Synlett 2014; 25(16): 2355-2359
DOI: 10.1055/s-0034-1378581
letter
© Georg Thieme Verlag Stuttgart · New York

Type 2 Ring-Opening Reactions of Cyclopropanated 7-Oxabenzonorbornadienes under Acid Catalysis

Andrew Tigchelaar
Guelph-Waterloo Centre for Graduate Work in Chemistry and Biochemistry, Department of Chemistry, University of Guelph, Guelph, Ontario, N1G 2W1, Canada   Fax: +1(519)7661499   eMail: wtam@uoguelph.ca
,
Jamie Haner
Guelph-Waterloo Centre for Graduate Work in Chemistry and Biochemistry, Department of Chemistry, University of Guelph, Guelph, Ontario, N1G 2W1, Canada   Fax: +1(519)7661499   eMail: wtam@uoguelph.ca
,
Emily Carlson
Guelph-Waterloo Centre for Graduate Work in Chemistry and Biochemistry, Department of Chemistry, University of Guelph, Guelph, Ontario, N1G 2W1, Canada   Fax: +1(519)7661499   eMail: wtam@uoguelph.ca
,
William Tam*
Guelph-Waterloo Centre for Graduate Work in Chemistry and Biochemistry, Department of Chemistry, University of Guelph, Guelph, Ontario, N1G 2W1, Canada   Fax: +1(519)7661499   eMail: wtam@uoguelph.ca
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Publikationsverlauf

Received: 27. März 2014

Accepted after revision: 11. Juli 2014

Publikationsdatum:
06. August 2014 (online)


Abstract

A novel ring-opening mode of cyclopropanated 7-oxa­benzonorbornadiene under acid catalysis has been discovered, providing various 2-(alkoxymethyl)naphthalenes through the use of alcohol nucleophiles. The reaction was most effective with catalytic p-TsOH∙H2O in methanol, offering yields up to 91%. The compatibility of secondary and tertiary alcohols, as well as functionalized substrates was also demonstrated.

Supporting Information

 
  • References and Notes

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  • 34 General Procedure: In a small screw-cap vial containing a stir-bar, cyclopropanated oxabenzonorbornadiene 2 (1.0 equiv.) was dissolved in alcohol (0.5 mL). The reaction was cooled to 0 °C, and PTSA (0.1 equiv.) was added as a solid. The reaction was stirred at 0 °C for 10 min, then slowly warmed to r.t. The vial was sealed and secured tightly with polytetrafluoroethylene (PTFE) thread-seal tape and paraffin film, and heated to 90 or 110 °C with continuous stirring for 24–330 h. The crude product was directly loaded onto a chromatography column and purified (EtOAc–hexanes). 2-(Methoxymethyl)naphthalene (6a; Table 2, entry 1): Yield: 34.3 mg (82%); clear oil; Rf = 0.33 (EtOAc–hexanes, 1:9). 1H NMR (400 MHz, CDCl3): δ = 7.82–7.84 (m, 3 H), 7.78 (s, 1 H), 7.45–7.48 (m, 3 H), 4.62 (s, 2 H), 3.43 (s, 3 H). 13C NMR (100 MHz, CDCl3): δ = 135.7, 133.3, 133.0, 128.2, 127.9, 127.7, 126.5, 126.1, 125.9, 125.7, 74.8, 58.2. Spectral data are consistent with those previously reported.24 2-(Ethoxymethyl)naphthalene (6b; Table 2, entry 2): Yield: 25.3 mg (77%); clear oil; Rf = 0.40 (EtOAc–hexanes, 1:9). 1H NMR (400 MHz, CDCl3): δ = 7.80–7.82 (m, 3 H), 7.77 (s, 1 H), 7.44–7.47 (m, 3 H), 4.66 (s, 2 H), 3.57 (q, J = 7.0 Hz, 2 H), 1.26 (t, J = 7.0 Hz, 3 H). 13C NMR (100 MHz, CDCl3): δ = 136.1, 133.3, 133.0, 128.1, 127.9, 127.7, 126.3, 126.0, 125.8, 125.7, 72.8, 65.8, 15.3. Spectral data are consistent with those previously reported.24 2-(Butoxymethyl)naphthalene (6c; Table 2, entry 3 ): Yield: 37.1 mg (61%); clear oil; Rf = 0.40 (EtOAc–hexanes, 1:9). IR (neat): 3055 (s), 2958 (s), 2932 (s), 2869 (s), 1603 (m), 1509 (s), 1464 (s), 1374 (s), 1170 (m), 1098 (s), 854 (s), 816 (s), 751 (s) cm–1. 1H NMR (400 MHz, CDCl3): δ = 7.80–7.82 (m, 3 H), 7.76 (s, 1 H), 7.43–7.47 (m, 3 H), 4.65 (s, 2 H), 3.50 (t, J = 6.6 Hz, 2 H), 1.62 (m, 2 H), 1.40 (m, 2 H), 0.91 (t, J = 7.3 Hz, 3 H). 13C NMR (100 MHz, CDCl3): δ = 136.3, 133.3, 133.0, 128.1, 127.9, 127.7, 126.3, 126.0, 125.8, 125.7, 73.0, 70.3, 31.9, 19.4, 14.0. HRMS: m/z [M]+ calcd. for C15H18O: 214.1358; found: 214.1364. Spectral data are consistent with those previously reported.25 2-(Isopropoxymethyl)naphthalene (6d; Table 2, entry 5): Yield: 33.9 mg (67%); clear oil; Rf = 0.41 (EtOAc–hexanes, 1:9). IR (neat): 3055 (m), 2971 (s), 2930 (m), 2868 (m), 2242 (w), 1950 (w), 1726 (w), 1602 (m), 1509 (m), 1467 (m), 1369 (s), 1329 (s), 1124 (s), 1070 (s), 909 (m), 855 (m), 814 (s), 734 (s) cm–1. 1H NMR (400 MHz, CDCl3): δ = 7.79–7.83 (m, 4 H), 7.44–7.49 (m, 3 H), 4.67 (s, 2 H), 3.73 (m, 1 H), 1.23 (d, J = 6.0 Hz, 6 H). 13C NMR (100 MHz, CDCl3): δ = 136.7, 133.4, 132.9, 128.1, 127.9, 127.7, 126.1, 126.0, 125.8, 125.7, 71.0, 70.2, 22.2. HRMS: m/z [M]+ calcd. for C14H16O: 200.1201; found: 200.1205. 2-(Cyclohexoxymethyl)naphthalene (6e; Table 2, entry 6): Yield: 39.3 mg (67%); clear oil; Rf = 0.44 (EtOAc–hexanes, 1:9). IR (neat): 3055 (s), 2930 (s), 2855 (s), 1602 (m), 1509 (s), 1450 (s), 1366 (s), 1090 (s), 854 (m), 816 (s), 734 (s) cm–1. 1H NMR (400 MHz, CDCl3): δ = 7.79–7.83 (m, 4 H), 7.44–7.49 (m, 3 H), 4.71 (s, 2 H), 3.40 (m, 1 H), 2.00 (m, 2 H), 1.76 (m, 2 H), 1.54 (m, 1 H), 1.39 (m, 2 H), 1.25 (m, 3 H). 13C NMR (100 MHz, CDCl3): δ = 136.9, 133.4, 132.9, 128.0, 127.9, 127.7, 126.0, 125.9, 125.8, 125.7, 77.0, 69.8, 32.3, 25.9, 24.2. HRMS: m/z [M]+ calcd. for C17H20O: 240.1514; found: 240.1522. Spectral data are consistent with those previously reported.26 2-(tert-Butoxymethyl)naphthalene (6f; Table 2, entry 7): Yield: 7.1 mg (11%); clear oil; Rf = 0.40 (EtOAc–hexanes, 1:9). 1H NMR (400 MHz, CDCl3): δ = 7.77–7.84 (m, 4 H), 7.39–7.48 (m, 3 H), 4.59 (s, 2 H), 1.32 (s, 9 H). 13C NMR (100 MHz, CDCl3): δ = 137.4, 133.5, 132.8, 128.0, 127.9, 127.8, 127.6, 125.9, 125.8, 125.5, 73.6, 64.3, 27.8. Spectral data are consistent with those previously reported.24 1,4-Dimethoxy-6-(methoxymethyl)naphthalene (6g; Table 3, entry 2): Yield: 18.9 mg (56%); clear oil; Rf = 0.29 (EtOAc–hexanes, 1:9). IR (KBr): 3076 (w), 2996 (m), 2934 (s), 2833 (s), 1633 (w), 1604 (s), 1463 (s), 1361 (w), 1271 (s), 1246 (m), 1095 (s), 804 (s) cm–1. 1H NMR (600 MHz, CDCl3): δ = 8.18 (d, J = 8.6 Hz, 1 H), 8.13 (s, 1 H), 7.49 (dd, J = 8.6, 1.4 Hz, 1 H), 6.68 (ABq, J AB = 8.4 Hz, ΔδAB = 8.8 Hz, 2 H), 4.62 (s, 2 H), 3.941 (s, 3 H), 3.937 (s, 3 H), 3.39 (s, 3 H). 13C NMR (125 MHz, CDCl3): δ = 149.5, 135.7, 126.1, 125.8, 125.6, 122.2, 120.6, 103.4, 103.2, 74.9, 58.0, 55.7. HRMS: m/z [M]+ calcd. for C14H16O3: 232.1099; found: 232.1106. Spectral data are consistent with those previously reported.27 2,3-Dibromo-6-(methoxymethyl)naphthalene (6h; Table 3, entry 3): Yield: 12.8 mg (20%); red solid; mp 40–42 °C; Rf = 0.38 (EtOAc–hexanes, 1:9). IR (KBr): 3058 (w), 2989 (m), 2926 (s), 2884 (m), 2851 (m), 1582 (m), 1453 (m), 1102 (s), 903 (s), 888 (s), 821 (m) cm–1. 1H NMR (600 MHz, CDCl3): δ = 8.11 (s, 1 H), 8.10 (s, 1 H), 7.69 (m, 1 H), 7.65 (s, 1 H), 7.46 (m, 1 H), 4.58 (s, 2 H), 3.42 (s, 3 H). 13C NMR (100 MHz, CDCl3): δ = 137.4, 133.0, 132.6, 132.2, 132.0, 127.1, 127.0, 125.0, 122.3, 121.9, 74.4, 58.4. HRMS: m/z [M]+ calcd. for C12H10OBr2: 327.9098; found: 327.9108.2-(Methoxymethyl)-1,4-dimethylnaphthalene (6i; Table 3, entry 4): Yield: 41.7 mg (79%); beige solid; mp 39–42 °C; Rf = 0.54 (EtOAc–hexanes, 1:9). IR (KBr): 3070 (w), 2974 (m), 2923 (s), 2815 (m), 1716 (w), 1602 (w), 1512 (w), 1447 (m), 1389 (m), 1192 (m), 1104 (s), 1077 (m), 754 (s) cm–1. 1H NMR (600 MHz, CDCl3): δ = 8.11 (m, 1 H), 8.00 (m, 1 H), 7.52 (m, 2 H), 7.32 (s, 1 H), 4.64 (s, 2 H), 3.44 (s, 3 H), 2.67 (s, 3 H), 2.65 (s, 3 H). 13C NMR (125 MHz, CDCl3): δ = 133.0, 132.4, 132.3, 131.9, 130.6, 127.9, 125.4, 125.2, 124.6, 124.5, 73.3, 58.1, 19.3, 13.9. HRMS: m/z [M]+ calcd for C14H16O: 200.1201; found: 200.1207. 3-(Methoxymethyl)-1-methylnaphthalene (6j; Table 3, entry 5): Yield: 30.7 mg (73%); yellow oil; Rf = 0.32 (EtOAc–hexanes, 1:9). IR (neat): 3052 (w), 2980 (m), 2924 (s), 2918 (m), 1604 (m), 1509 (m), 1450 (m), 1193 (m), 1132 (m), 1100 (s), 910 (s), 868 (s), 734 (s) cm–1. 1H NMR (400 MHz, CDCl3): δ = 7.98 (d, J = 7.8 Hz, 1 H), 7.83 (d, J = 7.2 Hz, 1 H), 7.64 (s, 1 H), 7.53–7.46 (m, 2 H), 7.31 (s, 1 H), 4.58 (s, 2 H), 3.42 (s, 3 H), 2.69 (s, 3 H). 13C NMR (100 MHz, CDCl3): δ = 135.3, 134.7, 133.5, 132.2, 128.5, 126.4, 125.8, 125.7, 125.0, 124.0, 74.9, 58.2, 19.4. HRMS: m/z [M]+ calcd for C13H14O: 186.1045; found 186.1041.