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

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

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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
Velardo, A. (Creator), Capaccio, V. (Creator), Caruso, T. (Creator), Di Mola, A. (Creator), Massa, A. (Creator), Tedesco, C. (Creator), Caporaso, L. (Creator), Falivene, L. (Creator), Palombi, L. (Creator), Velardo, A. (Creator), Capaccio, V. (Creator), Caruso, T. (Creator), Di Mola, A. (Creator), Massa, A. (Creator), Tedesco, C. (Creator), Caporaso, L. (Creator) & Palombi, L. (Creator), Cambridge Crystallographic Data Centre, Dec 16 2019
DOI: 10.5517/ccdc.csd.cc235jjc, http://hdl.handle.net/10754/664837
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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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DO - 10.1002/ejoc.201901499

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SP - 7584

EP - 7589

JO - European Journal of Organic Chemistry

JF - European Journal of Organic Chemistry

SN - 1434-193X

IS - 46

ER -

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

Cite this