Synlett 2019; 30(18): 2086-2090
DOI: 10.1055/s-0039-1690988
letter
© Georg Thieme Verlag Stuttgart · New York

Hydrogen-Bond-Promoted Metal-Free Hydroamination of Alkynes

a   École Nationale Supérieure de Chimie de Montpellier, Institut Charles Gerhardt, CNRS UMR 5253, AM2N, 8 rue de l’école normale, 34296 Montpellier Cedex 05, France   Email: marc.taillefer@enscm.fr
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b   Département de Chimie, 1045 avenue de la Médecine, Université Laval, Québec, QC, G1V 0A6, Canada   Email: thierry.ollevier@chm.ulaval.ca
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b   Département de Chimie, 1045 avenue de la Médecine, Université Laval, Québec, QC, G1V 0A6, Canada   Email: thierry.ollevier@chm.ulaval.ca
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a   École Nationale Supérieure de Chimie de Montpellier, Institut Charles Gerhardt, CNRS UMR 5253, AM2N, 8 rue de l’école normale, 34296 Montpellier Cedex 05, France   Email: marc.taillefer@enscm.fr
,
a   École Nationale Supérieure de Chimie de Montpellier, Institut Charles Gerhardt, CNRS UMR 5253, AM2N, 8 rue de l’école normale, 34296 Montpellier Cedex 05, France   Email: marc.taillefer@enscm.fr
c   IUF Institut Universitaire de France, 1 rue Descartes, 75231 Paris, France   Email: florian.monnier@enscm.fr
› Author Affiliations
Financial support from ANR CD2I (Agence Nationale de la Recherche), IUF, and CNRS is acknowledged. The authors thank the FRQNT Centre in Green Chemistry and Catalysis (CGCC) Strategic Cluster FRQNT-2020-RS4-265155-CCVC.
Further Information

Publication History

Received: 07 August 2019

Accepted after revision: 09 September 2019

Publication Date:
07 October 2019 (online)


Abstract

An original metal-free regio- and stereoselective intermolecular hydroamination of alkynes is described. Various (E)-enamines were obtained from arylacetylenes and aliphatic secondary amines in the presence of ethylene glycol as a solvent. The latter is assumed to play a major role in the mechanism through hydrogen bonding and proton exchange.

Supporting Information

 
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  • 20 It is also possible to recover the unused amine in a cold trap and then totally recycle it.
  • 21 Propargyl alcohol and oct-1-yne have also been tested; however, no product was obtained. This probably demonstrates that the solvent is the sole source of hydrogen bonding.
  • 22 Hydroamination of Alkynes with Amines; General Procedure Under an atmosphere of argon, a screw-cap vial was charged with ethylene glycol (250 μL, 8.9 equiv) and the appropriate alkyne (0.5 mmol, 1 equiv) and amine (2.5 mmol) at r.t. The tube was sealed under a positive pressure of argon and the mixture was stirred and heated to 150 °C for 8 h. The mixture was cooled to r.t., diluted with EtOAc (5 mL), and washed with H2O (3 × 2 mL) and brine (1 × 2 mL). The organic phase was dried (MgSO4), filtered, and concentrated under reduced pressure (rotary evaporator). Excess amine was then removed from the residue under high vacuum to give the desired enamine without any need for further purification. In the case of amines with high boiling points, such as dibutylamine or dipentylamine, the residues were dried by heating to 50 °C under high vacuum. (E)-N,N-Dipentyl-2-phenylethylenamine (3b) Solid; yield: 97 mg (75%). 1H NMR (400 MHz, CDCl3): δ = 7.20–7.14 (m, 4 H), 6.95–6.92 (m, 1 H), 6.76 (d, J = 14 Hz, 1 H), 5.07 (d, J = 14 Hz, 1 H), 3.07 (t, J = 7.1 Hz, 4 H), 1.60–1.54 (m, 4 H), 1.39–1.33 (m, 4 H), 1.33–1.28 (m, 4 H), 0.92 (t, J = 7.2 Hz, 6 H). 13C NMR (100 MHz, CDCl3): δ = 140.4, 138.5, 128.5, 123, 122.5, 96.3, 51.7, 29.2, 27.6, 22.5, 14.1. HRMS (ESI-TOF): m/z [M + H]+ Calcd for C18H30N: 260.2300; found: 260.2301.