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Thioboration of α,β-Unsaturated Ketones and Aldehydes toward the Synthesis of β-Sulfido Carbonyl Compounds

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Dept. Química Física i Inorgànica, Universitat Rovira i Virgili, C/Marcel·lí Domingo s/n, 43007 Tarragona, Spain
Institute of Chemical Research of Catalonia (ICIQ), Avda. Països Catalans, 16, 43007 Tarragona, Spain
§ Department of Chemistry and Biochemistry, Mount Allison University, Sackville, New Brunswick E4L 1G8, Canada
Department of Chemistry, University of New Brunswick, Fredericton, New Brunswick E3B 5A3, Canada
Cite this: J. Org. Chem. 2015, 80, 4, 2148–2154
Publication Date (Web):January 22, 2015
https://doi.org/10.1021/jo5026354
Copyright © 2015 American Chemical Society

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    Abstract

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    Herein a direct β-sulfido carbonyl compound synthesis by the easy activation of RS−Bpin reagents with α,β-unsaturated ketones and aldehydes is reported. This convenient methodology can be performed at room temperature with no other additives. The key point of this reactivity is based on the Lewis acidic properties of the boryl unit of the RS−Bpin reagent interacting with the C═O oxygen. Consequently, the SR unit becomes more nucleophilic and promotes the 1,4- versus the 1,2-addition, as a function of the involved substrate. The thioborated products can be further transformed into β-sulfido carbonyl compounds by addition of MeOH.

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    X-ray diffraction study for 12b, general method for β-sulfonylation of α,β-unsaturated ketones and aldehyde, 1H and 13C NMR of products, computational details, functional comparison, computed nucleophilicity indexes (N), structures and electronic energies of the involved species, and kinetic studies. This material is available free of charge via the Internet at http://pubs.acs.org.

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