Synthesis of Linear α,β-Unsaturated Amides from Isocyanates and Alkenylaluminum Reagents

Bo Chen; Xiao-Feng Wu

doi:10.1055/s-0037-1610753

Synlett, Table of Contents

Synlett 2020; 31(08): 788-792
DOI: 10.1055/s-0037-1610753

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Synthesis of Linear α,β-Unsaturated Amides from Isocyanates and Alkenylaluminum Reagents

Bo Chen

^aDepartment of Chemistry, Zhejiang Sci-Tech University,Xiasha Campus, Hangzhou 310018, P. R. of China

^bLeibniz-Institut für Katalyse e.V. an der Universität Rostock, Albert-Einstein-Straße 29a 18059 Rostock, Germany Email: Xiao-feng.wu@catalysis.de

,

Xiao-Feng Wu∗

^aDepartment of Chemistry, Zhejiang Sci-Tech University,Xiasha Campus, Hangzhou 310018, P. R. of China

^bLeibniz-Institut für Katalyse e.V. an der Universität Rostock, Albert-Einstein-Straße 29a 18059 Rostock, Germany Email: Xiao-feng.wu@catalysis.de

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Abstract

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Abstract

A new approach has been developed for the synthesis of linear α,β-unsaturated amides by the direct coupling of isocyanates with alkenylaluminum reagents. At room temperature, the desired α,β-unsaturated amides were isolated in good to excellent yields with good functional-group tolerance in the absence of any catalyst or additive.

Key words

enamides - alkenylaluminum reagents - isocyanates - coupling reaction - catalyst-free

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References and Notes

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11 Amides 3; General ProcedureUnder argon, a solution of the appropriate alkenylaluminum (0.6 mmol) in hexane (0.6 mL) was added dropwise to a fresh solution of the appropriate isocyanate (0.5 mmol) in THF (1 mL) at 0 °C. The mixture was then warmed slowly to r.t. (25 °C) and stirred until the reaction was complete (16 h). After removal of solvent under reduced pressure, the pure product was obtained by column chromatography [silica gel, heptane–ethyl acetate (5:1)]. (2E)-N-Phenylnon-2-enamide (3aa)Colorless oil; yield: 83 mg (72%). ¹H NMR (500 MHz, CDCl₃): δ = 7.64 (s, 1 H), 7.51 (d, J = 8.1 Hz, 2 H), 7.22 (t, J = 7.8 Hz, 2 H), 7.02 (t, J = 7.4 Hz, 1 H), 6.90 (dt, J = 15.1, 7.0 Hz, 1 H), 5.89 (dt, J = 15.3, 1.6 Hz, 1 H), 2.11 (qd, J = 7.1, 1.5 Hz, 2 H), 1.41–1.32 (m, 2 H), 1.21 (dddt, J = 14.6, 9.2, 6.6, 3.5 Hz, 6 H), 0.82 (t, J = 6.9 Hz, 3 H). ¹³C NMR (126 MHz, CDCl₃): δ = 164.4, 146.6, 138.2, 129.1, 129.0, 124.2, 120.0, 32.2, 31.6, 28.9, 28.2, 22.6, 14.1. HRMS (ESI): m/z [M + H]⁺ calcd for C₁₅H₂₂NO: 232.1701; found: 232.1702.

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