Artículo
Abstract:
The strategic tool of homo- and hetero-aggregates in the reactions of organometallic compounds involving C-Li, N-Li, C-Sn(IV) and C-Cr(III) is described. In the carbonylation of lithium amides complexation with different agents leads the reactions toward the synthesis of several carbamoyl compounds in good to quantitative yields. Hetero-aggregates of cyclic dialkylamides with hydrogen-bond donor persist even in solution giving rise to unusual results, the study of their reactions with dialkylformamides afforded a methodology for the synthesis of the first adduct amide-lithium amide. The study of the reaction of benzaldehyde with Li metal allowed characterization of the species formed on the surface of the Li metal, which can serve as a model for the Fischer-Tropsch reaction. The rate coefficients of the different steps in which each species is involved were determined. The tandem reaction of E-cynnamaldehyde with PhLi, followed by nucleophilic addition on the β-carbon affords a useful methodology for the preparation of β-alkyl substituted dihydrochalcones. Complexation by the dimeric PhLi is the responsible for the unusual mechanism that give rise to stereoselective β-addition. The inhibiting effect of CO in the reactions of trialkyltins with electrophiles indicates that the first step is an electron transfer. On the other hand, complexing of heterosubstituted alkyl tins with Cu(I) catalysts is an useful substitute of Pd catalysts for the Stille coupling reaction with alkyl halides. The beneficial effect of complexes of Cr(III) for the selective alkyl addition to α,β-unsaturated aldehydes is also discussed.
Registro:
| Documento: | Artículo |
| Título: | The role of complexes in defining organometallic reaction mechanisms |
| Autor: | Nudelman, N.S. |
| Filiación: | Depto. Quimica Orgánica, Fac. de Ciencias Exactas y Naturales, Ciudad Universitaria, 1428 Buenos Aires, Argentina |
| Año: | 1998 |
| Volumen: | 70 |
| Número: | 10 |
| Página de inicio: | 1939 |
| Página de fin: | 1946 |
| DOI: | http://dx.doi.org/10.1351/pac199870101939 |
| Título revista: | Pure and Applied Chemistry |
| Título revista abreviado: | Pure Appl. Chem. |
| ISSN: | 00334545 |
| CODEN: | PACHA |
| Registro: | https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00334545_v70_n10_p1939_Nudelman |
Referencias:
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Citas:
---------- APA ----------
(1998) . The role of complexes in defining organometallic reaction mechanisms. Pure and Applied Chemistry, 70(10), 1939-1946.http://dx.doi.org/10.1351/pac199870101939
---------- CHICAGO ----------
Nudelman, N.S. "The role of complexes in defining organometallic reaction mechanisms" . Pure and Applied Chemistry 70, no. 10 (1998) : 1939-1946.http://dx.doi.org/10.1351/pac199870101939
---------- MLA ----------
Nudelman, N.S. "The role of complexes in defining organometallic reaction mechanisms" . Pure and Applied Chemistry, vol. 70, no. 10, 1998, pp. 1939-1946.http://dx.doi.org/10.1351/pac199870101939
---------- VANCOUVER ----------
Nudelman, N.S. The role of complexes in defining organometallic reaction mechanisms. Pure Appl. Chem. 1998;70(10):1939-1946.http://dx.doi.org/10.1351/pac199870101939
