Intramolecular carbolithiation-cyclization-electrophilic substitution: Solvent effect and mechanistic study
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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2014
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| Acceso en línea: | https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_08943230_v34_n4_p322_Rodriguez http://hdl.handle.net/20.500.12110/paper_08943230_v34_n4_p322_Rodriguez |
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paper:paper_08943230_v34_n4_p322_Rodriguez2023-06-08T15:47:48Z Intramolecular carbolithiation-cyclization-electrophilic substitution: Solvent effect and mechanistic study 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. 2014 https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_08943230_v34_n4_p322_Rodriguez 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 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. |
| 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 |
| publishDate |
2014 |
| url |
https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_08943230_v34_n4_p322_Rodriguez http://hdl.handle.net/20.500.12110/paper_08943230_v34_n4_p322_Rodriguez |
| _version_ |
1768544871850704896 |