Copper-Catalyzed Ring Expansion of Vinyl Aziridines under Mild Conditions

Eleonora Tosi; Kim Spielmann; Renata Marcia de Figueiredo; Jean-Marc Campagne

doi:10.1055/s-0040-1706007

Synlett, Inhaltsverzeichnis

Synlett 2021; 32(05): 517-520
DOI: 10.1055/s-0040-1706007

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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

,

Renata Marcia de Figueiredo ∗

,

Jean-Marc Campagne∗

Abstract

Alle Artikel dieser Rubrik

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

Key words

ring expansion - vinyl aziridines - pyrrolines - copper catalysis - heterocycles

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Referenzen

References and Notes

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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.

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