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Synlett 2015; 26(13): 1875-1879
DOI: 10.1055/s-0034-1380863
DOI: 10.1055/s-0034-1380863
letter
Novel Route for the Construction of Chroman Ring System Using Cross-Coupling between Benzylic and Aliphatic Alcohols in the Presence of NaHSO4/SiO2
Weitere Informationen
Publikationsverlauf
Received: 30. März 2015
Accepted after revision: 24. April 2015
Publikationsdatum:
09. Juli 2015 (online)
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Abstract
Novel route for the construction of chromans from benzylic and aliphatic alcohols in the presence of NaHSO4/SiO2 has been developed. In this reaction, substituted olefins are formed from benzylic and aliphatic alcohols and then converted to chromans through intramolecular cyclization. Twenty novel chromans were synthesized by this simple procedure.
Supporting Information
- Supporting information for this article is available online at http://dx.doi.org/10.1055/s-0034-1380863.
- Supporting Information
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References and Notes
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- 19 Melting points were determined on Büchi Melting Point B-540 apparatus. NMR spectra were recorded on a JEOL ECX 400 spectrometer. Tetramethylsilane (δ = 0 ppm) was used as an internal standard for 1H NMR and CDCl3 (δ = 77.0 ppm) for 13C NMR measurements. Mass analyses were performed on an Agilent G1969 LC/MDS TOF instrument. IR spectra were recorded on a JASCO FT/IR-6100 equipment. Elemental analyses were performed on a J Science Lab. microcorder JM-10 instrument. Preparation of NaHSO4/SiO2 : SiO2 [Wakogel C-200 (Wako Pure Chemical Ind. Ltd.), 10 g] was added to a solution of NaHSO4·H2O (30 mmol, 4.14 g) in distilled H2O, and the mixture was stirred at r.t. for 0.5 h. The H2O was removed by rotary evaporator under reduced pressure, and the resulting reagent was dried in vacuo (10 mmHg) at 120 °C for 5 h. Typical Procedure: A mixture of 1 (2 mmol), 2 (4 or 15 mmol) and NaHSO4/SiO2 (2.1 mmol/g, 1.0 or 2.0 g) in DCE (10 mL) was stirred at 80 °C for 2 h, and then the used supported reagent was removed by filtration. The filtrate was evaporated to leave crude product, which was purified by column chromatography (hexane–CHCl3) to obtain substituted chromans 3. 6-Methyl-2,2,4-triphenylchroman (3bb): yield: 0.7315 g (97%); white solid; mp 173–175 °C (MeOH). 1H NMR (400 MHz, CDCl3): δ = 2.08 (s, 3 H), 2.60 (dd, J = 13.9, 12.6 Hz, 1 H), 3.06 (dd, J = 13.9, 5.4 Hz, 1 H), 3.86 (dd, J = 12.6, 5.4 Hz, 1 H), 6.42 (s, 1 H), 6.95 (dd, J = 8.2, 2.3 Hz, 1 H), 7.03 (d, J = 8.2 Hz, 1 H), 7.18–7.34 (m, 11 H), 7.47–7.52 (m, 4 H). 13C NMR (100 MHz, CDCl3): δ = 20.5, 40.1, 42.2, 81.6, 117.0, 124.8, 125.6, 126.3, 126.7, 127.0, 127.3, 128.2, 128.5, 128.6 (overlap), 128.8, 129.5, 129.7, 143.5, 144.5, 145.8, 152.0. IR (neat): 3057, 2920, 1591, 1487, 1445, 1283, 1231, 1110, 1061, 1007, 920, 846, 805, 784, 748, 732, 695, 628, 585, 539 cm–1. HRMS (TOF–CI): m/z [M + H]+ calcd for C28H25O: 377.1905; found: 377.1896. Anal. Calcd for C28H24O: C, 89.33; H, 6.43. Found: C, 89.58; H, 6.15. 6-Methoxy-2,2,4-triphenylchroman (3cb): yield: 0.7534 g (96%); white solid; mp 106–108 °C (MeOH). 1H NMR (400 MHz, CDCl3): δ = 2.59 (dd, J = 13.9, 12.6 Hz, 1 H), 3.08 (dd, J = 13.9, 5.4 Hz, 1 H), 3.52 (s, 3 H), 3.87 (dd, J = 12.6, 5.4 Hz, 1 H), 6.15 (d, J = 3.0 Hz, 1 H), 6.73 (dd, J = 8.9, 3.0 Hz, 1 H), 7.07 (d, J = 8.9 Hz, 1 H), 7.17–7.33 (m, 11 H), 7.47–7.52 (m, 4 H). 13C NMR (100 MHz, CDCl3): δ = 40.4, 42.0, 55.4, 81.5, 113.8, 114.1, 117.8, 125.6, 125.8, 126.3, 126.8, 127.0, 127.2, 128.2, 128.6, 128.6, 128.8, 143.4, 144.2, 145.8, 148.2, 153.2. IR (neat): 3055, 2827, 1604, 1489, 1451, 1417, 1252, 1211, 1155, 1100, 1036, 950, 912, 859, 809, 755, 698, 588, 512 cm–1. HRMS (TOF–CI): m/z [M+] calcd for C28H24O2: 392.1776; found: 392.1777. Anal. Calcd for C28H24O2: C, 85.68; H, 6.16. Found: C, 85.77; H, 6.16. 6-Bromo-2,2,4-triphenylchroman (3db): yield: 0.8474 g (96%); white solid; mp 158–160 °C (MeOH). 1H NMR (400 MHz, CDCl3): δ = 2.59 (dd, J = 14.0, 12.7 Hz, 1 H), 3.08 (dd, J = 14.0, 5.5 Hz, 1 H), 3.85 (dd, J = 12.7, 5.5 Hz, 1 H), 6.74 (d, J = 2.3 Hz, 1 H), 7.02 (d, J = 8.7 Hz, 1 H), 7.15–7.35 (m, 12 H), 7.45–7.48 (m, 4 H). 13C NMR (100 MHz, CDCl3): δ = 40.1, 41.6, 82.2, 112.7, 119.1, 125.6, 126.1, 127.1, 127.3, 127.5, 127.6, 128.3, 128.7, 128.7, 128.8, 130.8, 132.1, 143.0, 143.4, 145.2, 153.3. IR (neat): 3056, 1592, 1469, 1396, 1240, 1203, 1110, 1062, 1007, 915, 877, 842, 811, 777, 754, 694, 585, 542 cm–1. HRMS (TOF–CI): m/z [M+] calcd for C27H21BrO: 440.0775; found: 440.0776. Anal. Calcd for C27H21BrO: C, 73.48; H, 4.80. Found: C, 73.68; H, 4.71. 7-Methoxy-2,2,4-triphenylchroman (3eb): yield: 0.6579 g (83%); white solid; mp 148–149 °C (MeOH). 1H NMR (400 MHz, CDCl3): δ = 2.59 (dd, J = 13.8, 12.6 Hz, 1 H), 3.07 (dd, J = 13.8, 5.4 Hz, 1 H), 3.78 (s, 3 H), 3.88 (dd, J = 12.6, 5.4 Hz, 1 H), 6.33 (dd, J = 8.6, 2.6 Hz, 1 H), 6.51 (d, J = 8.6 Hz, 1 H), 6.70 (d, J = 2.6 Hz, 1 H), 7.16–7.35 (m, 11 H) 7.47–7.52 (m, 4 H). 13C NMR (100 MHz, CDCl3): δ = 39.5, 42.2, 55.3, 82.1, 101.7, 107.4, 117.6, 125.7, 126.3, 126.7, 127.1, 127.3, 128.2, 128.6 (overlap), 128.7, 130.2, 143.4, 144.6, 145.6, 155.0, 159.3. IR (neat): 2969, 1611, 1580, 1495, 1444, 1410, 1318, 1258, 1195, 1158, 1101, 1058, 1033, 1018, 966, 910, 835, 772, 734, 696, 627, 594, 556, 518 cm–1. HRMS (TOF–CI): m/z [M + H]+ calcd for C28H25O2: 393.1854; found: 393.1851. Anal. Calcd for C28H24O2: C, 85.68; H, 6.16. Found: C, 85.88; H, 6.02. 6,8-Dibromo-2,2,4-triphenylchroman (3gb): yield: 1.0283 g (98%); white solid; mp 166–167 °C (EtOH). 1H NMR (400 MHz, CDCl3): δ = 2.55 (dd, J = 14.1, 12.6 Hz, 1 H), 3.21 (dd, J = 14.1, 5.5 Hz, 1 H), 3.93 (dd, J = 14.1, 12.6 Hz, 1 H), 6.69 (d, J = 2.4 Hz, 1 H), 7.13–7.35 (m, 11 H), 7.48–7.60 (m, 5 H). 13C NMR (100 MHz, CDCl3): δ = 40.3, 41.2, 83.4, 112.5, 112.6, 125.0, 125.6, 127.3, 127.4, 127.5, 128.4, 128.6, 128.9, 129.0 (overlap), 131.4, 133.6, 142.7, 142.9, 144.9, 149.8. IR (neat): 3074, 3032, 1490, 1440, 1248, 1153, 1114, 1058, 1015, 941, 862, 771, 741, 695, 582 cm–1. HRMS (TOF–CI): m/z [M+] calcd for C27H20Br2O: 517.9880; found: 517.9872. Anal. Calcd for C27H20Br2O: C, 62.33; H, 3.87. Found: C, 62.45; H, 3.77. 6-Bromo-4-methyl-2,2-diphenylchroman (3jb): yield: 0.7257 g (95%); white solid; mp 146–147 °C. 1H NMR (400 MHz, CDCl3): δ = 1.32 (d, J = 6.8 Hz, 3 H), 2.15 (dd, J = 13.7, 12.2 Hz, 1 H), 2.67–2.77 (m, 1 H), 2.87 (dd, J = 13.7, 5.3 Hz, 1 H), 6.93–6.96 (m, 1 H), 7.18–7.33 (m, 8 H), 7.39–7.45 (m, 4 H). 13C NMR (100 MHz, CDCl3): δ = 19.8, 26.7, 41.0, 82.0, 112.7, 119.0, 125.7, 126.3, 127.1, 127.4, 128.2, 128.5, 129.1, 129.8, 130.3, 143.2, 145.6, 152.7. IR (neat): 3058, 2871, 1572, 1473, 1397, 1321, 1218, 1180, 1122, 1094, 1056, 982, 899, 824, 761, 727, 696, 670, 603, 512 cm–1. HRMS (TOF–CI): m/z [M+] calcd for C22H19BrO: 378.0619; found: 378.0620. Anal. Calcd for C22H19BrO: C, 69.67; H, 5.05. Found: C, 69.65; H, 5.07.