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Abstract:

The recent proliferation of structural studies of organolithium reagents has led to an extended knowledge of the aggregation state of these pervasive synthetic intermediates. Nevertheless, detailed investigations of organolithium reaction mechanisms are still very limited. The most popular techniques in the relatively few reported studies are UV, EPR and NMR spectroscopy, the use of radical clocks and investigation of the stereochemical course of the reaction when applied. This paper describes how the search for minor products can be an additional mechanistic tool. Metal-halogen exchange was studied with a new suitable fast radical clock bearing a phenyl group at the alkene C-terminus, even when the probe was able to trap very short-lived radical intermediates, the results showed that the reaction proceeds through an open lithiated intermediate. In another study, radicals of benzil were generated on the lithium surface and their reactions studied in THF. Characterization of the minor products, the rates of decay of the reagent and formation of products, and also periodical EPR of the reaction mixture, allowed the proposal of the whole reaction mechanism. In both reactions studied, the detailed understanding of the reaction mechanisms based on the side-products provided new more economical and environmentally friendly alternatives for the synthesis of substituted 2,3-dihydrobenzo[b]furans and aromatic esters. Copyright © 2002 John Wiley & Sons, Ltd.

Registro:

Documento: Artículo
Título:How the by-products hint at mechanisms and suggest new synthetic routes in some organolithium reactions
Autor:Nudelman, N.S.; García, G.V.; Velurtas, S.
Filiación:Depto. Quimica Organica, Ciudad Universitaria, Universidad de Buenos Aires, 1428 Buenos Aires, Argentina
Depto. de Química, Ciudad Universitaria, Universidad Nacional de Mar de Plata, 1428 Buenos Aires, Argentina
Palabras clave:Anionic cyclization; Ate complex; Halogen-lithium exchange; Li/oxygen carbenoid; Lithium surface reactions; Organolithium; Agglomeration; Decay (organic); Lithium; Nuclear magnetic resonance; Paramagnetic resonance; Stereochemistry; Ultraviolet spectroscopy; Synthetic intermediates; Chemical reactions
Año:2002
Volumen:15
Número:12
Página de inicio:903
Página de fin:910
DOI: http://dx.doi.org/10.1002/poc.575
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_v15_n12_p903_Nudelman

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Citas:

---------- APA ----------
Nudelman, N.S., García, G.V. & Velurtas, S. (2002) . How the by-products hint at mechanisms and suggest new synthetic routes in some organolithium reactions. Journal of Physical Organic Chemistry, 15(12), 903-910.
http://dx.doi.org/10.1002/poc.575
---------- CHICAGO ----------
Nudelman, N.S., García, G.V., Velurtas, S. "How the by-products hint at mechanisms and suggest new synthetic routes in some organolithium reactions" . Journal of Physical Organic Chemistry 15, no. 12 (2002) : 903-910.
http://dx.doi.org/10.1002/poc.575
---------- MLA ----------
Nudelman, N.S., García, G.V., Velurtas, S. "How the by-products hint at mechanisms and suggest new synthetic routes in some organolithium reactions" . Journal of Physical Organic Chemistry, vol. 15, no. 12, 2002, pp. 903-910.
http://dx.doi.org/10.1002/poc.575
---------- VANCOUVER ----------
Nudelman, N.S., García, G.V., Velurtas, S. How the by-products hint at mechanisms and suggest new synthetic routes in some organolithium reactions. J Phys Org Chem. 2002;15(12):903-910.
http://dx.doi.org/10.1002/poc.575