Practical Fischer Indolization Using Bench-Stable Arylhydrazine Sulfonate as the Surrogate of Arylhydrazine

Wenjuan Li; Chaoren Shen; Yanping Zhu; Kaiwu Dong

doi:10.1055/s-0043-1763622

Synlett, Table of Contents

Synlett 2024; 35(10): 1165-1169
DOI: 10.1055/s-0043-1763622

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Thieme Chemistry Journals Awardees 2023

Practical Fischer Indolization Using Bench-Stable Arylhydrazine Sulfonate as the Surrogate of Arylhydrazine

Wenjuan Li

^aSchool of Pharmacy, Key Laboratory of Molecular Pharmacology and Drug Evaluation, Ministry of Education, Collaborative Innovation Center of Advanced Drug Delivery System and Biotech Drugs in Universities of Shandong, Yantai University, Shandong, Yantai, 264005, P. R. of China

^bShanghai Frontiers Science Center of Molecule Intelligent Syntheses & Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai 200062, P. R. of China

,

Chaoren Shen

^bShanghai Frontiers Science Center of Molecule Intelligent Syntheses & Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai 200062, P. R. of China

,

Yanping Zhu∗

^aSchool of Pharmacy, Key Laboratory of Molecular Pharmacology and Drug Evaluation, Ministry of Education, Collaborative Innovation Center of Advanced Drug Delivery System and Biotech Drugs in Universities of Shandong, Yantai University, Shandong, Yantai, 264005, P. R. of China

,

Kaiwu Dong ∗

^bShanghai Frontiers Science Center of Molecule Intelligent Syntheses & Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai 200062, P. R. of China

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Abstract

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Abstract

Fischer indolization using bench-stable sodium arylhydrazine sulfonate as a surrogate of arylhydrazine was developed. The preparation of arylhydrazine sulfonate was also modified by replacing sodium sulfite reductant with Pd-catalyzed hydrogen transfer. The straightforward synthesis of tetrahydrocarbazoles from the corresponding anilines was successfully conducted in a one-pot manner. A practical application of this method was demonstrated in the formal synthesis of pharmaceutical molecules Rizatriptan and Zolmitriptan.

Key words

arylhydrazine sulfonate - desulfonation - Fischer indolization - tryptamine - Rizatriptan - Zolmitriptan

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References

References and Notes

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26 General Procedure: Ketone (1.0 mmol, 1.0 equiv) was added dropwise into a solution of sodium arylhydrazine sulfonate (1.0 mmol, 1.0 equiv) in AcOH (5 mL) and the mixture was stirred at 70 °C for 1 hour. The reaction mixture was then cooled to room temperature and diluted with water. The mixture was extracted with ethyl acetate (2 × 50 mL), and the combined organic layer was washed with water and dried over anhydrous Na₂SO₄. The solvent was removed under reduced pressure and the obtained crude product was purified by silica-gel column chromatography using petroleum ether/EtOAc as eluent.
27 Selected analytical data for new compounds: 6-Butyl-2,3,4,9-tetrahydro-1H-carbazole (3c): Purified using petroleum ether/ethyl acetate (100:1, v/v) as eluent. Yield: 0.168 g (74%); yellow solid. ¹H NMR (600 MHz, CDCl₃): δ = 7.57 (s, 1 H), 7.25–7.24 (m, 1 H), 7.18 (d, J = 8.4, 1 H), 6.95 (dd, J = 7.8, 1.2 Hz, 1 H), 2.74–2.67 (m, 6 H), 1.97–1.84 (m, 4 H), 1.70–1.61 (m, 2 H), 1.38–1.34 (m, 2 H), 0.93 (t, J = 7.8 Hz, 3 H). ¹³C NMR (151 MHz, CDCl₃): δ = 134.2, 134.0, 133.6, 128.0, 122.0, 117.0, 109.9, 109.8, 35.9, 34.6, 23.33, 23.30, 23.2, 22.4, 20.9, 14.0. HRMS (ESI): m/z [M + H]⁺ calcd. for C₁₆H₂₁N: 228.1752; found: 228.1754. 6-Phenoxy-2,3,4,9-tetrahydro-1H-carbazole (3d): Purified using petroleum ether/ethyl acetate (95:5, v/v) as eluent. Yield: 0.179 g (68%); white solid. ¹H NMR (600 MHz, CDCl₃): δ = 7.72 (s, 1 H), 7.33–7.27 (m, 3 H), 7.17 (d, J = 2.4 Hz, 1 H), 7.05–7.00 (m, 1 H), 6.99–6.96 (m, 2 H), 6.89 (dd, J = 8.4, 2.4 Hz, 1 H), 2.77–2.74 (m, 2 H), 2.67–2.65 (m, 2 H), 1.99–1.85 (m, 4 H). ¹³C NMR (151 MHz, CDCl₃): δ = 159.7, 149.4, 135.7, 132.6, 129.4, 128.6, 121.6, 117.0, 114.6, 111.1, 110.4, 109.0, 23.3, 23.2, 23.1, 20.9. HRMS (ESI): m/z [M + H]⁺ calcd. for C₁₈H₁₇NO: 264.1388; found: 264.1391. 7-Butoxy-2,3,4,9-tetrahydro-1H-carbazole (3h): Purified using petroleum ether/ethyl acetate (95:5, v/v) as eluent. Yield: 0.163 g (67%); orange solid. ¹H NMR (600 MHz, CDCl₃): δ = 7.54 (s, 1 H), 7.15 (d, J = 8.4 Hz, 1 H), 6.93 (d, J = 2.4 Hz, 1 H), 6.77 (dd, J = 8.4, 2.4 Hz, 1 H), 4.01 (t, J = 6.6 Hz, 2 H), 2.73–2.65 (m, 4 H), 1.95–1.83 (m, 4 H), 1.84–1.74 (m, 2 H), 1.56–1.47 (m, 2 H), 0.98 (t, J = 7.4 Hz, 3 H). ¹³C NMR (151 MHz, CDCl₃): δ = 153.3, 135.0, 130.7, 128.2, 111.2, 110.8, 110.1, 101.6, 68.7, 31.6, 23.4, 23.3, 23.2, 21.0, 19.3, 13.9. HRMS (ESI): m/z [M + H]⁺ calcd. for C₁₆H₂₁NO: 243.1623; found: 243.1626.

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