Oxone-Promoted Cyclization/Hydrolysis of 1,5-Enenitriles Initiated via Direct C(sp3)–H Oxidative Functionalization: Access to Pyrrolidine-2,4-diones

Yu-Tao Guan; Jiao-Zhe Li; Xue-Er Cai; Sen-Jie Hu; Jun-Hao Zhang; Ke-Wei Lei; Hongxin Liu; Wen-Ting Wei

doi:10.1055/a-1930-7294

Synlett, Table of Contents

Synlett 2022; 33(19): 1917-1924
DOI: 10.1055/a-1930-7294

letter

Oxone-Promoted Cyclization/Hydrolysis of 1,5-Enenitriles Initiated via Direct C(sp³)–H Oxidative Functionalization: Access to Pyrrolidine-2,4-diones

Yu-Tao Guan

^aSchool of Materials Science and Chemical Engineering, Ningbo University, Ningbo, Zhejiang, 315211, P. R. of China

,

Jiao-Zhe Li

^aSchool of Materials Science and Chemical Engineering, Ningbo University, Ningbo, Zhejiang, 315211, P. R. of China

,

Xue-Er Cai

^aSchool of Materials Science and Chemical Engineering, Ningbo University, Ningbo, Zhejiang, 315211, P. R. of China

,

Sen-Jie Hu

^aSchool of Materials Science and Chemical Engineering, Ningbo University, Ningbo, Zhejiang, 315211, P. R. of China

,

Jun-Hao Zhang

^aSchool of Materials Science and Chemical Engineering, Ningbo University, Ningbo, Zhejiang, 315211, P. R. of China

,

Ke-Wei Lei∗

^aSchool of Materials Science and Chemical Engineering, Ningbo University, Ningbo, Zhejiang, 315211, P. R. of China

,

Hongxin Liu∗

^bCollege of Chemistry and Materials Engineering, Wenzhou University, Wenzhou, 325035, P. R. of China

,

Wen-Ting Wei∗

^aSchool of Materials Science and Chemical Engineering, Ningbo University, Ningbo, Zhejiang, 315211, P. R. of China

› Author Affiliations

Abstract

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Abstract

A novel method for assembling pyrrolidine-2,4-diones from 1,5-enenitriles and acetone/acetonitrile via a cyclization/hydrolysis has been established under metal-catalyst- and base-free conditions, with Oxone as a green oxidant and H₂O as an additive at 90–110 ℃. This strategy is highlighted by cyclization/hydrolysis of alkyl cyanides, achieving direct C(sp³)–H oxidative functionalization, and giving full conversion of the substrates with excellent functional group compatibility.

Key words

metal-catalyst-free - base-free - Oxone as a green oxidant - cyclization/hydrolysis

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References

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13 General Procedure To a Schlenk tube were added 1,5-enenitrile 1 (0.2 mmol), Oxone (2.0 equiv), H₂O (10.0 equiv), and acetone or acetonitrile 2 (1.0 mL). Then the tube was stirred at 90 °C or 110 °C, sealed in air for the indicated time until complete consumption of starting material as monitored by TLC and/or GC–MS analysis. After the reaction was finished, the solution was concentrated under reduced pressure, and the mixture was purified by flash column chromatography over silica gel (hexane/ethyl acetate = 2:1) to afford the desired product 3 and was analyzed by ¹H NMR and ¹³C NMR spectroscopy (see the Supporting Information). Typical Data for Representative Compound 1-(4-Methoxyphenyl)-3-methyl-3-(3-oxobutyl)pyrrolidine-2,4-dione (3a) Yellow oil (0.0509 g, 88% yield). ¹H NMR (400 MHz, CDCl₃): δ = 7.56–7.54 (m, 2 H), 6.96–6.93 (m, 2 H), 4.33–4.21 (m, 2 H), 3.82 (s, 3 H), 2.55 (t, J = 7.2 Hz, 2 H), 2.12 (s, 3 H), 2.08–2.03 (m, 2 H), 1.33 (s, 3 H). ¹³C NMR (101 MHz, CDCl₃): δ = 209.0, 207.3, 173.5, 157.2, 130.9, 122.3, 114.3, 56.3, 55.5, 51.1, 38.0, 29.8, 28.9, 19.8. HRMS (ESI): m/z calcd for C₁₆H₂₀NO₄ [M + H]⁺: 290.1387; found: 290.1381.

Supplementary Material

Supporting Information