Switchable Diastereoselectivity in the Fluoride Promoted Vinylogous Mukaiyama-Michael Reaction of 2-Trimethylsilyloxyfuran Catalyzed by Crown Ethers

Giorgio Della Sala; Marina Sicignano; Rosaria Schettini; Francesco De Riccardis; Luigi Cavallo; Yury Minenkov; Chloé Batisse; Gilles Hanquet; Frederic Leroux; Irene IZZO

doi:10.1021/acs.joc.7b00743

Switchable Diastereoselectivity in the Fluoride Promoted Vinylogous Mukaiyama-Michael Reaction of 2-Trimethylsilyloxyfuran Catalyzed by Crown Ethers

Giorgio Della Sala, Marina Sicignano, Rosaria Schettini, Francesco De Riccardis, Luigi Cavallo, Yury Minenkov, Chloé Batisse, Gilles Hanquet, Frederic Leroux, Irene IZZO

Research output: Contribution to journal › Article › peer-review

9 Scopus citations

Abstract

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.

Original language	English (US)
Pages (from-to)	6629-6637
Number of pages	9
Journal	The Journal of Organic Chemistry
Volume	82
Issue number	13
DOIs	https://doi.org/10.1021/acs.joc.7b00743
State	Published - Jun 13 2017

Bibliographical note

KAUST Repository Item: Exported on 2020-10-01
Acknowledgements: 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.

Access to Document

10.1021/acs.joc.7b00743

https://repository.kaust.edu.sa/bitstream/10754/624886/1/acs2Ejoc2E7b00743.pdf

Cite this

Della Sala, G., Sicignano, M., Schettini, R., De Riccardis, F., Cavallo, L., Minenkov, Y., Batisse, C., Hanquet, G., Leroux, F., & IZZO, I. (2017). Switchable Diastereoselectivity in the Fluoride Promoted Vinylogous Mukaiyama-Michael Reaction of 2-Trimethylsilyloxyfuran Catalyzed by Crown Ethers. The Journal of Organic Chemistry, 82(13), 6629-6637. https://doi.org/10.1021/acs.joc.7b00743

@article{5f9b3d260a9a4fceae0397a4a920f2d6,

title = "Switchable Diastereoselectivity in the Fluoride Promoted Vinylogous Mukaiyama-Michael Reaction of 2-Trimethylsilyloxyfuran Catalyzed by Crown Ethers",

abstract = "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.",

author = "{Della Sala}, Giorgio and Marina Sicignano and Rosaria Schettini and {De Riccardis}, Francesco and Luigi Cavallo and Yury Minenkov and Chlo{\'e} Batisse and Gilles Hanquet and Frederic Leroux and Irene IZZO",

note = "KAUST Repository Item: Exported on 2020-10-01 Acknowledgements: 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 Fr{\'e}d{\'e}ric Leroux thank the CNRS (Centre National de la Recherche Scientifique, France). Chlo{\'e} 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.",

year = "2017",

month = jun,

day = "13",

doi = "10.1021/acs.joc.7b00743",

language = "English (US)",

volume = "82",

pages = "6629--6637",

journal = "The Journal of Organic Chemistry",

issn = "0022-3263",

publisher = "American Chemical Society",

number = "13",

}

Della Sala, G, Sicignano, M, Schettini, R, De Riccardis, F, Cavallo, L, Minenkov, Y, Batisse, C, Hanquet, G, Leroux, F & IZZO, I 2017, 'Switchable Diastereoselectivity in the Fluoride Promoted Vinylogous Mukaiyama-Michael Reaction of 2-Trimethylsilyloxyfuran Catalyzed by Crown Ethers', The Journal of Organic Chemistry, vol. 82, no. 13, pp. 6629-6637. https://doi.org/10.1021/acs.joc.7b00743

TY - JOUR

T1 - Switchable Diastereoselectivity in the Fluoride Promoted Vinylogous Mukaiyama-Michael Reaction of 2-Trimethylsilyloxyfuran Catalyzed by Crown Ethers

AU - Della Sala, Giorgio

AU - Sicignano, Marina

AU - Schettini, Rosaria

AU - De Riccardis, Francesco

AU - Cavallo, Luigi

AU - Minenkov, Yury

AU - Batisse, Chloé

AU - Hanquet, Gilles

AU - Leroux, Frederic

AU - IZZO, Irene

N1 - KAUST Repository Item: Exported on 2020-10-01 Acknowledgements: 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.

PY - 2017/6/13

Y1 - 2017/6/13

N2 - 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.

AB - 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.

UR - http://hdl.handle.net/10754/624886

UR - http://pubs.acs.org/doi/abs/10.1021/acs.joc.7b00743

UR - http://www.scopus.com/inward/record.url?scp=85022224929&partnerID=8YFLogxK

U2 - 10.1021/acs.joc.7b00743

DO - 10.1021/acs.joc.7b00743

M3 - Article

C2 - 28561585

SN - 0022-3263

VL - 82

SP - 6629

EP - 6637

JO - The Journal of Organic Chemistry

JF - The Journal of Organic Chemistry

IS - 13

ER -

Switchable Diastereoselectivity in the Fluoride Promoted Vinylogous Mukaiyama-Michael Reaction of 2-Trimethylsilyloxyfuran Catalyzed by Crown Ethers

Abstract

Bibliographical note

Access to Document

Other files and links

Fingerprint

Cite this