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

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

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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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