Synlett 2015; 26(13): 1875-1879
© Georg Thieme Verlag Stuttgart · New York
Novel Route for the Construction of Chroman Ring System Using Cross-Coupling between Benzylic and Aliphatic Alcohols in the Presence of NaHSO4 /SiO2
Tadashi Aoyama*
a
Department of Materials and Applied Chemistry, College of Science and Technology, Nihon University, Kanda Surugadai, Chiyoda-ku, Tokyo 101-8308, Japan Email:
aoyama.tadashi@nihon-u.ac.jp
b
The Center for Creative Materials Research, Research Institute of Science and Technology, College of Science and Technology, Nihon University, Tokyo 101-8308, Japan
,
Takuya Furukawa
a
Department of Materials and Applied Chemistry, College of Science and Technology, Nihon University, Kanda Surugadai, Chiyoda-ku, Tokyo 101-8308, Japan Email:
aoyama.tadashi@nihon-u.ac.jp
,
Mamiko Hayakawa
a
Department of Materials and Applied Chemistry, College of Science and Technology, Nihon University, Kanda Surugadai, Chiyoda-ku, Tokyo 101-8308, Japan Email:
aoyama.tadashi@nihon-u.ac.jp
,
Toshio Takido
a
Department of Materials and Applied Chemistry, College of Science and Technology, Nihon University, Kanda Surugadai, Chiyoda-ku, Tokyo 101-8308, Japan Email:
aoyama.tadashi@nihon-u.ac.jp
,
Mitsuo Kodomari
c
The Institute of Natural Sciences, College of Humanities and Science, Nihon University, Tokyo 156-8550, Japan
› Author Affiliations
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.
Key words chroman - tandem reaction - heterogeneous reaction - coupling reaction - solid acid
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 1 H NMR and CDCl3 (δ = 77.0 ppm) for 13 C 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 ·H2 O (30 mmol, 4.14 g) in distilled H2 O, and the mixture was stirred at r.t. for 0.5 h. The H2 O 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). 1 H 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). 13 C 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 C28 H25 O: 377.1905; found: 377.1896. Anal. Calcd for C28 H24 O: 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). 1 H 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). 13 C 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 C28 H24 O2 : 392.1776; found: 392.1777. Anal. Calcd for C28 H24 O2 : 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). 1 H 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). 13 C 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 C27 H21 BrO: 440.0775; found: 440.0776. Anal. Calcd for C27 H21 BrO: 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). 1 H 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). 13 C 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 C28 H25 O2 : 393.1854; found: 393.1851. Anal. Calcd for C28 H24 O2 : 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). 1 H 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). 13 C 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 C27 H20 Br2 O: 517.9880; found: 517.9872. Anal. Calcd for C27 H20 Br2 O: 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. 1 H 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). 13 C 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 C22 H19 BrO: 378.0619; found: 378.0620. Anal. Calcd for C22 H19 BrO: C, 69.67; H, 5.05. Found: C, 69.65; H, 5.07.
