Organic Chemistry

Wittig olefination “baking powder”: a hexameric halogen-bonded phosphonium salt cage for encapsulation and mechanochemical transformation of small-molecule carbonyl compounds

Authors

Abstract

We report a hexameric supramolecular cage assembled from the components of a Wittig-type phosphonium salt, held together by charge-assisted R-Br· · ·Br-· · ·Br-R halogen bonds. The cage reliably encapsulates small polar molecules, including aldehydes and ketones, to provide host-guest systems in which components are pre-formulated in a near-ideal stoichiometry for a base-activated Wittig olefination in the solid-state. These pre-formulated solids enable a molecular-level “baking powder” approach for solvent-free Wittig reactions, based on a design of solid-state reactivity in which the host for molecular inclusion also acts as a complementary reagent for the chemical transformation of an array of guests. These host-guest solid-state complexes can also act as supramolecular surrogates to their Wittig olefination vinylbromide products, in a Sonogashira-type coupling that enables one-pot mechanochemical conversion of an aldehyde to an enediyne.

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Supplementary material

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Supplementary Information
Details of experiments, selected X-ray crystallography, powder X-ray diffraction, infrared spectroscopy, thermal analysis, mass spectrometry, 1H and 13C NMR spectroscopy data, with corresponding references.