Desymmetrization of 2-Cyano-N-tosylbenzylidenimine with Thiols and Organocatalytic Heterocyclization by Dynamic Resolution: Mechanism Investigation

Amalia Velardo; Vito Capaccio; Tonino Caruso; Antonia Di Mola; Antonio Massa; Consiglia Tedesco; Lucia Caporaso; Laura Falivene; Laura Palombi

doi:10.1002/ejoc.201901499

Desymmetrization of 2-Cyano-N-tosylbenzylidenimine with Thiols and Organocatalytic Heterocyclization by Dynamic Resolution: Mechanism Investigation

Amalia Velardo, Vito Capaccio, Tonino Caruso, Antonia Di Mola, Antonio Massa, Consiglia Tedesco, Lucia Caporaso, Laura Falivene, Laura Palombi

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

1 Scopus citations

Abstract

Integrated experimental and computational approach provides a rationale for the mode of action of cinchona-based alkaloids as chiral receptors in the observed dynamic chiral resolution of the titled tandem reaction. In particular, a mechanism based on a dynamic kinetic asymmetric transformation has been unravelled in detail. Furthermore, the crucial role of “distal” H-bonding donor functionality in directing the enantioselectivity reversal of homochiral cinchona-based catalysts has been convincingly explained. The access to enantiopure tertiary isoindolinone N,S-acetals has been achieved for the first time.

Original language	English (US)
Pages (from-to)	7584-7589
Number of pages	6
Journal	European Journal of Organic Chemistry
Volume	2019
Issue number	46
DOIs	https://doi.org/10.1002/ejoc.201901499
State	Published - Nov 28 2019

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10.1002/ejoc.201901499

https://repository.kaust.edu.sa/bitstream/10754/660563/1/Velardo_et_al-2019-European_Journal_of_Organic_Chemistry.pdf

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Velardo, A., Capaccio, V., Caruso, T., Di Mola, A., Massa, A., Tedesco, C., Caporaso, L., Falivene, L., & Palombi, L. (2019). Desymmetrization of 2-Cyano-N-tosylbenzylidenimine with Thiols and Organocatalytic Heterocyclization by Dynamic Resolution: Mechanism Investigation. European Journal of Organic Chemistry, 2019(46), 7584-7589. https://doi.org/10.1002/ejoc.201901499

Velardo, Amalia ; Capaccio, Vito ; Caruso, Tonino ; Di Mola, Antonia ; Massa, Antonio ; Tedesco, Consiglia ; Caporaso, Lucia ; Falivene, Laura ; Palombi, Laura. / Desymmetrization of 2-Cyano-N-tosylbenzylidenimine with Thiols and Organocatalytic Heterocyclization by Dynamic Resolution: Mechanism Investigation. In: European Journal of Organic Chemistry. 2019 ; Vol. 2019, No. 46. pp. 7584-7589.

@article{3b99a8ed70b64b529761ada3fca30689,

title = "Desymmetrization of 2-Cyano-N-tosylbenzylidenimine with Thiols and Organocatalytic Heterocyclization by Dynamic Resolution: Mechanism Investigation",

abstract = "Integrated experimental and computational approach provides a rationale for the mode of action of cinchona-based alkaloids as chiral receptors in the observed dynamic chiral resolution of the titled tandem reaction. In particular, a mechanism based on a dynamic kinetic asymmetric transformation has been unravelled in detail. Furthermore, the crucial role of “distal” H-bonding donor functionality in directing the enantioselectivity reversal of homochiral cinchona-based catalysts has been convincingly explained. The access to enantiopure tertiary isoindolinone N,S-acetals has been achieved for the first time.",

author = "Amalia Velardo and Vito Capaccio and Tonino Caruso and {Di Mola}, Antonia and Antonio Massa and Consiglia Tedesco and Lucia Caporaso and Laura Falivene and Laura Palombi",

note = "KAUST Repository Item: Exported on 2020-10-01 Acknowledgements: We thank Miur and University of Salerno for financial supports.",

year = "2019",

month = nov,

day = "28",

doi = "10.1002/ejoc.201901499",

language = "English (US)",

volume = "2019",

pages = "7584--7589",

journal = "European Journal of Organic Chemistry",

issn = "1434-193X",

publisher = "Wiley",

number = "46",

}

Velardo, A, Capaccio, V, Caruso, T, Di Mola, A, Massa, A, Tedesco, C, Caporaso, L, Falivene, L & Palombi, L 2019, 'Desymmetrization of 2-Cyano-N-tosylbenzylidenimine with Thiols and Organocatalytic Heterocyclization by Dynamic Resolution: Mechanism Investigation', European Journal of Organic Chemistry, vol. 2019, no. 46, pp. 7584-7589. https://doi.org/10.1002/ejoc.201901499

Desymmetrization of 2-Cyano-N-tosylbenzylidenimine with Thiols and Organocatalytic Heterocyclization by Dynamic Resolution: Mechanism Investigation. / Velardo, Amalia; Capaccio, Vito; Caruso, Tonino; Di Mola, Antonia; Massa, Antonio; Tedesco, Consiglia; Caporaso, Lucia; Falivene, Laura; Palombi, Laura.

In: European Journal of Organic Chemistry, Vol. 2019, No. 46, 28.11.2019, p. 7584-7589.

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

TY - JOUR

T1 - Desymmetrization of 2-Cyano-N-tosylbenzylidenimine with Thiols and Organocatalytic Heterocyclization by Dynamic Resolution: Mechanism Investigation

AU - Velardo, Amalia

AU - Capaccio, Vito

AU - Caruso, Tonino

AU - Di Mola, Antonia

AU - Massa, Antonio

AU - Tedesco, Consiglia

AU - Caporaso, Lucia

AU - Falivene, Laura

AU - Palombi, Laura

N1 - KAUST Repository Item: Exported on 2020-10-01 Acknowledgements: We thank Miur and University of Salerno for financial supports.

PY - 2019/11/28

Y1 - 2019/11/28

N2 - Integrated experimental and computational approach provides a rationale for the mode of action of cinchona-based alkaloids as chiral receptors in the observed dynamic chiral resolution of the titled tandem reaction. In particular, a mechanism based on a dynamic kinetic asymmetric transformation has been unravelled in detail. Furthermore, the crucial role of “distal” H-bonding donor functionality in directing the enantioselectivity reversal of homochiral cinchona-based catalysts has been convincingly explained. The access to enantiopure tertiary isoindolinone N,S-acetals has been achieved for the first time.

AB - Integrated experimental and computational approach provides a rationale for the mode of action of cinchona-based alkaloids as chiral receptors in the observed dynamic chiral resolution of the titled tandem reaction. In particular, a mechanism based on a dynamic kinetic asymmetric transformation has been unravelled in detail. Furthermore, the crucial role of “distal” H-bonding donor functionality in directing the enantioselectivity reversal of homochiral cinchona-based catalysts has been convincingly explained. The access to enantiopure tertiary isoindolinone N,S-acetals has been achieved for the first time.

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SN - 1434-193X

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Desymmetrization of 2-Cyano-N-tosylbenzylidenimine with Thiols and Organocatalytic Heterocyclization by Dynamic Resolution: Mechanism Investigation

Abstract

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CCDC 1941732: Experimental Crystal Structure Determination : 3-((4-methoxyphenyl)sulfanyl)-2-(4-methylbenzene-1-sulfonyl)-2,3-dihydro-1H-isoindol-1-one

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Desymmetrization of 2-Cyano-N-tosylbenzylidenimine with Thiols and Organocatalytic Heterocyclization by Dynamic Resolution: Mechanism Investigation

Abstract

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Datasets

CCDC 1941732: Experimental Crystal Structure Determination : 3-((4-methoxyphenyl)sulfanyl)-2-(4-methylbenzene-1-sulfonyl)-2,3-dihydro-1H-isoindol-1-one

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