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Radical Cyclisation of α-Halo Aluminium Acetals: A Mechanistic Study

Abstract : α‐Bromo aluminium acetals are suitable substrates for Ueno–Stork‐like radical cyclisations affording γ‐lactols and acid‐sensitive methylene‐γ‐lactols in high yields. The mechanistic study herein sets the scope and limitation of this reaction. The influence of the halide (or chalcogenide) atom X (X=Cl, Br, I, SPh, SePh) in the precursors α‐haloesters, as well as influence of the solvent and temperature was studied. The structure of the aluminium acetal intermediates resulting from the reduction of the corresponding α‐haloesters has been investigated by low‐temperature 13C‐INEPT diffusion‐ordered NMR spectroscopy (DOSY) experiments and quantum calculations, providing new insights into the structures of these thermally labile intermediates. Oxygen‐bridged dimeric structures with a planar Al2O2 ring are proposed for the least hindered aluminium acetals, while monomeric structures seem to prevail for the most hindered species. A comparison against the radical cyclisation of aluminium acetals derived from allyl and propargyl alcohols with the parent Ueno–Stork has been made at the BHandHLYP/6‐311++G(d,p) level of theory, highlighting mechanistic similarities and differences.
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https://hal-normandie-univ.archives-ouvertes.fr/hal-02046185
Contributor : Madeleine Roux-Merlin <>
Submitted on : Friday, February 22, 2019 - 3:36:11 PM
Last modification on : Thursday, July 2, 2020 - 3:29:46 AM

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R. Bénéteau, A. Boussonnière, J.-C. Rouaud, J. Lebreton, J. Graton, et al.. Radical Cyclisation of α-Halo Aluminium Acetals: A Mechanistic Study. Chemistry - A European Journal, Wiley-VCH Verlag, 2016, 22 (14), pp.4809-4824. ⟨10.1002/chem.201504780⟩. ⟨hal-02046185⟩

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