalyst (MMC:O = 1.30) of {up to|as much as} 44% {compared to|in comparison to|in comparison with|when compared with} the homogeneous catalyst (MMC:O = 0.90) was observed {along with|together with|in addition to|as well as|in conjunction with} a substrate-size dependency in selectivity, pointing to diffusion limitations induced by the pore confinement. 2-Chloro-5-iodo-4-pyridinamine Chemscene Formula of 1314538-55-0 PMID:25105126
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