Brønsted Acid Catalyzed Intramolecular Allylic Substitution Reaction of Allylic Alcohols: A Facile Synthesis of 2-Vinylchromans

Yun-Fan Li; Yu-Ting Xi; Kai-Ji Hu; Qitao Tan; Chang-Hua Ding; Bin Xu

doi:10.1055/a-2301-9223

Synlett, Inhaltsverzeichnis

Synlett 2024; 35(18): 2148-2152
DOI: 10.1055/a-2301-9223

letter

Brønsted Acid Catalyzed Intramolecular Allylic Substitution Reaction of Allylic Alcohols: A Facile Synthesis of 2-Vinylchromans

Autor*innen

Yun-Fan Li

^aDepartment of Chemistry, Shanghai Engineering Research Center of Organ Repair, Innovative Drug Research Center, Shanghai University, Shanghai 200444, P. R. of China
Yu-Ting Xi

^aDepartment of Chemistry, Shanghai Engineering Research Center of Organ Repair, Innovative Drug Research Center, Shanghai University, Shanghai 200444, P. R. of China
Kai-Ji Hu

^aDepartment of Chemistry, Shanghai Engineering Research Center of Organ Repair, Innovative Drug Research Center, Shanghai University, Shanghai 200444, P. R. of China
Qitao Tan

^aDepartment of Chemistry, Shanghai Engineering Research Center of Organ Repair, Innovative Drug Research Center, Shanghai University, Shanghai 200444, P. R. of China
Chang-Hua Ding∗

^aDepartment of Chemistry, Shanghai Engineering Research Center of Organ Repair, Innovative Drug Research Center, Shanghai University, Shanghai 200444, P. R. of China
Bin Xu∗

^aDepartment of Chemistry, Shanghai Engineering Research Center of Organ Repair, Innovative Drug Research Center, Shanghai University, Shanghai 200444, P. R. of China

^bState Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, P. R. of China

Abstract

Alle Artikel dieser Rubrik

Abstract

Brønsted acid catalyzed intramolecular allylic substitution reaction of secondary and tertiary allylic alcohols has been developed. A variety of 2-vinylchromans were efficiently prepared in moderate to excellent yields. The given method features wide substrate scope, operational simplicity, and mild, metal-free reaction conditions. The practicability of the method was demonstrated by a gram-scale reaction and further derivations of the product. Preliminarily studies on a catalytic asymmetric reaction were also undertaken.

Key words

Brønsted acid - allylic substitution reaction - allylic alcohol - chroman - metal-free reactions

Volltext

Referenzen

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12 Synthesis of Products 2; General ProcedureTo a flame-dried Schlenk tube with a magnetic stirring bar were charged compound 1 (0.3 mmol), anhydrous CH₂Cl₂ (3.0 mL), and Tf₂NH (8.4 mg, 0.03 mmol) in sequence. The resulting mixture was stirred at 25 °C under an N₂ atmosphere until full conversion as monitored by TLC. The reaction was quenched with water. The aqueous phase was extracted with CH₂Cl₂ (3 × 5 mL) and the combined organic phases were dried over anhydrous Na₂SO₄. After filtration through a thin pad of Celite, the filtrate was concentrated under reduced pressure. The residue was purified by flash column chromatography on silica gel (petroleum ether/EtOAc, 20:1 v/v) to afford 2.8-Fluoro-2-vinylchromane (2b): Yield: 30.4 mg (57%); yellow oil. ¹H NMR (400 MHz, CDCl₃): δ = 6.95–6.87 (m, 1 H), 6.86–6.78 (m, 1 H), 6.76–6.72 (m, 1 H), 6.00 (ddd, J = 17.5, 10.6, 5.5 Hz, 1 H), 5.40 (d, J = 17.3 Hz, 1 H), 5.26 (d, J = 10.6 Hz, 1 H), 4.66–4.62 (m, 1 H), 2.88–2.73 (m, 2 H), 2.13–2.07 (m, 1 H), 1.92–1.80 (m, 1 H). ¹³C NMR (101 MHz, CDCl₃): δ = 151.7 (d, J = 244.6 Hz), 142.8 (d, J = 10.8 Hz), 136.9, 124.5, 124.4, 119.5 (d, J = 7.3 Hz), 116.8, 113.8 (d, J = 18.1 Hz), 76.4, 27.1, 23.8 (d, J = 2.6 Hz). ¹⁹F NMR (376 MHz, CDCl₃): δ = –137.1 (m, Ar-F). IR (KBr): 2927, 2851, 1506, 1420, 1301, 1251, 1121, 1044, 926, 853, 797 cm^–1. HRMS (EI): m/z [M]⁺ calcd for C₁₁H₁₁FO: 178.0788; found: 178.0786.7-Methyl-2-vinylchromane (2c): Yield: 39.2 mg (75%); yellow oil. ¹H NMR (400 MHz, CDCl₃): δ = 7.00–6.91 (m, 1 H), 6.77–6.62 (m, 2 H), 6.00 (ddd, J = 17.3, 10.6, 5.6 Hz, 1 H), 5.40 (d, J = 17.3 Hz, 1 H), 5.25 (d, J = 10.6 Hz, 1 H), 4.58–4.52 (m, 1 H), 2.92–2.68 (m, 2 H), 2.30 (s, 3 H), 2.10–2.04 (m, 1 H), 1.90–1.79 (m, 1 H). ¹³C NMR (101 MHz, CDCl₃): δ = 154.4, 137.8, 137.3, 129.4, 121.2, 118.8, 117.3, 116.3, 76.2, 27.7, 23.9, 21.2. IR (KBr): 2927, 2851, 1572, 1506, 1420, 1301, 1251, 1121, 1044, 997, 926, 799 cm^–1. HRMS (ESI): m/z [M + H]⁺ calcd for C₁₂H₁₅O: 175.1117; found: 175.1120.7-Chloro-2-vinylchromane (2d): Yield: 47.6 mg (81%); yellow oil. ¹H NMR (400 MHz, CDCl₃): δ = 6.95 (d, J = 8.2 Hz, 1 H), 6.87 (d, J = 2.1 Hz, 1 H), 6.81 (dd, J = 8.1, 2.1 Hz, 1 H), 5.96 (ddd, J = 17.3, 10.6, 5.5 Hz, 1 H), 5.37 (d, J = 17.3 Hz, 1 H), 5.24 (d, J = 10.6 Hz, 1 H), 4.58–4.53 (m, 1 H), 2.86–2.68 (m, 2 H), 2.10–2.03 (m, 1 H), 1.91–1.77 (m, 1 H). ¹³C NMR (101 MHz, CDCl₃): δ = 155.2, 137.2, 132.3, 130.4, 120.43, 120.42, 117.1, 116.6, 76.3, 27.2, 23.7. IR (KBr): 2932, 1573, 1483, 1415, 1295, 1224, 1116, 1074, 1040, 993, 918, 854, 796 cm^–1. HRMS (EI): m/z [M]⁺ calcd for C₁₁H₁₁ClO: 194.0493; found: 194.0496.6-(tert-Butyl)-2-vinylchromane (2f): Yield: 51.3 mg (79%); yellow oil. ¹H NMR (400 MHz, CDCl₃): δ = 7.17–7.13 (m, 1 H), 7.07–7.05 (m, 1 H), 6.82 (d, J = 8.5 Hz, 1 H), 6.01 (ddd, J = 17.3, 10.6, 5.7 Hz, 1 H), 5.40 (d, J = 17.2 Hz, 1 H), 5.25 (d, J = 10.5 Hz, 1 H), 4.57–4.51 (m, 1 H), 2.92–2.66 (m, 2 H), 2.11–2.04 (m, 1 H), 1.91–1.81 (m, 1 H), 1.31 (s, 9 H). ¹³C NMR (101 MHz, CDCl₃): δ = 152.3, 142.9, 137.9, 126.3, 124.5, 120.9, 116.4, 116.3, 76.3, 34.1, 31.7, 27.8, 24.6. IR (KBr): 2956, 2863, 1498, 1297, 1238, 1129, 991, 923, 819 cm^–1. HRMS (ESI): m/z [M + H]⁺ calcd for C₁₅H₂₁O: 217.1587: found: 217.1582.5-Chloro-2-vinylchromane (2k): Yield: 48.2 mg (83%); yellow oil. ¹H NMR (600 MHz, CDCl₃): δ = 7.03 (t, J = 8.1 Hz, 1 H), 6.93 (d, J = 7.9 Hz, 1 H), 6.78 (d, J = 8.4 Hz, 1 H), 5.97 (ddd, J = 16.8, 10.6, 5.6 Hz, 1 H), 5.37 (d, J = 17.2 Hz, 1 H), 5.25 (d, J = 10.7 Hz, 1 H), 4.55–4.45 (m, 1 H), 2.90–2.83 (m, 1 H), 2.80–2.72 (m, 1 H), 2.14–2.08 (m, 1 H), 1.87–1.80 (m, 1 H). ¹³C NMR (101 MHz, CDCl₃): δ = 155.7, 137.1, 134.6, 127.6, 121.0, 120.7, 116.7, 115.6, 76.0, 27.2, 22.6. IR (KBr): 2939, 1570, 1456, 1291, 1249, 1186, 1042, 996, 902, 774 cm^–1. HRMS (EI): m/z [M]⁺ calcd for C₁₁H₁₁ClO: 194.0493; found: 194.0494.2-Vinyl-3,4-dihydro-2H-benzo[g]chromene (2l): Yield: 47.9 mg (76%); white solid; mp 55.0–57.0 °C. ¹H NMR (400 MHz, CDCl₃): δ = 7.71–7.64 (m, 2 H), 7.54 (s, 1 H), 7.38–7.32 (m, 1 H), 7.30–7.23 (m, 2 H), 6.03 (ddd, J = 17.3, 10.6, 5.5 Hz, 1 H), 5.43 (d, J = 17.3 Hz 1 H), 5.27 (d, J = 10.5 Hz, 1 H), 4.71–4.63 (m, 1 H), 3.13–2.96 (m, 2 H), 2.22–2.11 (m, 1 H), 1.99–1.87 (m, 1 H). ¹³C NMR (101 MHz, CDCl₃): δ = 153.2, 137.7, 133.7, 128.8, 128.0, 127.1, 126.5, 125.7, 124.1, 123.5, 116.5, 111.4, 76.6, 27.7, 24.9. IR (KBr): 2928, 2850, 1504, 1456, 1431, 1251, 1160, 1113, 985, 914, 870, 746 cm^–1. HRMS (ESI): m/z [M + H]⁺ calcd for C₁₅H₁₅O: 211.1117; found: 211.1116.
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