Journal of Organic Chemistry
Journal of Organic Chemistry
5 years ago

Switchable Diastereoselectivity in the Fluoride-Promoted Vinylogous Mukaiyama–Michael Reaction of 2-[(Trimethylsilyl)oxy]furan Catalyzed by Crown Ethers

Switchable Diastereoselectivity in the Fluoride-Promoted Vinylogous Mukaiyama–Michael Reaction of 2-[(Trimethylsilyl)oxy]furan Catalyzed by Crown Ethers
Rosaria Schettini, Irene Izzo, Frédéric Leroux, Chloé Batisse, Luigi Cavallo, Giorgio Della Sala, Francesco De Riccardis, Marina Sicignano, Gilles Hanquet, Yury Minenkov
The fluoride-promoted vinylogous Mukaiyama–Michael reaction of 2-[(trimethylsilyl)oxy]furan with diverse α,β-unsaturated ketones is described. The TBAF-catalyzed VMMR afforded high anti-diastereoselectivity irrespective of the solvents used. The KF/crown ethers catalytic systems proved to be highly efficient in terms of yields and resulted in a highly diastereoselective unprecedented solvent/catalyst switchable reaction. Anti-adducts were obtained as single diastereomers or with excellent diastereoselectivities when benzo-15-crown-5 in CH2Cl2 was employed. On the other hand, high syn-diastereoselectivities (from 73:27 to 96:4) were achieved by employing dicyclohexane-18-crown-6 in toluene. On the basis of DFT calculations, the catalysts/solvent-dependent switchable diastereoselectivities are proposed to be the result of loose or tight cation–dienolate ion pairs.

Publisher URL: http://dx.doi.org/10.1021/acs.joc.7b00743

DOI: 10.1021/acs.joc.7b00743

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