Intramolecular carbolithiation-cyclization-electrophilic substitution: Solvent effect and mechanistic study

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The intramolecular carbolithiation-cyclization-electrophilic substitution sequence proves to be a promising strategy for synthetic organic chemists. Our current research in this area focuses on the one-pot halogen/lithium exchange of 2-bromophenyl-3-phenylprop-2-enyl ether, followed by intramolecula...

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Autores principales:	Rodriguez, C., Nudelman, N.S.
Formato:	JOUR
Materias:	carbolithiation-cyclization-electrophilic substitution conducted tour mechanism inversion mechanism SE2 electrophilic substitution solvent effect Cyclization Reaction intermediates Stereoselectivity 2 ,3-dihydrobenzofurans Diastereo-selectivity Electrophilic substitutions Intramolecular carbolithiation Inversion of configuration Product distributions Solvent effects Theoretical calculations Solvents
Acceso en línea:	http://hdl.handle.net/20.500.12110/paper_08943230_v34_n4_p322_Rodriguez
Aporte de:	Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires

id	todo:paper_08943230_v34_n4_p322_Rodriguez
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spelling	todo:paper_08943230_v34_n4_p322_Rodriguez2023-10-03T15:42:05Z Intramolecular carbolithiation-cyclization-electrophilic substitution: Solvent effect and mechanistic study Rodriguez, C. Nudelman, N.S. carbolithiation-cyclization-electrophilic substitution conducted tour mechanism inversion mechanism SE2 electrophilic substitution solvent effect Cyclization Reaction intermediates Stereoselectivity 2 ,3-dihydrobenzofurans Diastereo-selectivity Electrophilic substitutions Intramolecular carbolithiation Inversion of configuration Product distributions Solvent effects Theoretical calculations Solvents The intramolecular carbolithiation-cyclization-electrophilic substitution sequence proves to be a promising strategy for synthetic organic chemists. Our current research in this area focuses on the one-pot halogen/lithium exchange of 2-bromophenyl-3-phenylprop-2-enyl ether, followed by intramolecular carbolithiation, and trapping of the new lithiated cyclic intermediate by several electrophiles, affording 3-substituted 2,3-dihydrobenzofurans with some diastereoselectivity. Within this context, a study on the product distribution solvent dependence was carried out using different types of solvents, namely: polar coordinating, polar non-coordinating, and non-polar solvents. The results show that the coordinating features of the solvent affect specially the carbolithiation step, whereas the halogen/lithium exchange seems to be barely affected. Theoretical calculations were carried out to investigate the unexpected diastereoselectivity of the tandem reaction, where two stereocenters are generated. Insights gained from our mechanistic investigations enabled us to propose an inversion of configuration at the lithiated intermediate prior to the reaction, being the electrophile the likely cause for the observed distereoselectivity. © 2014 John Wiley & Sons, Ltd. JOUR info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by/2.5/ar http://hdl.handle.net/20.500.12110/paper_08943230_v34_n4_p322_Rodriguez
institution	Universidad de Buenos Aires
institution_str	I-28
repository_str	R-134
collection	Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA)
topic	carbolithiation-cyclization-electrophilic substitution conducted tour mechanism inversion mechanism SE2 electrophilic substitution solvent effect Cyclization Reaction intermediates Stereoselectivity 2 ,3-dihydrobenzofurans Diastereo-selectivity Electrophilic substitutions Intramolecular carbolithiation Inversion of configuration Product distributions Solvent effects Theoretical calculations Solvents
spellingShingle	carbolithiation-cyclization-electrophilic substitution conducted tour mechanism inversion mechanism SE2 electrophilic substitution solvent effect Cyclization Reaction intermediates Stereoselectivity 2 ,3-dihydrobenzofurans Diastereo-selectivity Electrophilic substitutions Intramolecular carbolithiation Inversion of configuration Product distributions Solvent effects Theoretical calculations Solvents Rodriguez, C. Nudelman, N.S. Intramolecular carbolithiation-cyclization-electrophilic substitution: Solvent effect and mechanistic study
topic_facet	carbolithiation-cyclization-electrophilic substitution conducted tour mechanism inversion mechanism SE2 electrophilic substitution solvent effect Cyclization Reaction intermediates Stereoselectivity 2 ,3-dihydrobenzofurans Diastereo-selectivity Electrophilic substitutions Intramolecular carbolithiation Inversion of configuration Product distributions Solvent effects Theoretical calculations Solvents
description	The intramolecular carbolithiation-cyclization-electrophilic substitution sequence proves to be a promising strategy for synthetic organic chemists. Our current research in this area focuses on the one-pot halogen/lithium exchange of 2-bromophenyl-3-phenylprop-2-enyl ether, followed by intramolecular carbolithiation, and trapping of the new lithiated cyclic intermediate by several electrophiles, affording 3-substituted 2,3-dihydrobenzofurans with some diastereoselectivity. Within this context, a study on the product distribution solvent dependence was carried out using different types of solvents, namely: polar coordinating, polar non-coordinating, and non-polar solvents. The results show that the coordinating features of the solvent affect specially the carbolithiation step, whereas the halogen/lithium exchange seems to be barely affected. Theoretical calculations were carried out to investigate the unexpected diastereoselectivity of the tandem reaction, where two stereocenters are generated. Insights gained from our mechanistic investigations enabled us to propose an inversion of configuration at the lithiated intermediate prior to the reaction, being the electrophile the likely cause for the observed distereoselectivity. © 2014 John Wiley & Sons, Ltd.
format	JOUR
author	Rodriguez, C. Nudelman, N.S.
author_facet	Rodriguez, C. Nudelman, N.S.
author_sort	Rodriguez, C.
title	Intramolecular carbolithiation-cyclization-electrophilic substitution: Solvent effect and mechanistic study
title_short	Intramolecular carbolithiation-cyclization-electrophilic substitution: Solvent effect and mechanistic study
title_full	Intramolecular carbolithiation-cyclization-electrophilic substitution: Solvent effect and mechanistic study
title_fullStr	Intramolecular carbolithiation-cyclization-electrophilic substitution: Solvent effect and mechanistic study
title_full_unstemmed	Intramolecular carbolithiation-cyclization-electrophilic substitution: Solvent effect and mechanistic study
title_sort	intramolecular carbolithiation-cyclization-electrophilic substitution: solvent effect and mechanistic study
url	http://hdl.handle.net/20.500.12110/paper_08943230_v34_n4_p322_Rodriguez
work_keys_str_mv	AT rodriguezc intramolecularcarbolithiationcyclizationelectrophilicsubstitutionsolventeffectandmechanisticstudy AT nudelmanns intramolecularcarbolithiationcyclizationelectrophilicsubstitutionsolventeffectandmechanisticstudy
_version_	1782026941945085952

Intramolecular carbolithiation-cyclization-electrophilic substitution: Solvent effect and mechanistic study

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