Formalizing the mechanism of the allylic substitution reaction (SN'): Application to the highly enantio- and diastereo-selective syntheses of 1-phenyl-2-vinylcyclopentanes

Alain Krief; Johan Wouters; Bernadette Norberg; Adrian Kremer

doi:10.24820/ark.5550190.p010.571

Formalizing the mechanism of the allylic substitution reaction (S_N'): Application to the highly enantio- and diastereo-selective syntheses of 1-phenyl-2-vinylcyclopentanes

Alain Krief, Johan Wouters, Bernadette Norberg, Adrian Kremer

University of Namur

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Abstract

We report efficient stereoselective and high yielding syntheses of each of the four enantiomers of phenylcyclopentanes bearing a quaternary center and a E-propenyl chain on the adjacent carbon that involves intramolecular allylic substitution reactions. In complement to its synthetic value, this process models the S_N' reaction and allows prediction of its stereochemical outcome.

Original language	English
Pages (from-to)	308-333
Number of pages	26
Journal	ARKIVOC
Volume	2018
Issue number	5
DOIs	https://doi.org/10.24820/ark.5550190.p010.571
Publication status	Published - 7 Jul 2018

Funding

The work presented in this paper was initiated in 2004 by Francois Adam (FA) assistant and enrolled as a PhD student, then carried out in 2007 by Hélène Vanderhauwaer (HV) a PhD student supported by the FRIA Belgium (Laboratoire de Chimie Organique de Synthèse, Facultés N.D de la Paix, Namur). Both of them decided to stop their work for personal reasons. Their fragmentary results have been consigned in their progress reports (a) January-July 2005 and (b) January-July 2007 respectively. All the results reported here, except those involving the transformation of 4cE to 11 and 4a (FA, research report 2005) have been carried out by Dr Adrian Kremer in the laboratory of Prof. D. Bonifazi. The Authors thanks Prof. Davide Bonifazi for strongly supporting this work and Prof. Guillaume Berionni for helpful discussions.

Keywords

Aryl cyclopentanes
Benzyl selenides
Se/Li exchange
SN' reaction
Stereospecific carbocyclization

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10.24820/ark.5550190.p010.571

2018_KriefWoutersNorbergKremer_articleFinal published version, 1.97 MB

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abstract = "We report efficient stereoselective and high yielding syntheses of each of the four enantiomers of phenylcyclopentanes bearing a quaternary center and a E-propenyl chain on the adjacent carbon that involves intramolecular allylic substitution reactions. In complement to its synthetic value, this process models the SN' reaction and allows prediction of its stereochemical outcome.",

keywords = "Aryl cyclopentanes, Benzyl selenides, Se/Li exchange, SN' reaction, Stereospecific carbocyclization",

author = "Alain Krief and Johan Wouters and Bernadette Norberg and Adrian Kremer",

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AU - Wouters, Johan

AU - Norberg, Bernadette

AU - Kremer, Adrian

PY - 2018/7/7

Y1 - 2018/7/7

N2 - We report efficient stereoselective and high yielding syntheses of each of the four enantiomers of phenylcyclopentanes bearing a quaternary center and a E-propenyl chain on the adjacent carbon that involves intramolecular allylic substitution reactions. In complement to its synthetic value, this process models the SN' reaction and allows prediction of its stereochemical outcome.

AB - We report efficient stereoselective and high yielding syntheses of each of the four enantiomers of phenylcyclopentanes bearing a quaternary center and a E-propenyl chain on the adjacent carbon that involves intramolecular allylic substitution reactions. In complement to its synthetic value, this process models the SN' reaction and allows prediction of its stereochemical outcome.

KW - Aryl cyclopentanes

KW - Benzyl selenides

KW - Se/Li exchange

KW - SN' reaction

KW - Stereospecific carbocyclization

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ER -

Formalizing the mechanism of the allylic substitution reaction (S_N'): Application to the highly enantio- and diastereo-selective syntheses of 1-phenyl-2-vinylcyclopentanes

Abstract

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Physical Chemistry and characterization(PC2)

CCDC 923103: Experimental Crystal Structure Determination

CCDC 923102: Experimental Crystal Structure Determination

CCDC 923100: Experimental Crystal Structure Determination

Cite this

Formalizing the mechanism of the allylic substitution reaction (SN'): Application to the highly enantio- and diastereo-selective syntheses of 1-phenyl-2-vinylcyclopentanes

Abstract

Funding

Keywords

Access to Document

Other files and links

Fingerprint

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Physical Chemistry and characterization(PC2)

Datasets

CCDC 923103: Experimental Crystal Structure Determination

CCDC 923102: Experimental Crystal Structure Determination

CCDC 923100: Experimental Crystal Structure Determination

Cite this

Formalizing the mechanism of the allylic substitution reaction (S_N'): Application to the highly enantio- and diastereo-selective syntheses of 1-phenyl-2-vinylcyclopentanes