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Abstract:

The halogen-lithium exchange reaction is of one of the most powerful method for the preparation of organolithium compounds, but its mechanism is still controversial. To afford some new elements, we synthesized a new suitable fast radical clock, bearing a phenyl group at the alkene C-terminal. The examination of some mechanistic clues, as well as the identification of the unexpected by-products allowed the conclusion that the reaction proceeds by a polar mechanism and no evidence for radicals were found. The second reaction discussed is the insertion of NO in the N-Li bond of lithium amides. Evidence for the involving of paramagnetic and nitrosonium intermediates, as well as equilibria between different reactive species were essential for the proposal of a whole complex mechanism, which was confirmed by theoretical calculations. Finally, results on the addition of heteroaromatic organocuprates to a,b-unsaturated substrates are presented. Several reaction conditions were looked for to lead the reaction toward the more interesting 1,4-conjugated addition. Thus, addition of up to 6 equivalents of TMSCl to the reaction with arylcuprates leads to a clean addition yielding more than 95% of the 1,4-addition product. A further objective of the paper is to show how the search of unexpected routes of reaction allowed developing original pathways to lead them toward the formation of appealing functionalized compounds. Copyright © 2010 John Wiley and Sons, Ltd.

Registro:

Documento: Artículo
Título:A wide mechanistic spectrum observed in three different reactions with organometallic reagents
Autor:Rodríguez, C.; Vázquez, A.J.; Nudelman, N.S.
Filiación:Department of Organic Chemistry, Facultad de Ciencias Exactas y Naturales, University of Buenos Aires, P.3 1428 Buenos Aires, Argentina
Palabras clave:halogen-lithium exchange; heteroaromatic organocuprates; NO insertion; TMSCl; Addition products; Complex mechanisms; Functionalized compounds; halogen-lithium exchange; Halogen-lithium exchange reaction; heteroaromatic organocuprates; Lithium amide; Nitrosonium; NO insertion; Organolithium compounds; Organometallic reagent; Phenyl group; Radical clocks; Reaction conditions; Reactive species; Theoretical calculations; TMSCl; Amides; Halogen compounds; Halogen elements; Lead compounds; Lithium; Lithium compounds; Olefins; Organometallics; Addition reactions
Año:2010
Volumen:23
Número:10
Página de inicio:978
Página de fin:984
DOI: http://dx.doi.org/10.1002/poc.1761
Título revista:Journal of Physical Organic Chemistry
Título revista abreviado:J Phys Org Chem
ISSN:08943230
CODEN:JPOCE
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_08943230_v23_n10_p978_Rodriguez

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Citas:

---------- APA ----------
Rodríguez, C., Vázquez, A.J. & Nudelman, N.S. (2010) . A wide mechanistic spectrum observed in three different reactions with organometallic reagents. Journal of Physical Organic Chemistry, 23(10), 978-984.
http://dx.doi.org/10.1002/poc.1761
---------- CHICAGO ----------
Rodríguez, C., Vázquez, A.J., Nudelman, N.S. "A wide mechanistic spectrum observed in three different reactions with organometallic reagents" . Journal of Physical Organic Chemistry 23, no. 10 (2010) : 978-984.
http://dx.doi.org/10.1002/poc.1761
---------- MLA ----------
Rodríguez, C., Vázquez, A.J., Nudelman, N.S. "A wide mechanistic spectrum observed in three different reactions with organometallic reagents" . Journal of Physical Organic Chemistry, vol. 23, no. 10, 2010, pp. 978-984.
http://dx.doi.org/10.1002/poc.1761
---------- VANCOUVER ----------
Rodríguez, C., Vázquez, A.J., Nudelman, N.S. A wide mechanistic spectrum observed in three different reactions with organometallic reagents. J Phys Org Chem. 2010;23(10):978-984.
http://dx.doi.org/10.1002/poc.1761