Carbon-Carbon Bond Formation through the Carbonylation of Lithium Dialkylamides. One-Pot Synthesis of N-Alkyl-Substituted Formamides, Glyoxylamides, and Hydroxymalonamides

The reaction of lithium dialkylamides 1 (dialkyl = dibutyl, dipentyl, dicyclohexyl, 3-oxapentamethylene, and isopropyl cyclohexyl) with carbon monoxide was examined under several reaction conditions. It is shown that the corresponding lithium carbamoyl is the first intermediate and its further react...

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Autor principal: Perez, Daniel Gustavo
Publicado: 1988
Acceso en línea:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00223263_v53_n2_p408_Perez
http://hdl.handle.net/20.500.12110/paper_00223263_v53_n2_p408_Perez
Aporte de:
Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires
id paper:paper_00223263_v53_n2_p408_Perez
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spelling paper:paper_00223263_v53_n2_p408_Perez2023-06-08T14:49:27Z Carbon-Carbon Bond Formation through the Carbonylation of Lithium Dialkylamides. One-Pot Synthesis of N-Alkyl-Substituted Formamides, Glyoxylamides, and Hydroxymalonamides Perez, Daniel Gustavo The reaction of lithium dialkylamides 1 (dialkyl = dibutyl, dipentyl, dicyclohexyl, 3-oxapentamethylene, and isopropyl cyclohexyl) with carbon monoxide was examined under several reaction conditions. It is shown that the corresponding lithium carbamoyl is the first intermediate and its further reactions can lead to dialkylformamides 2, dialkylglyoxylamides 3, or tetraalkylhydroxymalonamides 4. Dialkylamides were previously assumed to come from hydrolysis of lithium carbamoyls, and these represent an unexplained “island of stability” among the area of acyl anions. Evidence is given that casts doubts on this assumption and suggests that 2 comes from the cleavage of lithium tetraalkylurea dianion. The yields of 2, 3, or 4 obtained by this one-step, rapid procedure are much higher than those afforded by the usual several steps methods of preparation, especially for compounds 3 and 4. Tetraalkylureas, tetraalkyloxalamines, or tetraalkylketomalonamides can be obtained in good yield by the same general procedure, followed by treatment of the reaction mixture with oxygen after the carbon monoxide absorption has ceased and before the regular workup. © 1988, American Chemical Society. All rights reserved. Fil:Pérez, D.G. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. 1988 https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00223263_v53_n2_p408_Perez http://hdl.handle.net/20.500.12110/paper_00223263_v53_n2_p408_Perez
institution Universidad de Buenos Aires
institution_str I-28
repository_str R-134
collection Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA)
description The reaction of lithium dialkylamides 1 (dialkyl = dibutyl, dipentyl, dicyclohexyl, 3-oxapentamethylene, and isopropyl cyclohexyl) with carbon monoxide was examined under several reaction conditions. It is shown that the corresponding lithium carbamoyl is the first intermediate and its further reactions can lead to dialkylformamides 2, dialkylglyoxylamides 3, or tetraalkylhydroxymalonamides 4. Dialkylamides were previously assumed to come from hydrolysis of lithium carbamoyls, and these represent an unexplained “island of stability” among the area of acyl anions. Evidence is given that casts doubts on this assumption and suggests that 2 comes from the cleavage of lithium tetraalkylurea dianion. The yields of 2, 3, or 4 obtained by this one-step, rapid procedure are much higher than those afforded by the usual several steps methods of preparation, especially for compounds 3 and 4. Tetraalkylureas, tetraalkyloxalamines, or tetraalkylketomalonamides can be obtained in good yield by the same general procedure, followed by treatment of the reaction mixture with oxygen after the carbon monoxide absorption has ceased and before the regular workup. © 1988, American Chemical Society. All rights reserved.
author Perez, Daniel Gustavo
spellingShingle Perez, Daniel Gustavo
Carbon-Carbon Bond Formation through the Carbonylation of Lithium Dialkylamides. One-Pot Synthesis of N-Alkyl-Substituted Formamides, Glyoxylamides, and Hydroxymalonamides
author_facet Perez, Daniel Gustavo
author_sort Perez, Daniel Gustavo
title Carbon-Carbon Bond Formation through the Carbonylation of Lithium Dialkylamides. One-Pot Synthesis of N-Alkyl-Substituted Formamides, Glyoxylamides, and Hydroxymalonamides
title_short Carbon-Carbon Bond Formation through the Carbonylation of Lithium Dialkylamides. One-Pot Synthesis of N-Alkyl-Substituted Formamides, Glyoxylamides, and Hydroxymalonamides
title_full Carbon-Carbon Bond Formation through the Carbonylation of Lithium Dialkylamides. One-Pot Synthesis of N-Alkyl-Substituted Formamides, Glyoxylamides, and Hydroxymalonamides
title_fullStr Carbon-Carbon Bond Formation through the Carbonylation of Lithium Dialkylamides. One-Pot Synthesis of N-Alkyl-Substituted Formamides, Glyoxylamides, and Hydroxymalonamides
title_full_unstemmed Carbon-Carbon Bond Formation through the Carbonylation of Lithium Dialkylamides. One-Pot Synthesis of N-Alkyl-Substituted Formamides, Glyoxylamides, and Hydroxymalonamides
title_sort carbon-carbon bond formation through the carbonylation of lithium dialkylamides. one-pot synthesis of n-alkyl-substituted formamides, glyoxylamides, and hydroxymalonamides
publishDate 1988
url https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00223263_v53_n2_p408_Perez
http://hdl.handle.net/20.500.12110/paper_00223263_v53_n2_p408_Perez
work_keys_str_mv AT perezdanielgustavo carboncarbonbondformationthroughthecarbonylationoflithiumdialkylamidesonepotsynthesisofnalkylsubstitutedformamidesglyoxylamidesandhydroxymalonamides
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