Affiliation:
1. Organisch Chemisches Institut Westfälische Wilhelms-Universität Münster Corrensstraße 36 48149 Münster Germany
2. Department of Chemistry Johannes Gutenberg University Mainz Duesbergweg 10–14 55128 Mainz Germany
Abstract
AbstractAmide groups are pervasive across the chemical space continuum, where their structural and pharmacological importance, juxtaposed with the hydrolytic vulnerabilities, continues to fuel bioisostere development. Alkenyl fluorides have a venerable history as effective mimics (Ψ[CF=CH]) owing to the planarity of the motif and intrinsic polarity of the C(sp2)−F bond. However, emulating the s‐cis to the s‐trans isomerisation of a peptide bond with fluoro‐alkene surrogates remains challenging, and current synthetic solutions only enable access to a single configuration. Through the design of an ambiphilic linchpin based on a fluorinated β‐borylacrylate, it has been possible to leverage energy transfer catalysis to affect this unprecedented isomerisation process: this provides geometrically‐programmable building blocks that can be functionalised at either terminus. Irradiation at λmax=402 nm with inexpensive thioxanthone as a photocatalyst enables rapid, effective isomerisation of tri‐ and tetra‐substituted species (up to E/Z 98 : 2 in 1 h), providing a stereodivergent platform for small molecule amide and polyene isostere discovery. Application of the methodology in target synthesis and initial laser spectroscopic studies are disclosed together with crystallographic analyses of representative products.
Funder
Westfälische Wilhelms-Universität Münster
Alexander von Humboldt-Stiftung
Horizon 2020 Framework Programme
Johannes Gutenberg-Universität Mainz
Deutsche Bundesstiftung Umwelt
Subject
General Chemistry,Catalysis
Cited by
9 articles.
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