Iron-Catalyzed Regioselective Decarboxylative Alkylation of Coumarins and Chromones with Alkyl Diacyl Peroxides

Can Jin; Xun Zhang; Bin Sun; Zhiyang Yan; Tengwei Xu

doi:10.1055/s-0037-1611864

Synlett, Table of Contents

Synlett 2019; 30(13): 1585-1591
DOI: 10.1055/s-0037-1611864

letter

Iron-Catalyzed Regioselective Decarboxylative Alkylation of Coumarins and Chromones with Alkyl Diacyl Peroxides

Can Jin∗

^aCollege of Pharmaceutical Sciences, Zhejiang University of Technology, Hangzhou 310014, P. R. of China Email: jincan@zjut.edu.cn

,

Xun Zhang

^aCollege of Pharmaceutical Sciences, Zhejiang University of Technology, Hangzhou 310014, P. R. of China Email: jincan@zjut.edu.cn

,

Bin Sun∗

^bCollaborative Innovation Center of Yangtze River Delta Region Green Pharmaceuticals, Zhejiang University of Technology, Hangzhou 310014, P. R. of China Email: sunbin@zjut.edu.cn

,

Zhiyang Yan

^aCollege of Pharmaceutical Sciences, Zhejiang University of Technology, Hangzhou 310014, P. R. of China Email: jincan@zjut.edu.cn

,

Tengwei Xu

^aCollege of Pharmaceutical Sciences, Zhejiang University of Technology, Hangzhou 310014, P. R. of China Email: jincan@zjut.edu.cn

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Abstract

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Abstract

A facile iron-catalyzed decarboxylative radical coupling of alkyl diacyl peroxides with coumarins or chromones has been developed, affording a highly efficient approach to synthesize a variety of α-alkylated coumarins and β-alkylated chromones. The reaction proceeded smoothly without adding any ligand or additive and provided the corresponding products containing a wide scope of functional groups in moderate to excellent yields. This protocol was highlighted by its high regioselectivity, readily available starting materials, and operational simplicity.

Key words

coumarins - chromones - C–C bond - iron-catalyzed - decarboxylation

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References

References and Notes

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13 General Procedure for the Synthesis of 3 or 5 (3aa as an Example) A 10 mL Schlenk tube was charged with coumarin (1a, 88 mg, 0.6mmol), LPO (2a, 477 mg, 1.2 mmol), Fe(OTf)₃ (15 mg, 0.03 mmol), and dioxane (3.0 mL). The tube was evacuated and backfilled with N₂ for three times. The mixture was then heated at 70 ℃ and stirred for 8 h. After the reaction finished, the reaction mixture was extracted with DCM (30 mL). The organic layer was dried over Na₂SO₄ and concentrated under reduced pressure. The crude product was purified by flash chromatography on silica gel column (ethyl acetate/hexane, 1:80) to afford 3aa (149 mg, 83%) as a white solid. Compound 3aa: white solid; mp 59.6–60.3 ℃, 83% (149 mg). ¹H NMR (400 MHz, CDCl₃): δ = 7.47 (s, 1 H), 7.45–7.42 (m, 2 H), 7.31 (d, J = 8.0 Hz, 1 H), 7.26 (d, J = 8.0 Hz, 1 H), 2.56 (t, J = 7.8 Hz, 2 H), 1.68–1.60 (m, 2 H), 1.39–1.25 (m, 16 H), 0.88 (t, J = 6.8 Hz, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 161.8, 153.1, 138.3, 130.4, 130.1, 127.1, 124.2, 119.6, 116.4, 31.9, 30.8, 29.63, 29.60, 29.56, 29.4, 29.3, 28.0, 22.7, 14.1. HRMS: m/z calcd for C₂₀H₂₉O₂ [M + H]⁺: 301.2162; found: 301.2170.

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