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

Physical Sciences and Engineering

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

5 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

Bibliographical note

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

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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

Cite this

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

@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",

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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, vol. 2019, no. 46, pp. 7584-7589. https://doi.org/10.1002/ejoc.201901499

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.

UR - http://hdl.handle.net/10754/660563

UR - http://doi.wiley.com/10.1002/ejoc.201901499

UR - http://www.scopus.com/inward/record.url?scp=85075952333&partnerID=8YFLogxK

U2 - 10.1002/ejoc.201901499

DO - 10.1002/ejoc.201901499

M3 - Article

SN - 1434-193X

VL - 2019

SP - 7584

EP - 7589

JO - European Journal of Organic Chemistry

JF - European Journal of Organic Chemistry

IS - 46

ER -

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

Abstract

Bibliographical note

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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

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

Abstract

Bibliographical note

Access to Document

Other files and links

Fingerprint

Datasets

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

Cite this