Room Temperature, Metal-Free, Radical Chloroazidation of 1,6-Enynes

Wei-Wei Ying; Wei-Ting Chen; Wen-Hui Bao; Le-Han Gao; Xin-Ye Wang; Gan-Ping Chen; Guo-Ping Ge; Wen-Ting Wei

doi:10.1055/s-0037-1609752

Synlett, Table of Contents

Synlett 2018; 29(12): 1664-1668
DOI: 10.1055/s-0037-1609752

letter

Room Temperature, Metal-Free, Radical Chloroazidation of 1,6-Enynes

Wei-Wei Ying

School of Materials Science and Chemical Engineering, Ningbo University, Ningbo 315211, P. R. of China Email: weiwenting@nbu.edu.cn

,

Wei-Ting Chen

School of Materials Science and Chemical Engineering, Ningbo University, Ningbo 315211, P. R. of China Email: weiwenting@nbu.edu.cn

,

Wen-Hui Bao

School of Materials Science and Chemical Engineering, Ningbo University, Ningbo 315211, P. R. of China Email: weiwenting@nbu.edu.cn

,

Le-Han Gao

School of Materials Science and Chemical Engineering, Ningbo University, Ningbo 315211, P. R. of China Email: weiwenting@nbu.edu.cn

,

Xin-Ye Wang

School of Materials Science and Chemical Engineering, Ningbo University, Ningbo 315211, P. R. of China Email: weiwenting@nbu.edu.cn

,

Gan-Ping Chen

School of Materials Science and Chemical Engineering, Ningbo University, Ningbo 315211, P. R. of China Email: weiwenting@nbu.edu.cn

,

Guo-Ping Ge

School of Materials Science and Chemical Engineering, Ningbo University, Ningbo 315211, P. R. of China Email: weiwenting@nbu.edu.cn

,

Wen-Ting Wei*

School of Materials Science and Chemical Engineering, Ningbo University, Ningbo 315211, P. R. of China Email: weiwenting@nbu.edu.cn

› Author Affiliations

Abstract

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Abstract

Without employing any transition metal, a mild, practical, and environmentally attractive methodology has been developed for the chloroazidation of 1,6-enynes at room temperature. In this radical cascade process, three new chemical bonds, including C–Cl (Br, I), C–N, and C–C bonds, are formed in one step for the construction of 2-pyrrolidinones. The method is valuable because of its mild reaction conditions, operational simplicity, and the rich biological activity of the corresponding 2-pyrrolidinone products.

Key words

room-temperature reactions - metal-free reactions - radicals - cascade processes

Full Text

References

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13 General Procedure: To a Schlenk tube were added 1,6-enyne (0.2 mmol), TMSN₃ (0.4 mmol), NCS (0.4 mmol), PIDA (0.4 mmol, 2.0 equiv), and DCE (2 mL). The mixture was then stirred open in air at r.t. for the indicated time until complete consumption of starting material as monitored by TLC analysis. When the reaction was complete, the solution was concentrated under reduced pressure, and the mixture was purified by flash column chromatography over silica gel (hexane/ethyl acetate) to afford the desired product 4, which was analyzed by ¹H NMR, ¹³C NMR, and HRMS (see the Supporting Information). Typical Data for a Representative Compound: 3-(Azidomethyl)-4-(chloromethylene)-3-methyl-1-phenylpyrrolidin-2-one (4aaa): Yield: 38.6 mg (70%); yellow oil; 9:1 Z/E mixture. ¹H NMR (400 MHz, CDCl₃): δ = 7.72 (d, J = 8.4 Hz, 2 H), 7.42 (t, J = 7.6 Hz, 2 H), 7.21 (t, J = 7.6 Hz, 1 H), 6.44 (s, 0.1 H), 6.23 (s, 0.9 H), 4.52 (d, J = 2.0 Hz, 2 H), 3.73 (d, J = 11.6 Hz, 1 H), 3.45 (d, J = 12.0 Hz, 1 H), 1.38 (s, 2.7 H), 1.37 (s, 0.3 H); ¹³C NMR (100 MHz, CDCl₃): δ = 173.7, 138.4, 138.1, 129.1, 129.0, 127.6, 127.5, 125.4 (2), 120.3, 120.2, 114.6, 58.9, 50.6, 50.3, 21.8; HRMS (ESI): m/z [M+H]⁺ calcd for C₁₃H₁₄ClN₄O⁺: 277.0851; found: 277.0848.
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Supplementary Material

Supporting Information