Synthesis of N-picolylcarboxamides via palladium-catalysed aminocarbonylation of iodobenzene and iodoalkenes

Máté Gergely, Roland Farkas, Attila Takács, Andrea Petz, L. Kollár

Research output: Contribution to journalArticle

11 Citations (Scopus)

Abstract

A systematic investigation of the palladium-catalysed aminocarbonylation of iodobenzene, 1-iodocyclohexene and 1′-iodostyrene in the presence of N-nucleophiles containing pyridyl moieties (2-, 3- and 4-picolylamine, N-ethyl-4-picolylamine, di-(2-picolyl)amine) was carried out. The two types of iodo substrates differ substantially regarding the selectivity towards carbonylation: while the aminocarbonylation of iodobenzene resulted in the formation of carboxamide and ketocarboxamide mixtures under various conditions, with the predominant formation of ketocarboxamide even at low carbon monoxide pressure, the aminocarbonylation of iodoalkenes under same conditions gave the corresponding unsaturated carboxamide exclusively. Most of the carboxamides and phenylglyoxylamides, obtained via single and double carbon monoxide insertion, respectively, were isolated in yields of synthetic interest (up to 86%). Low reaction rates and unexpected chemoselectivity towards carboxamide formation have been observed with di-(2-picolyl)amine as N-nucleophile in the aminocarbonylation of iodobenzene.

Original languageEnglish
Pages (from-to)218-224
Number of pages7
JournalTetrahedron
Volume70
Issue number2
DOIs
Publication statusPublished - Jan 14 2014

Fingerprint

Palladium
Nucleophiles
Carbon Monoxide
Amines
Carbonylation
Reaction rates
Pressure
Substrates
iodobenzene

Keywords

  • Carbon monoxide
  • Carbonylation
  • Homogeneous catalysis
  • Palladium
  • Picolylamine

ASJC Scopus subject areas

  • Biochemistry
  • Organic Chemistry
  • Drug Discovery

Cite this

Synthesis of N-picolylcarboxamides via palladium-catalysed aminocarbonylation of iodobenzene and iodoalkenes. / Gergely, Máté; Farkas, Roland; Takács, Attila; Petz, Andrea; Kollár, L.

In: Tetrahedron, Vol. 70, No. 2, 14.01.2014, p. 218-224.

Research output: Contribution to journalArticle

Gergely, Máté ; Farkas, Roland ; Takács, Attila ; Petz, Andrea ; Kollár, L. / Synthesis of N-picolylcarboxamides via palladium-catalysed aminocarbonylation of iodobenzene and iodoalkenes. In: Tetrahedron. 2014 ; Vol. 70, No. 2. pp. 218-224.
@article{47336c5d36ab4f7ebc50b311f4f56bff,
title = "Synthesis of N-picolylcarboxamides via palladium-catalysed aminocarbonylation of iodobenzene and iodoalkenes",
abstract = "A systematic investigation of the palladium-catalysed aminocarbonylation of iodobenzene, 1-iodocyclohexene and 1′-iodostyrene in the presence of N-nucleophiles containing pyridyl moieties (2-, 3- and 4-picolylamine, N-ethyl-4-picolylamine, di-(2-picolyl)amine) was carried out. The two types of iodo substrates differ substantially regarding the selectivity towards carbonylation: while the aminocarbonylation of iodobenzene resulted in the formation of carboxamide and ketocarboxamide mixtures under various conditions, with the predominant formation of ketocarboxamide even at low carbon monoxide pressure, the aminocarbonylation of iodoalkenes under same conditions gave the corresponding unsaturated carboxamide exclusively. Most of the carboxamides and phenylglyoxylamides, obtained via single and double carbon monoxide insertion, respectively, were isolated in yields of synthetic interest (up to 86{\%}). Low reaction rates and unexpected chemoselectivity towards carboxamide formation have been observed with di-(2-picolyl)amine as N-nucleophile in the aminocarbonylation of iodobenzene.",
keywords = "Carbon monoxide, Carbonylation, Homogeneous catalysis, Palladium, Picolylamine",
author = "M{\'a}t{\'e} Gergely and Roland Farkas and Attila Tak{\'a}cs and Andrea Petz and L. Koll{\'a}r",
year = "2014",
month = "1",
day = "14",
doi = "10.1016/j.tet.2013.11.087",
language = "English",
volume = "70",
pages = "218--224",
journal = "Tetrahedron",
issn = "0040-4020",
publisher = "Elsevier Limited",
number = "2",

}

TY - JOUR

T1 - Synthesis of N-picolylcarboxamides via palladium-catalysed aminocarbonylation of iodobenzene and iodoalkenes

AU - Gergely, Máté

AU - Farkas, Roland

AU - Takács, Attila

AU - Petz, Andrea

AU - Kollár, L.

PY - 2014/1/14

Y1 - 2014/1/14

N2 - A systematic investigation of the palladium-catalysed aminocarbonylation of iodobenzene, 1-iodocyclohexene and 1′-iodostyrene in the presence of N-nucleophiles containing pyridyl moieties (2-, 3- and 4-picolylamine, N-ethyl-4-picolylamine, di-(2-picolyl)amine) was carried out. The two types of iodo substrates differ substantially regarding the selectivity towards carbonylation: while the aminocarbonylation of iodobenzene resulted in the formation of carboxamide and ketocarboxamide mixtures under various conditions, with the predominant formation of ketocarboxamide even at low carbon monoxide pressure, the aminocarbonylation of iodoalkenes under same conditions gave the corresponding unsaturated carboxamide exclusively. Most of the carboxamides and phenylglyoxylamides, obtained via single and double carbon monoxide insertion, respectively, were isolated in yields of synthetic interest (up to 86%). Low reaction rates and unexpected chemoselectivity towards carboxamide formation have been observed with di-(2-picolyl)amine as N-nucleophile in the aminocarbonylation of iodobenzene.

AB - A systematic investigation of the palladium-catalysed aminocarbonylation of iodobenzene, 1-iodocyclohexene and 1′-iodostyrene in the presence of N-nucleophiles containing pyridyl moieties (2-, 3- and 4-picolylamine, N-ethyl-4-picolylamine, di-(2-picolyl)amine) was carried out. The two types of iodo substrates differ substantially regarding the selectivity towards carbonylation: while the aminocarbonylation of iodobenzene resulted in the formation of carboxamide and ketocarboxamide mixtures under various conditions, with the predominant formation of ketocarboxamide even at low carbon monoxide pressure, the aminocarbonylation of iodoalkenes under same conditions gave the corresponding unsaturated carboxamide exclusively. Most of the carboxamides and phenylglyoxylamides, obtained via single and double carbon monoxide insertion, respectively, were isolated in yields of synthetic interest (up to 86%). Low reaction rates and unexpected chemoselectivity towards carboxamide formation have been observed with di-(2-picolyl)amine as N-nucleophile in the aminocarbonylation of iodobenzene.

KW - Carbon monoxide

KW - Carbonylation

KW - Homogeneous catalysis

KW - Palladium

KW - Picolylamine

UR - http://www.scopus.com/inward/record.url?scp=84890799061&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84890799061&partnerID=8YFLogxK

U2 - 10.1016/j.tet.2013.11.087

DO - 10.1016/j.tet.2013.11.087

M3 - Article

AN - SCOPUS:84890799061

VL - 70

SP - 218

EP - 224

JO - Tetrahedron

JF - Tetrahedron

SN - 0040-4020

IS - 2

ER -