Unprecedented Diastereoselective Arylogous Michael Addition of Unactivated Phthalides

Marina Sicignano; Rosaria Schettini; Luisa Sica; Giovanni Pierri; Francesco De Riccardis; Irene IZZO; Bholanath Maity; Yury Minenkov; Luigi Cavallo; Giorgio Della Sala

doi:10.1002/chem.201900168

Unprecedented Diastereoselective Arylogous Michael Addition of Unactivated Phthalides

Marina Sicignano, Rosaria Schettini, Luisa Sica, Giovanni Pierri, Francesco De Riccardis, Irene IZZO, Bholanath Maity, Yury Minenkov, Luigi Cavallo, Giorgio Della Sala

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

8 Scopus citations

Abstract

The first highly enantioselective arylogous Michael reaction (AMR) of 3-unsubstituted phthalides has been described. This phase-transfer methodology, which uses catalytic amounts of KOH/18-crown-6 catalyst in mesitylene in the presence of N,O-bis(trimethylsilyl)acetamide (BSA), gives access to a broad range of 3-monosubstituted phthalides with high levels of syn diastereoselectivity and good yields, starting from 3-unsubstituted derivatives and diverse α,β-unsaturated carbonyl compounds. The reaction also applies to unactivated 3-alkyl phthalides to afford 3,3-dialkyl derivatives. A plausible mechanism has been suggested. DFT analysis of possible transition states gives a rationale of the high syn diastereoselectivity observed and its correlation with the solvent's dielectric constant.

Original language	English (US)
Pages (from-to)	7131-7141
Number of pages	11
Journal	Chemistry – A European Journal
Volume	25
Issue number	29
DOIs	https://doi.org/10.1002/chem.201900168
State	Published - Apr 8 2019

Bibliographical note

KAUST Repository Item: Exported on 2020-10-01
Acknowledgements: Financial support was provided from the University of Salerno (FARB). The computing resources used within this project have been provided by CRESCO/ENEAGRID High Performance Computing infrastructure and its staff. We thank Dr Patrizia Iannece for HR-ESI-MS

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10.1002/chem.201900168

https://repository.kaust.edu.sa/bitstream/10754/656080/1/Accepted%20article%20-%20manuscript%20chem.201900168.pdf

Cite this

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title = "Unprecedented Diastereoselective Arylogous Michael Addition of Unactivated Phthalides",

abstract = "The first highly enantioselective arylogous Michael reaction (AMR) of 3-unsubstituted phthalides has been described. This phase-transfer methodology, which uses catalytic amounts of KOH/18-crown-6 catalyst in mesitylene in the presence of N,O-bis(trimethylsilyl)acetamide (BSA), gives access to a broad range of 3-monosubstituted phthalides with high levels of syn diastereoselectivity and good yields, starting from 3-unsubstituted derivatives and diverse α,β-unsaturated carbonyl compounds. The reaction also applies to unactivated 3-alkyl phthalides to afford 3,3-dialkyl derivatives. A plausible mechanism has been suggested. DFT analysis of possible transition states gives a rationale of the high syn diastereoselectivity observed and its correlation with the solvent's dielectric constant.",

author = "Marina Sicignano and Rosaria Schettini and Luisa Sica and Giovanni Pierri and Francesco De Riccardis and Irene IZZO and Bholanath Maity and Yury Minenkov and Luigi Cavallo and Giorgio Della Sala",

note = "KAUST Repository Item: Exported on 2020-10-01 Acknowledgements: Financial support was provided from the University of Salerno (FARB). The computing resources used within this project have been provided by CRESCO/ENEAGRID High Performance Computing infrastructure and its staff. We thank Dr Patrizia Iannece for HR-ESI-MS",

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AU - Schettini, Rosaria

AU - Sica, Luisa

AU - Pierri, Giovanni

AU - De Riccardis, Francesco

AU - IZZO, Irene

AU - Maity, Bholanath

AU - Minenkov, Yury

AU - Cavallo, Luigi

AU - Della Sala, Giorgio

N1 - KAUST Repository Item: Exported on 2020-10-01 Acknowledgements: Financial support was provided from the University of Salerno (FARB). The computing resources used within this project have been provided by CRESCO/ENEAGRID High Performance Computing infrastructure and its staff. We thank Dr Patrizia Iannece for HR-ESI-MS

PY - 2019/4/8

Y1 - 2019/4/8

N2 - The first highly enantioselective arylogous Michael reaction (AMR) of 3-unsubstituted phthalides has been described. This phase-transfer methodology, which uses catalytic amounts of KOH/18-crown-6 catalyst in mesitylene in the presence of N,O-bis(trimethylsilyl)acetamide (BSA), gives access to a broad range of 3-monosubstituted phthalides with high levels of syn diastereoselectivity and good yields, starting from 3-unsubstituted derivatives and diverse α,β-unsaturated carbonyl compounds. The reaction also applies to unactivated 3-alkyl phthalides to afford 3,3-dialkyl derivatives. A plausible mechanism has been suggested. DFT analysis of possible transition states gives a rationale of the high syn diastereoselectivity observed and its correlation with the solvent's dielectric constant.

AB - The first highly enantioselective arylogous Michael reaction (AMR) of 3-unsubstituted phthalides has been described. This phase-transfer methodology, which uses catalytic amounts of KOH/18-crown-6 catalyst in mesitylene in the presence of N,O-bis(trimethylsilyl)acetamide (BSA), gives access to a broad range of 3-monosubstituted phthalides with high levels of syn diastereoselectivity and good yields, starting from 3-unsubstituted derivatives and diverse α,β-unsaturated carbonyl compounds. The reaction also applies to unactivated 3-alkyl phthalides to afford 3,3-dialkyl derivatives. A plausible mechanism has been suggested. DFT analysis of possible transition states gives a rationale of the high syn diastereoselectivity observed and its correlation with the solvent's dielectric constant.

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Unprecedented Diastereoselective Arylogous Michael Addition of Unactivated Phthalides

Abstract

Bibliographical note

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CCDC 1874899: Experimental Crystal Structure Determination : 3-(3-oxo-1,3-diphenylpropyl)-2-benzofuran-1(3H)-one

CCDC 1874897: Experimental Crystal Structure Determination : 3-[1-(4-fluorophenyl)-3-oxo-3-phenylpropyl]-2-benzofuran-1(3H)-one

CCDC 1874898: Experimental Crystal Structure Determination : ethyl 3-(3-oxo-1,3-dihydro-2-benzofuran-1-yl)-3-phenylpropanoate

Cite this

Unprecedented Diastereoselective Arylogous Michael Addition of Unactivated Phthalides

Abstract

Bibliographical note

Access to Document

Other files and links

Fingerprint

Datasets

CCDC 1874899: Experimental Crystal Structure Determination : 3-(3-oxo-1,3-diphenylpropyl)-2-benzofuran-1(3H)-one

CCDC 1874897: Experimental Crystal Structure Determination : 3-[1-(4-fluorophenyl)-3-oxo-3-phenylpropyl]-2-benzofuran-1(3H)-one

CCDC 1874898: Experimental Crystal Structure Determination : ethyl 3-(3-oxo-1,3-dihydro-2-benzofuran-1-yl)-3-phenylpropanoate

Cite this