Synlett 2016; 27(06): 934-940
DOI: 10.1055/s-0035-1561333
letter
© Georg Thieme Verlag Stuttgart · New York

Triflic Acid Catalyzed Intermolecular α-Amination of Pterolactams To Give 5-Arylaminopyrrolidinones via N-Acyliminium Species

Gina-Mirabela Dumitriu
a   Department of Organic Chemistry, Faculty of Chemistry, ‘Al. I. Cuza’ University of Iasi, B-dul Carol I, Nr. 11, Corp A, 700506, Iasi, Romania
,
Elena Bîcu
a   Department of Organic Chemistry, Faculty of Chemistry, ‘Al. I. Cuza’ University of Iasi, B-dul Carol I, Nr. 11, Corp A, 700506, Iasi, Romania
,
Ulku Eryuruk
b   Hautes Etudes d’Ingénieur (HEI), Groupe HEI-ISA-ISEN, UCLille, Laboratoire de Pharmacochimie, 13 rue de Toul, BP 41290, 59014 Lille Cedex, France   eMail: alina.ghinet@hei.fr
,
Dalila Belei
a   Department of Organic Chemistry, Faculty of Chemistry, ‘Al. I. Cuza’ University of Iasi, B-dul Carol I, Nr. 11, Corp A, 700506, Iasi, Romania
,
Benoît Rigo
b   Hautes Etudes d’Ingénieur (HEI), Groupe HEI-ISA-ISEN, UCLille, Laboratoire de Pharmacochimie, 13 rue de Toul, BP 41290, 59014 Lille Cedex, France   eMail: alina.ghinet@hei.fr
c   Univ. Lille, Inserm, CHU Lille, U995-LIRIC-Lille Inflammation Research International Center, 59000 Lille, France
,
Adam Daïch*
d   URCOM, EA 3221, INC3M CNRS-FR 3038, UFR des Sciences & Techniques, Université du Havre, BP: 1123, 25 rue Philipe Lebon, 76063 Le Havre Cedex, France   eMail: adam.daich@univ-lehavre.fr
,
Alina Ghinet*
a   Department of Organic Chemistry, Faculty of Chemistry, ‘Al. I. Cuza’ University of Iasi, B-dul Carol I, Nr. 11, Corp A, 700506, Iasi, Romania
b   Hautes Etudes d’Ingénieur (HEI), Groupe HEI-ISA-ISEN, UCLille, Laboratoire de Pharmacochimie, 13 rue de Toul, BP 41290, 59014 Lille Cedex, France   eMail: alina.ghinet@hei.fr
c   Univ. Lille, Inserm, CHU Lille, U995-LIRIC-Lille Inflammation Research International Center, 59000 Lille, France
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Publikationsverlauf

Received: 01. November 2015

Accepted after revision: 30. Dezember 2015

Publikationsdatum:
26. Januar 2016 (online)


Abstract

A mild and efficient α-aza-amidoalkylation for the synthesis of 5-arylaminopyrrolidinones is presented. The key step of this reaction is the intermolecular interception of an N-acyliminium species, generated under the acidic conditions, with nitrogen nucleophiles such as N-silylamines.

Supporting Information

 
  • References and Notes

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  • 33 General Procedure for the Synthesis of 1-Alkyl-5-Arylaminopyrrolidinones Method A: Under an inert atmosphere, aniline 19ad (1.2 equiv) was added to hydroxylactam 18ae in anhydrous CH2Cl2. TfOH (10–15% vol.) was slowly added by using a syringe, and the resulting brown, homogeneous solution was stirred at 50 °C for 24–48 h. H2O (50 mL) and CH2Cl2 (50 mL) were added, and the mixture was shaken in an extraction funnel, whereupon the organic phase lost most of its brown color. The organic phase was washed with H2O (3 × 50 mL), dried over MgSO4, and filtered. The residue obtained after evaporation was purified by flash chromatography. Method B: Under an inert atmosphere, silylated aniline 20ad (1.2 equiv) was added to hydroxylactam 18ae. TfOH (1–2% vol.) was slowly added by using a syringe, and the now brown, homogeneous solution was stirred at room temperature for 1 min to 24 h. H2O (50 mL) and CH2Cl2 (50 mL) were added slowly to the reaction mixture, which was then shaken in an extraction funnel, whereupon the organic phase lost most of its brown color. The organic phase was washed with H2O (3 × 50 mL), dried over MgSO4, and filtered. The residue obtained after evaporation was purified by flash chromatography.
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