Olefin Metathesis in Confinement: Towards Covalent Organic Framework Scaffolds for Increased Macrocyclization Selectivity

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Abstract

Covalent organic frameworks (COFs) offer vast structural and chemical diversity enabling a wide and growing range of applications. While COFs are well-established as heterogeneous catalysts, so far, their high and ordered porosity has scarcely been utilized to its full potential when it comes to spatially confined reactions in COF pores to alter the outcome of reactions. Here, we present a highly porous and crystalline, large-pore COF as catalytic support in α,ω-diene ring-closing metathesis reactions, leading to increased macrocyclization selectivity. COF pore-wall modification by immobilization of a Grubbs-Hoveyda-type catalyst via a mild silylation reaction provides a molecularly precise heterogeneous olefin metathesis catalyst. An increased macro(mono)cyclization (MMC) selectivity over oligomerization (O) for the heterogeneous COF-catalyst (MMC:O=1.35) of up to 51 % compared to the homogeneous catalyst (MMC:O=0.90) was observed along with a substrate-size dependency in selectivity, pointing to diffusion limitations induced by the pore confinement.

Details

Original languageEnglish
Article numbere202104108
JournalChemistry - A European Journal
Volume28
Issue number8
Early online date9 Dec 2021
Publication statusPublished - 7 Feb 2022
Peer-reviewedYes

External IDs

PubMed 34882848
ORCID /0000-0001-8423-6173/work/142250828

Keywords

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ASJC Scopus subject areas

Keywords

  • catalysis, confinement, covalent organic frameworks, metathesis, reticular chemistry, Metal-Organic Frameworks, Alkenes, Cyclization, Catalysis, Porosity