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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Detalles Bibliográficos
Autores principales: Rodriguez, C., Nudelman, N.S.
Formato: INPR
Lenguaje:English
Materias:
Carbolithiation-cyclization-electrophilic substitution
Conducted tour mechanism
Inversion mechanism
SE2 electrophilic substitution
Solvent effect
Acceso en línea:http://hdl.handle.net/20.500.12110/paper_08943230_v_n_p_Rodriguez
Aporte de:
Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires
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spelling todo:paper_08943230_v_n_p_Rodriguez2023-10-03T15:42:07Z 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 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. © 2013 John Wiley & Sons, Ltd. INPR English info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by/2.5/ar http://hdl.handle.net/20.500.12110/paper_08943230_v_n_p_Rodriguez
institution Universidad de Buenos Aires
institution_str I-28
repository_str R-134
collection Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA)
language English
orig_language_str_mv English
topic Carbolithiation-cyclization-electrophilic substitution
Conducted tour mechanism
Inversion mechanism
SE2 electrophilic substitution
Solvent effect
spellingShingle Carbolithiation-cyclization-electrophilic substitution
Conducted tour mechanism
Inversion mechanism
SE2 electrophilic substitution
Solvent effect
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
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. © 2013 John Wiley & Sons, Ltd.
format INPR
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_v_n_p_Rodriguez
work_keys_str_mv AT rodriguezc intramolecularcarbolithiationcyclizationelectrophilicsubstitutionsolventeffectandmechanisticstudy
AT nudelmanns intramolecularcarbolithiationcyclizationelectrophilicsubstitutionsolventeffectandmechanisticstudy
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