LiNTf2-Catalyzed Aminolysis of Lactones with Stoichiometric Quantities of Amines

Claudia Lalli; Andrea Trabocchi; Gloria Menchi; Antonio Guarna

doi:10.1055/s-2007-1000882

LETTER

LiNTf₂-Catalyzed Aminolysis of Lactones with Stoichiometric Quantities of Amines

Claudia Lalli, Andrea Trabocchi, Gloria Menchi, Antonio Guarna*
Dipartimento di Chimica Organica ‘Ugo Schiff’ and Laboratorio per la Progettazione, Sintesi e Studio di Eterocicli Bioattivi (HeteroBioLab), Università degli Studi di Firenze, Polo Scientifico e Tecnologico, Via della Lastruccia 13, 50019 Sesto Fiorentino (FI), Italy
Fax: +39(055)4573569; e-Mail: antonio.guarna@unifi.it;

Abstract

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Abstract

LiNTf₂ in the reaction of lactones with amines is able to activate cyclic esters towards ring opening, thus leading to clean open-chain amides under mild conditions and using a stoichiometric amount of amine. The generality of the method was demonstrated by a range of selected lactones and amines.

Key words

amides - ring opening - Lewis acids - lactones - catalysis

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References

References and Notes

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Unpublished data.

General Procedure for Lactone Aminolysis; Synthesis of N -Allyl-4-hydroxybutyramide(3): To a solution of γ-butyrolactone (1; 1 equiv) and allylamine (2; 1 equiv) in anhyd CHCl₃ (0.5 mL/mmol) was added under a nitrogen atmosphere LiNTf₂ (0.5 equiv). The mixture was stirred in a sealed vial at 85 °C (oil bath) for 40 h, then it was washed with a sat. NaHCO₃ solution, and the organic phase was evaporated to give the title product as a clean viscous oil (99%). ¹H NMR (200 MHz, CDCl₃): δ = 6.62 (br, 1 H, NH), 5.73-6.03 (m, 1 H, =CH), 5.04-5.23 (m, 2 H, =CH₂), 4.02 (br, 1 H, OH), 3.88 (t, J = 5.5 Hz, 2 H), 3.72 (t, J = 5.5 Hz, 2 H), 2.40 (t, J = 6.2 Hz, 2 H), 1.79-1.96 (m, 2 H). ¹³C NMR (50 MHz, CDCl₃): δ = 178.2 (s, C=O), 137.1 (d, =CH), 119.4 (t, =CH₂), 65.1 (t, CH₂), 45.4 (t, CH₂), 36.4 (t, CH₂), 31.5 (t, CH₂). MS (EI, 70 eV): m/z (%) = 143 (1) [M⁺], 99 (28), 84 (10), 69 (14), 57 (100). Anal. Calcd for C₇H₁₃NO₂: C, 58.72; H, 9.15; N, 9.78. Found: C, 58.70; H, 9.14; N, 9.76.