Synlett 2021; 32(05): 517-520
DOI: 10.1055/s-0040-1706007
cluster
The Power of Transition Metals: An Unending Well-Spring of New Reactivity

Copper-Catalyzed Ring Expansion of Vinyl Aziridines under Mild Conditions

Eleonora Tosi
,
Kim Spielmann
,
,
Jean-Marc Campagne
This work was supported by the Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM) (K.S.), the ANR (ANR- 18-CE07-0038-01; E.T.), and the CNRS (Centre National de la Recherche Scientifique). Brigita Mudráková is kindly thanked for her help with the synthesis of some aziridines.


In expression of our respect to Professor Barry M. Trost on the occasion of his 80th birthday.

Abstract

Vinyl aziridines are versatile starting materials toward ring-expansion transformations. Such processes are widely used to give various medium or larger N-heterocycles of synthetic interest. This letter describes a copper-catalyzed ring expansion of vinyl aziridines to 3-pyrrolines by using a Cu(I) salt [(CuOTf)2·toluene or Cu(MeCN)4·PF6]. In particular, this transformation occurs under mild conditions (THF, rt).

Supporting Information



Publication History

Received: 29 October 2020

Accepted after revision: 08 December 2020

Publication Date:
05 January 2021 (online)

© 2021. Thieme. All rights reserved

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  • 14 4-Benzyl-2-methyl-1-tosyl-2,5-dihydro-1H-pyrrole (6a): Typical Procedure A flame-dried 10 mL flask equipped with a stirrer bar was charged with vinyl aziridine 1a (46 mg, 0.14 mmol, 1.00 equiv), (CuOTf)2·toluene (3.5 mg, 0.007 mmol, 0.05 equiv), and THF (0.7 mL), and the mixture was stirred for 2 h under argon at rt. The solvent evaporated under reduced pressure, and the crude product was purified by chromatography [silica gel, pentane–EtOAc (100:0 to 70:30)] to give a pale-yellow solid; yield: 28 mg (60%); mp 80–83 °C. FTIR (neat): 1402, 1355, 1178, 1163, 1090, 993, 945, 858, 840, 765, 664 cm–1. 1H NMR (400 MHz, CDCl3): δ = 7.65–7.63 (m, 2 H), 7.27–7.20 (m, 5 H), 7.01–6.99 (m, 2 H), 5.19–5.17 (m, 1 H), 4.48–4.46 (m, 1 H), 4.04–3.90 (m, 2 H), 3.33–3.23 (m, 2 H), 2.43 (s, 3 H), 1.38 (d, J = 6.40 Hz, 3 H). 13C NMR (100 MHz, CDCl3): δ = 143.2, 137.6, 137.1, 134.8, 129.6 (2 C), 128.5 (2 C), 128.5 (2 C), 127.4 (2 C), 126.5, 126.3, 63.4, 56.6, 35.1, 22.9, 21.5. HRMS-ASAP: m/z [M + H]+ calcd for C19H22NO2S: 328.1371; found: 328.1381.