Switchable Diastereoselectivity in the Fluoride Promoted Vinylogous Mukaiyama-Michael Reaction of 2-Trimethylsilyloxyfuran Catalyzed by Crown Ethers
Type
ArticleAuthors
Della Sala, GiorgioSicignano, Marina
Schettini, Rosaria
De Riccardis, Francesco
Cavallo, Luigi

Minenkov, Yury

Batisse, Chloé
Hanquet, Gilles
Leroux, Frederic
IZZO, Irene
KAUST Department
Chemical Science ProgramKAUST Catalysis Center (KCC)
Physical Science and Engineering (PSE) Division
Date
2017-06-13Online Publication Date
2017-06-13Print Publication Date
2017-07-07Permanent link to this record
http://hdl.handle.net/10754/624886
Metadata
Show full item recordAbstract
The fluoride promoted vinylogous Mukaiyama-Michael reaction (VMMR) of 2-trimethylsilyloxyfuran 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 76:24 to 96:4) were achieved by employing dicyclohexane-18-crown-6 in toluene. Based on DFT calculations, the catalysts/solvents-dependent switchable diastereoselectivities are proposed to be the result of loose or tight cation-dienolate ion pairs.Citation
Della Sala G, Sicignano M, Schettini R, De Riccardis F, Cavallo L, et al. (2017) Switchable Diastereoselectivity in the Fluoride Promoted Vinylogous Mukaiyama-Michael Reaction of 2-Trimethylsilyloxyfuran Catalyzed by Crown Ethers. The Journal of Organic Chemistry. Available: http://dx.doi.org/10.1021/acs.joc.7b00743.Sponsors
Financial support from the University of Salerno (FARB) and Regione Campania under POR Campania FESR 2007-2013 – O.O. 2.1 (Farma-BioNet). We thank Dr. Patrizia Iannece for HRMS. Gilles Hanquet and Frédéric Leroux thank the CNRS (Centre National de la Recherche Scientifique, France). Chloé Batisse is very grateful to the IcFRC (International Center for Frontier Research in Chemistry), grant Cyclo-CF2-ASYM. Luigi Cavallo thanks the King Abdullah University of Science and technology for supporting this work. Computing resources used within this project have been provided by the KAUST Supercomputing Laboratory and by CRESCO/ENEAGRID High Performance Computing infrastructure and its staff.Publisher
American Chemical Society (ACS)Journal
The Journal of Organic ChemistryPubMed ID
28561585Additional Links
http://pubs.acs.org/doi/abs/10.1021/acs.joc.7b00743ae974a485f413a2113503eed53cd6c53
10.1021/acs.joc.7b00743
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