Cu(II)/TBAI-Catalyzed Esterification of Acid Hydrazides via C(sp3)–H Oxidative Coupling

Guifeng Liu; Can Jin; Guomin Wu

doi:10.1055/s-0034-1379478

Synlett, Table of Contents

Synlett 2014; 25(20): 2908-2912
DOI: 10.1055/s-0034-1379478

letter

Cu(II)/TBAI-Catalyzed Esterification of Acid Hydrazides via C(sp³)–H Oxidative Coupling

Guifeng Liu*

^aInstitute of Chemical Industry of Forest Products, Chinese Academy of Forestry, Key Laboratory of Biomass Energy and Material of Jiangsu Province, Key and Open Laboratory on Forest Chemical Engineering, State Forestry Administration, National Engineering Laboratory for Biomass Chemical Utilization, Nanjing 210042, P. R. of China Fax: +86(25)85482457 Email: liuguifeng067@163.com

^bResearch Institute of New Technology, Chinese Academy of Forestry, Beijing 10091, P. R. of China

,

Can Jin

^aInstitute of Chemical Industry of Forest Products, Chinese Academy of Forestry, Key Laboratory of Biomass Energy and Material of Jiangsu Province, Key and Open Laboratory on Forest Chemical Engineering, State Forestry Administration, National Engineering Laboratory for Biomass Chemical Utilization, Nanjing 210042, P. R. of China Fax: +86(25)85482457 Email: liuguifeng067@163.com

^bResearch Institute of New Technology, Chinese Academy of Forestry, Beijing 10091, P. R. of China

,

Guomin Wu

^aInstitute of Chemical Industry of Forest Products, Chinese Academy of Forestry, Key Laboratory of Biomass Energy and Material of Jiangsu Province, Key and Open Laboratory on Forest Chemical Engineering, State Forestry Administration, National Engineering Laboratory for Biomass Chemical Utilization, Nanjing 210042, P. R. of China Fax: +86(25)85482457 Email: liuguifeng067@163.com

^bResearch Institute of New Technology, Chinese Academy of Forestry, Beijing 10091, P. R. of China

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Abstract

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Abstract

A Cu²⁺/TBAI-cocatalyzed allylic ester synthesis was developed, which allows a direct coupling of acid hydrazides and cycloalkanes. This process makes use of commercially available, inexpensive, and abundant starting materials. Based on the extensive experimental data, a plausible radical mechanism was suggested.

Key words

Cu²⁺/TBAI cocatalysis - direct coupling - acid hydrazides

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References

References and Notes

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12 Synthesis of 3a–p A mixture of 1 (0.2 mmol), cycloalkane (2 mL), Cu(OAc)₂ (10 mol%), TBAI (20 mol%), and TBHP (3 equiv) was stirred at 140 °C under N₂ atmosphere for 36 h. The reaction mixture was washed with H₂O and the aqueous phase was extracted with EtOAc (3×). The combined organic layer was washed with brine, dried over Na₂SO₄, and evaporated under reduced pressure. The crude product was purified by silica gel column chromatography to give the corresponding product. Compound 3a: yield 61%. ¹H NMR (500 MHz, CDCl₃): δ = 8.06 (d, J = 8.4 Hz, 2 H), 7.55 (m, 1 H), 7.42 (dd, J = 8.2, 7.0 Hz, 2 H), 6.01 (m, 1 H), 5.85 (m, 1 H), 5.51 (m, 1 H), 2.15 (m, 1 H), 2.04 (m, 1 H), 1.96 (m, 1 H), 1.84 (m, 1 H), 1.68 (m, 1 H). ¹³C NMR (125 MHz, CDCl₃): δ = 166.2, 132.8, 132.7, 130.8, 129.5, 128.2, 125.7, 68.5, 28.4, 24.9, 18.9. HRMS: m/z calcd for C₁₃H₁₄O₂ [M]⁺: 202.2491; found: 202.2488. Compound 3b: yield 70%. ¹H NMR (500 MHz, CDCl₃): δ = 8.00 (d, J = 9.0 Hz, 2 H), 6.90 (d, J = 9.0 Hz, 2 H), 5.96 (m, 1 H), 5.81 (m, 1 H), 5.45 (m, 1 H), 3.82 (s, 3 H), 2.04 (m, 3 H), 1.82 (m, 2 H), 1.67 (m, 1 H). ¹³C NMR (125 MHz, CDCl₃): δ = 165.9, 163.2, 132.5, 131.5, 125.9, 123.2, 113.4, 68.2, 55.3, 28.4, 24.9, 18.9. HRMS: m/z calcd for C₁₄H₁₆O₃ [M]⁺: 232.2750; found: 232.2755. Compound 3c: yield 58%. ¹H NMR (500 MHz, CDCl₃): δ = 7.70 (m, 2 H), 7.13 (m, 2 H), 5.80 (m, 1 H), 5.68 (m, 1 H), 5.35 (m, 1 H), 2.20 (m, 3 H), 1.99–1.65 (m, 6 H). ¹³C NMR (125 MHz, CDCl₃): δ = 165.8, 137.5, 133.1, 132.2, 130.3, 129.6, 127.7, 126.4, 125.2, 68.0, 28.1, 24.6, 20.8, 18.6.. HRMS: m/z calcd for C₁₄H₁₆O₃ [M]⁺: 232.2750; found: 232.2753 Compound 3d: yield 72%. ¹H NMR (500 MHz, CDCl₃): δ = 7.52 (dd, J = 8.4, 2.0 Hz, 1 H), 7.40 (d, J = 2.0 Hz, 1 H), 6.69 (m, 1 H), 5.83 (m, 1 H), 5.68 (m, 1 H), 5.28 (m, 1 H), 3.75 (s, 3 H), 3.70 (s, 3 H), 2.20–1.40 (m, 6 H). ¹³C NMR (125 MHz, CDCl₃): δ = 165.4, 152.4, 148.1, 132.0, 125.5, 123.0, 122.8, 111.5, 109.7, 67.9, 55.4, 28.1, 24.5, 18.2. HRMS: m/z calcd for C₁₅H₁₈O₄ [M]⁺: 262.3010; found: 262.3013. Compound 3e: yield 39%. ¹H NMR (500 MHz, CDCl₃): δ = 7.90 (d, J = 8.6 Hz, 2 H), 7.56 (d, J = 8.6 Hz, 2 H), 6.01 (m, 1 H), 5.832 (m, 1 H), 5.50 (m, 1 H), 2.05 (m, 3 H), 1.83 (m, 2 H), 1.70 (m, 1 H). ¹³C NMR (125 MHz, CDCl₃): δ = 165.3, 132.8, 131.4, 130.99, 129.7, 127.67, 125.9, 68.8, 28.4, 24.8, 18.2.. HRMS: m/z calcd for C₁₃H₁₃BrO₂ [M]⁺: 281.1451; found: 281.1450. Compound 3f: yield 30%. ¹H NMR (500 MHz, CDCl₃): δ = 8.28 (d, J = 8.8 Hz, 2 H), 8.22 (d, J = 8.8 Hz, 2 H), 6.05 (m, 1 H), 5.84 (m, 1 H), 5.55 (m, 1 H), 2.19–1.72 (m, 6 H). ¹³C NMR (125 MHz, CDCl₃): δ = 164.0, 150.1, 135.9, 133.9, 130.4, 124.7, 123.2, 69.6, 28.0, 24.7, 18.6. HRMS: m/z calcd for C₁₃H₁₃NO₄ [M]⁺: 247.2466; found: 247.2463. Compound 3g: yield 33%. ¹H NMR (500 MHz, CDCl₃): δ = 8.07 (m, 2 H), 7.10 (m, 2 H), 6.01 (m, 1 H), 5.82 (m, 1 H), 5.50 (m, 1 H), 2.06 (m, 3 H), 1.85 (m, 2 H), 1.70 (m, 1 H). ¹³C NMR (125 MHz, CDCl₃): δ = 166.9, 165.2, 164.3, 132.9, 132.1, 132.0, 126.9, 125.5, 115.4, 115.2, 68.7, 28.3, 24.9, 18.9. HRMS: m/z calcd for C₁₃H₁₃FO₂ [M]⁺: 220.2395; found: 220.2393. Compound 3h: yield 45%. ¹H NMR (500 MHz, CDCl3): δ = 7.98 (d, J = 8.4 Hz, 2 H), 7.40 (d, J = 8.4 Hz, 2 H), 6.01 (m, 1 H), 5.82 (m, 1 H), 5.50 (m, 1 H), 2.05 (m, 3 H), 1.83 (m, 2 H), 1.70 (m, 1 H). ¹³C NMR (125 MHz, CDCl₃): δ = 165.2, 139.0, 132.9, 130.9, 129.1, 128.5, 125.4, 68.8, 28.3, 24.8, 18.8. HRMS: m/z calcd for C₁₃H₁₃ClO₂ [M]⁺: 236.6941; found: 236.6945. Compound 3i: yield 37%. ¹H NMR (500 MHz, CDCl3): δ = 7.80 (m, 1 H), 7.53 (m, 1 H), 7.08 (m, 1 H), 6.00 (m, 1 H), 5.81 (m, 1 H), 5.47 (m, 1 H), 2.03 (m, 3 H), 1.84 (m, 2 H), 1.68 (m, 1 H). ¹³C NMR (125 MHz, CDCl₃): δ = 161.8, 134.3, 133.1, 132.9, 132.0, 127.5, 125.4, 68.8, 28.2, 24.8, 18.8. HRMS: m/z calcd for C₁₁H₁₂SO₂ [M]⁺: 208.2768; found: 208.2770. Compound 3j: yield 21%. ¹H NMR (500 MHz, CDCl₃): δ = 7.92 (m, 1 H), 7.64 (m, 1 H), 7.15 (m, 1 H), 6.21 (m, 1 H), 5.89 (m, 1 H), 5.67 (m, 1 H), 2.3 (m, 3 H), 1.88 (m, 2 H), 1.78 (m, 1 H). ¹³C NMR (125 MHz, CDCl₃): δ = 162.5, 134.9, 134.1, 132.9, 132.0, 128.3, 125.9, 68.8, 28.5, 24.3, 18.1. HRMS: m/z calcd for C₁₁H₁₂O₃ [M]⁺: 192.2112; found: 192.2110. Compound 3m: yield 65%. ¹H NMR (500 MHz, CDCl₃): δ = 8.02 (d, J = 8.4 Hz, 2 H), 7.53 (t, J = 7.2 Hz, 1 H), 7.40 (m, 2 H), 6.18 (m, 1 H), 5.92 (m, 2 H), 2.65 (m, 1 H), 2.33 (m, 2 H), 1.90 (m, 1 H). ¹³C NMR (125 MHz, CDCl₃): δ = 166.6, 137.7, 132.7, 130.7, 129.5, 129.4, 128.2, 81.1, 31.2, 29.9. HRMS: m/z calcd for C₁₂H₁₂O₂ [M]⁺: 288.2225; found: 188.2220. Compound 3n: yield 43%. ¹H NMR (500 MHz, CDCl₃): δ = 8.08 (m, 2 H), 7.57 (m, 1 H), 7.42 (m, 2 H), 5.91 (m, 1 H), 5.79 (m, 1 H), 5.66 (m, 1 H), 2.27 (m, 1 H), 2.14 (m, 1 H), 2.01 (m, 2 H), 1.90–1.66 (m, 3 H), 1.53–1.45 (m, 1 H). ¹³C NMR (125 MHz, CDCl₃): δ = 166.1, 133.7, 133.0, 132.2, 130.9, 129.8, 128.5, 74.9, 33.1, 28.8, 26.9, 26.8. HRMS: m/z calcd for C₁₄H₁₆O₂ [M]⁺: 216.2756; found: 216.2751. Compound 3o: yield 68%. ¹H NMR (500 MHz, CDCl₃): δ = 8.02 (d, J = 8.4 Hz, 2 H), 7.55 (t, J = 8.4 Hz, 1 H), 7.43 (t, J = 7.6 Hz, 2 H), 5.93 (m, 1 H), 5.72 (m, 1 H), 5.61 (m, 1 H), 2.33 (m, 1 H), 2.15 (m, 1 H), 2.04 (m, 1 H), 1.66 (m, 6 H), 1.42 (m, 1 H). ¹³C NMR (125 MHz, CDCl₃): δ = 166.0, 132.7, 130.7, 130.7, 129.8, 129.5, 128.2, 73.0, 35.1, 28.8, 26.4, 25.9, 23.4. HRMS: m/z calcd for C₁₅H₁₈O₂ [M]⁺: 230.3022; found: 230.3019.

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