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Synlett 2011(20): 2971-2976  
DOI: 10.1055/s-0031-1290083
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Direct Carbon-Carbon Bond Formation from Alcohols and Active Methylenes using NaHSO4/SiO2

Tadashi Aoyama*a,b, Saki Miyotaa, Toshio Takidoa, Mitsuo Kodomaric
a Department of Materials and Applied Chemistry, College of Science and Technology, Nihon University, Kanda Surugadai, Chiyoda-ku, Tokyo 101-8308, Japan
Fax: +81(3)32590818; e-Mail: 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, Kanda Surugadai, Chiyoda-ku, Tokyo 101-8308, Japan
c Department of Bioscience and Engineering, Shibaura Institute of Technology, Fukasaku, Minuma-ku, Saitama 337-8570, Japan
Further Information

Publication History

Received 8 September 2011
Publication Date:
28 November 2011 (online)

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Abstract

A simple and efficient procedure for carbon-carbon bond formation has been developed starting from alcohols and ­active methylene-containing compounds using silica gel supported sodium hydrogen sulfate (NaHSO4/SiO2) under mild conditions. NaHSO4/SiO2 can be reused without loss of catalytic activity at least ten times.

Key words

carbon-carbon coupling - silica gel - alcohol - supported catalysts

    References and notes

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Preparation of NaHSO 4 /SiO 2 : 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 water, and the mixture was stirred at room temperature for 0.5 h. The water was removed by rotary evaporation under reduced pressure, and the resulting reagent was dried in vacuo (10 mmHg) at 120 ˚C for 5 h

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Typical procedure: A mixture of 1 (2.0 mmol), 2 (2.0 mmol), and NaHSO4/SiO2 (2.1 mmol, 1.0 g) in DCE (10 mL) was stirred at 60 ˚C for 0.5 h, and then the used supported reagent was removed by filtration. The filtrate was concentrated and dried in vacuo to obtain 3 (>98% by GC).

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Compound 3ca: White solid; mp 68-70 ˚C. IR (neat): 1739, 1707 cm-¹. ¹H NMR (CDCl3): δ = 2.09 (s, 3 H), 4.42 (dt, J = 6.0, 1.4 Hz, 2 H), 4.56 (d, J = 12.4 Hz, 1 H), 4.78 (d, J = 12.4 Hz, 1 H), 5.07-5.13 (m, 2 H), 5.57-5.67 (m, 1 H), 7.14-7.36 (m, 10 H). ¹³C NMR (CDCl3): δ = 30.1, 50.9, 65.1, 66.0, 118.7, 126.9, 127.0, 127.7, 127.8, 128.6, 128.8, 131.2, 141.1, 141.4, 167.3, 201.6. HRMS (EI): m/z [M]+ calcd for C20H20O3: 308.1412; found: 308.1417. Anal. Calcd for C20H20O3: C, 77.90; H, 6.54. Found: C, 78.07; H, 6.58.
Compound 3da: White solid; mp 95-97 ˚C. IR (neat): 1740, 1709 cm-¹. ¹H NMR (CDCl3): δ = 2.05 (s, 3 H), 4.58 (d, J = 12.1 Hz, 1 H), 4.78 (d, J = 12.1 Hz, 1 H), 4.93 (d, J = 13.7 Hz, 1 H), 4.96 (d, J = 13.7 Hz, 1 H), 7.03-7.29 (m, 15 H). ¹³C NMR (CDCl3): δ = 30.0, 50.9, 65.1, 67.2, 126.8, 127.0, 127.6, 127.8, 128.1, 128.2, 128.5, 128.7, 128.8, 135.0, 141.1, 141.4, 167.5, 201.4. HRMS (EI): m/z [M]+ calcd for C24H22O3: 358.1569; found: 358.1569. Anal. Calcd for C24H22O3: C, 80.42; H, 6.19. Found: C, 80.16; H, 5.82.
Compound 3ga: White solid; mp 101-102 ˚C. IR (neat): 1729, 1705 cm-¹. ¹H NMR (CDCl3): δ = 0.91 (s, 9 H), 0.94 (t, J = 7.1 Hz, 3 H), 3.84-3.99 (m, 2 H), 4.86 (d, J = 12.1 Hz, 1 H), 4.89 (d, J = 12.1 Hz, 1 H), 7.09-7.37 (m, 10 H). ¹³C NMR (CDCl3): δ = 13.7, 25.9, 45.7, 52.0, 58.8, 61.2, 126.7, 126.8, 128.1, 128.4, 128.5, 141.3, 141.7, 167.6, 207.4. HRMS (EI): m/z [M]+ calcd for C22H26O3: 338.1882; found: 338.1879. Anal. Calcd for C22H26O3: C, 78.07; H, 7.74. Found: C, 77.96; H, 7.73.
Compound 3ja: White solid; mp 99-101 ˚C. IR (neat): 1769, 1716 cm-¹. ¹H NMR (CDCl3): δ = 1.92 (s, 3 H), 4.83 (d, J = 11.9 Hz, 1 H), 5.16 (d, J = 11.9 Hz, 1 H), 7.17-7.32 (m, 10 H). ¹³C NMR (CDCl3): δ = 31.1, 51.6, 65.9, 115.2 (q, J = 291.9 Hz, CF3), 127.3, 127.3, 127.6, 128.1, 129.0, 129.1, 139.7, 140.2, 184.2 (q, J = 36.9 Hz, COCF3), 199.0. HRMS (EI): m/z [M]+ calcd for C18H15F3O2: 320.1024; found: 320.1033. Anal. Calcd for C18H15F3O2: C, 67.50; H, 4.72. Found: C, 67.27; H, 4.48.
Compound 3na: White solid; mp 138-139 ˚C. IR (neat): 1704, 1636 cm-¹. ¹H NMR (CDCl3): δ = 2.09 (s, 3 H), 2.77 (s, 3 H), 2.91 (s, 3 H), 4.63 (d, J = 11.9 Hz, 1 H), 4.96 (d, J = 11.9 Hz, 1 H), 7.13-7.33 (m, 10 H). ¹³C NMR (CDCl3): δ = 27.7, 36.1, 37.6, 51.5, 63.2, 126.8, 127.0, 127.8, 128.1, 128.5, 128.9, 141.1, 142.0, 167.1, 204.9. HRMS (EI): m/z [M]+ calcd for C19H21NO2: 295.1572; found: 295.1571. Anal. Calcd for C19H21NO2: C, 77.26; H, 7.17; N, 4.74. Found: C, 77.34; H, 7.17; N, 4.70