4-Amino-TEMPO as N-Nucleophile in Palladium-Catalyzed Aminocarbonylation

Máté Gergely, Attila Takács, L. Kollár

Research output: Contribution to journalArticle

Abstract

Palladium-catalyzed aminocarbonylation of iodobenzene and iodoalkenes (1-iodocyclohexene, 4-tert-butyl-1-iodocyclohexene, α-iodostyrene, 17-iodoandrost-16-ene) was carried out using a free radical (4-amino-TEMPO) for the first time. Its reduced form (4-amino-2,2,6,6-tetramethylpiperidine) was also used as N-nucleophile. The free radical was partially reduced under aminocarbonylation conditions; however, the isolation of carbonylated products bearing a stable radical moiety was successfully accomplished. It was proved that the reduction of the 1-oxyl functionality took place to higher extent when more severe conditions (40bar CO pressure) were used. The mixture of carboxamide and 2-ketocarboxamide products was obtained using iodobenzene because of single and double carbon monoxide insertion, respectively. In turn, carboxamide derivatives were formed exclusively when iodoalkenes were used as substrates.

Original languageEnglish
JournalJournal of Heterocyclic Chemistry
DOIs
Publication statusAccepted/In press - 2016

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Nucleophiles
Palladium
Carbon Monoxide
Free Radicals
Bearings (structural)
Derivatives
Substrates
4-amino-2,2,6,6-tetramethylpiperidine oxide
iodobenzene
4-amino-2,2,6,6-tetramethylpiperidine

ASJC Scopus subject areas

  • Organic Chemistry

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4-Amino-TEMPO as N-Nucleophile in Palladium-Catalyzed Aminocarbonylation. / Gergely, Máté; Takács, Attila; Kollár, L.

In: Journal of Heterocyclic Chemistry, 2016.

Research output: Contribution to journalArticle

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N2 - Palladium-catalyzed aminocarbonylation of iodobenzene and iodoalkenes (1-iodocyclohexene, 4-tert-butyl-1-iodocyclohexene, α-iodostyrene, 17-iodoandrost-16-ene) was carried out using a free radical (4-amino-TEMPO) for the first time. Its reduced form (4-amino-2,2,6,6-tetramethylpiperidine) was also used as N-nucleophile. The free radical was partially reduced under aminocarbonylation conditions; however, the isolation of carbonylated products bearing a stable radical moiety was successfully accomplished. It was proved that the reduction of the 1-oxyl functionality took place to higher extent when more severe conditions (40bar CO pressure) were used. The mixture of carboxamide and 2-ketocarboxamide products was obtained using iodobenzene because of single and double carbon monoxide insertion, respectively. In turn, carboxamide derivatives were formed exclusively when iodoalkenes were used as substrates.

AB - Palladium-catalyzed aminocarbonylation of iodobenzene and iodoalkenes (1-iodocyclohexene, 4-tert-butyl-1-iodocyclohexene, α-iodostyrene, 17-iodoandrost-16-ene) was carried out using a free radical (4-amino-TEMPO) for the first time. Its reduced form (4-amino-2,2,6,6-tetramethylpiperidine) was also used as N-nucleophile. The free radical was partially reduced under aminocarbonylation conditions; however, the isolation of carbonylated products bearing a stable radical moiety was successfully accomplished. It was proved that the reduction of the 1-oxyl functionality took place to higher extent when more severe conditions (40bar CO pressure) were used. The mixture of carboxamide and 2-ketocarboxamide products was obtained using iodobenzene because of single and double carbon monoxide insertion, respectively. In turn, carboxamide derivatives were formed exclusively when iodoalkenes were used as substrates.

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