Aminocarbonylation (hydrazinocarbonylation) of iodoalkenes and iodoarenes

Máté Gergely, L. Kollár

Research output: Contribution to journalArticle

2 Citations (Scopus)

Abstract

Iodoalkenes such as 1-iodocyclohexene, 4-tert-butyl-1-iodocyclohexene, α-iodostyrene and 17-iodoandrost-16-ene were aminocarbonylated in palladium-catalysed reaction using 1,1-disubstituted (cyclic) hydrazines (3-amino-3-azabicyclo[3.3.0]octane and (S)-1-amino-2-methoxymethylpyrrolidine (SAMP)/(R)-1-amino-2-methoxymethyl-pyrrolidine (RAMP)) as N-nucleophiles. The corresponding hydrazides were formed in moderate to high yields. The hydrazinocarbonylation of iodobenzene using the above 1,1-disubstituted hydrazines resulted in a rather complex reaction mixture due to two major types of side-reactions: i) the deamination of the 3-amino-3-azabicyclo[3.3.0]octane, and ii) the double carbon monoxide insertion. In this way, in addition to the expected benzoylhydrazide derivative, phenylglyoxylhydrazide (double CO insertion product) and benzamide (‘deamination’ product) were also formed. By the appropriate modification of the reaction conditions, good selectivities towards the target compounds were achieved even in these cases. The formation of the products/side-products were rationalized on the basis of a simplified catalytic cycle.

Original languageEnglish
Pages (from-to)838-844
Number of pages7
JournalTetrahedron
Volume73
Issue number7
DOIs
Publication statusPublished - Feb 16 2017

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Hydrazines
Deamination
Carbon Monoxide
Nucleophiles
Palladium
Complex Mixtures
Derivatives
azabicyclo(3.3.0)-octane

Keywords

  • Carbon monoxide
  • Carbonylation
  • Hydrazide
  • Hydrazine
  • Palladium

ASJC Scopus subject areas

  • Biochemistry
  • Drug Discovery
  • Organic Chemistry

Cite this

Aminocarbonylation (hydrazinocarbonylation) of iodoalkenes and iodoarenes. / Gergely, Máté; Kollár, L.

In: Tetrahedron, Vol. 73, No. 7, 16.02.2017, p. 838-844.

Research output: Contribution to journalArticle

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AB - Iodoalkenes such as 1-iodocyclohexene, 4-tert-butyl-1-iodocyclohexene, α-iodostyrene and 17-iodoandrost-16-ene were aminocarbonylated in palladium-catalysed reaction using 1,1-disubstituted (cyclic) hydrazines (3-amino-3-azabicyclo[3.3.0]octane and (S)-1-amino-2-methoxymethylpyrrolidine (SAMP)/(R)-1-amino-2-methoxymethyl-pyrrolidine (RAMP)) as N-nucleophiles. The corresponding hydrazides were formed in moderate to high yields. The hydrazinocarbonylation of iodobenzene using the above 1,1-disubstituted hydrazines resulted in a rather complex reaction mixture due to two major types of side-reactions: i) the deamination of the 3-amino-3-azabicyclo[3.3.0]octane, and ii) the double carbon monoxide insertion. In this way, in addition to the expected benzoylhydrazide derivative, phenylglyoxylhydrazide (double CO insertion product) and benzamide (‘deamination’ product) were also formed. By the appropriate modification of the reaction conditions, good selectivities towards the target compounds were achieved even in these cases. The formation of the products/side-products were rationalized on the basis of a simplified catalytic cycle.

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