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Phosphorus, Sulfur, and Silicon and the Related Elements Volume 184, 2009 - Issue 5: Honoring the 70th Birthday of Marian Mikolajczyk, Part 2
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Original Articles

π-Face-Selective 1,3-Dipolar Cycloadditions of 3,4-Di-tert-butylthiophene 1-Oxide with 1,3-Dipoles

Juzo Nakayama Department of Chemistry, School of Science and Engineering, Saitama University, Saitama, Japan
,
Tomohiro Furuya Department of Chemistry, School of Science and Engineering, Saitama University, Saitama, Japan
,
Yasuko Suzuki Department of Chemistry, School of Science and Engineering, Saitama University, Saitama, Japan
,
Suguru Hiraiwa Department of Chemistry, School of Science and Engineering, Saitama University, Saitama, Japan
&
Yoshiaki Sugihara Department of Chemistry, School of Science and Engineering, Saitama University, Saitama, Japan
Pages 1175-1183 | Received 27 Dec 2007, Accepted 29 Feb 2008, Published online: 28 Apr 2009

REFERENCES

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  • Hake , H. , Landen , H. , Martin , H.-D. , Mayer , B. , Steigel , A. , Distefano , G. and Modelli , A. 1988 . Tetrahedron Lett. , 29 : 6601
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  • Supporting information of cycloadducts 4a– 4g (satisfactory elemental analyses were obtained except 4d whose analysis sample could not be supplied 19 ). 4a: colorless crystals; mp 193–194°C;IR (KBr) ν 1048 cm−1 (S═O); 1H NMR (CDCl3) δ1.05 (s, 9H), 1.35 (s, 9H), 2.18 (d, 3H, J = 1.1 Hz), 4.86 (d, 1H, J = 1.1 Hz, Ha), 6.61 (s, 1H, Hb); 1H NMR (C6D6) δ1.74 (s, 9H), 1.11 (s, 9H), 2.14 (d, 3H, J = 1.5 Hz), 4.26 (d, 1H, J = 1.5 Hz, Ha), 6.18 (s, 1H, Hb); 1H NMR (CDCl3/0.2 mol eq. Eu(thd)3) δ1.19 (s, 9H), 1.47 (s, 9H), 2.73 (broad s, 3H), 5.38 (broad s, 1H, Ha), 7.06 (broad s, 1H, Hb); 13C NMR (CDCl3) δ 13.9, 27.9, 32.6, 36.1, 36.6, 74.9, 108.4, 134.4, 153.2, 163.1. 4b: colorless crystals; mp 167–168 °C; IR (KBr) ν 1048 cm−1 (S═O); 1H NMR (CDCl3) δ 1.14 (s, 9H), 1.41 (s, 9H), 5.54 (s, 1H, Ha), 6.61 (s, 1H, Hb), 7.35–7.40 (m, 3H), 7.68–7.75 (m, 2H); 1H NMR (C6D6) δ 0.80 (s, 9H), 1.12 (s, 9H), 5.14 (s, 1H, Ha), 6.14 (s, 1H, Hb), 7.02–7.12 (m, 3H), 7.80 (d, 2H, J = 1.1); 1H NMR (CDCl3/0.2 mol eq. Eu(thd)3) δ 1.29 (s, 9H), 1.53 (s, 9H), 6.04 (broad s, 1H, Ha), 7.10 (broad s, 1H, Hb), 7.32–7.35 (m, 3H), 8.32 (br, 2H); 13C NMR (CDCl3) δ 27.6, 32.5, 36.2, 37.6, 73.4, 111.0, 127.1, 128.3, 128.7, 130.0, 134.4, 153.0, 163.5. 4b′: colorless crystals; mp 169–170°C; IR (KBr) ν 1039 cm−1 (S═O); 1H NMR (CDCl3) δ 1.25 (s, 9H), 1.41 (s, 9H), 4.80 (s, 1H, Ha), 6.63 (s, 1H, Hb), 7.44–7.50 (m, 3H), 7.79–7.86 (m, 2H); 1H NMR (C6D6) δ 1.06 (s, 9H), 1.08 (s, 9H), 4.83 (s, 1H, Ha), 6.04 (s, 1H, Hb), 7.01–7.04 (m, 3H), 7.90–7.93 (m, 2H); 1H NMR (CDCl3/0.2 mol eq. Eu(thd)3) δ 1.39 (s, 9H), 1.46 (s, 9H), 5.25 (s, 1H, Ha), 6.81 (s, 1H, Hb), 7.43–7.47 (m, 3H), 7.90–7.95 (m, 2H); 13C NMR (CDCl3) δ 27.2, 32.5, 36.7, 37.3, 79.8, 111.0, 126.9, 127.8, 129.1, 130.3, 130.7, 151.8, 166.8. 4c: colorless crystals; mp 153–154 °C; IR (KBr) ν 1031 cm−1 (S═O); 1H NMR (CDCl3) δ 1.12 (s, 9H), 1.34 (s, 9H), 3.83 (dd, 1H, J = 8.0, 9.5 Hz, Ha), 4.78 (dd, 1H, J = 8.0, 18.7 Hz), 4.81 (dd, 1H, J = 9.5, 18.7 Hz), 6.35 (s, 1H, Hb); 1H NMR (C6D6) δ 0.74 (s, 9H), 1.03 (s, 9H), 2.99 (dd, 1H, J = 8.3, 9.8 Hz, Ha), 4.43 (dd, 1H, J = 9.8, 19.0 Hz), 4.93 (dd, 1H, J = 8.1, 18.8 Hz), 5.87 (s, 1H, Hb); 1H NMR (CDCl3/0.2 mol eq. Eu(thd)3) δ 1.16 (s, 9H), 1.49 (s, 9H), 4.35 (t, 1H, J = 9.0 Hz, Ha), 5.30 (dd, 1H, J = 9.5, 18.8 Hz), 5.92 (br, 1H), 6.98 (broad s, 1H, Hb); 13C NMR (CDCl3) δ 28.4, 33.4, 36.4, 37.6, 60.1, 74.1, 119.4, 134.7, 161.7. 4d: colorless crystals; 1H NMR (CDCl3) δ 0.84 (s, 9H), 1.25 (broad s, 9H), 4.87 (s, 1H, Ha), 6.84 (s, 1H, Hb), 7.28–7.31 (m, 4H), 7.33–7.38 (m, 2H), 7.59–7.61 (m, 2H, J = 7.6 Hz), 7.80–7.82 (m, 2H, J = 7.8 Hz); 13C NMR (CDCl3) δ 28.1 (broad s), 33.7, 37.2, 40.1, 74.6, 97.0, 125.7, 128.2, 128.66, 128.72, 128.9, 131.2, 131.8, 135.4, 143.5, 146.9, 168.6. 4e: colorless crystals; mp 127–128 °C; IR (KBr) ν 1038 cm−1 (S═O); 1H NMR (CDCl3): δ 1.09 (s, 9H), 1.40 (s, 9H), 2.61 (s, 3H), 4.33 (d, 1H, J = 7.6 Hz, Hc), 4.61 (d, 1H, J = 7.6 Hz, Ha), 6.41 (s, 1H, Hb), 7.20–7.37 (m, 3H), 7.42–7.48 (m, 2H);1H NMR (C6D6) δ 0.87 (s, 9H), 1.20 (s, 9H), 2.46 (s, 3H), 4.35 (d, 1H, J = 8.3 Hz, Ha), 4.57 (d, 1H, J = 8.8 Hz, Hc), 6.04 (s, 1H, Hb), 7.07–7.22 (m, 3H), 7.67 (d, 2H, J = 6.8 Hz); 1H NMR (CDCl3, 0.2 mol eq. Eu(fod)3,fod = 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedionate) δ 1.27 (s, 9H), 1.55 (s, 9H), 2.91 (s, 3H), 4.34 (broad s, 1H, Hc), 5.37 (m, 1H, Ha), 7.02 (broad s, 1H, Hb), 7.32–7.46 (m, 3H), 8.27 (broad s, 2H);13C NMR (CDCl3) δ 28.0, 33.1, 35.9, 37.7, 43.1, 70.8, 78.0, 104.0, 128.0, 128.5, 128.7, 132.8, 137.1, 165.1. 4f: colorless crystals; mp 193.5–194.5 °C; IR (KBr) ν 1040 cm−1 (S═O); 1H NMR (CDCl3) δ 1.02 (s, 9H), 1.34 (s, 9H), 1.68–1.83 (m, 2H), 1.95–2.14 (m, 2H), 2.77–2.89 (m, 1H, J = 13.6 Hz), 3.38–3.48 (m, 1H, J = 13.6 Hz), 4.04 (d, 1H, J = 3.3 Hz, Ha), 4.18–4.26 (m, 1H, J = 4.2 Hz, Hc), 6.39 (s, 1H, Hb); 1H NMR (C6D6) δ 0.79 (s, 9H), 1.26 (s, 9H), 1.52–1.84 (m, 4H), 2.39–2.54 (m, 1H, J = 13.6 Hz), 3.15–3.25 (m, 1H, J = 13.6 Hz), 3.60 (d, 1H, J = 3.4 Hz, Ha), 4.45–4.54 (m, 1H, J = 4.2 Hz, Hc), 6.14 (s, 1H, Hb); 1H NMR (CDCl3/0.2 mol eq. Eu(thd)3) δ 1.08 (s, 9H), 1.39 (s, 9H), 1.69–1.84 (m, 2H), 2.00–2.19 (m, 2H), 2.84–2.95 (m, 1H), 3.44–3.53 (m, 1H), 4.24 (broad s, 1H, Ha), 4.58–4.69 (m, 1H, Hc), 6.61 (s, 1H, Hb); 13C NMR (CDCl3) δ 25.0, 28.1, 32.3, 32.4, 35.90, 35.91, 57.0, 62.4, 78.4, 104.0, 133.5, 166.0. 4g: colorless crystals; mp 128–129 °C; IR (KBr) ν 1044 cm−1 (S═O); 1H NMR (CDCl3) δ 1.00 (s, 9H), 1.27 (s, 9H), 2.66 (d, 1H, J = 9.9 Hz), 2.84–3.03 (m, 3H), 3.61 (s, 2H), 4.12 (t, 1H, J = 8.3 Hz, Ha), 6.35 (s, 1H, Hb), 7.23–7.31 (m, 5H); 1H NMR (C6D6) δ 0.71 (s, 9H), 0.96 (s, 9H), 2.50 (d, 1H, J = 9.6 Hz), 2.65–2.72 (m, 2H), 3.24–3.41 (m, 3H), 3.66 (t, 1H, J = 8.1 Hz, Ha), 6.07 (s, 1H, Hb), 7.23–7.31 (m, 5H); 1H NMR (CDCl3/0.2 mol eq. Eu(thd)3) δ 1.09 (s, 9H), 1.36 (s, 9H), 2.84 (m, 1H), 3.07–3.20 (m, 3H), 3.71 (s, 2H), 4.43 (broad s, 1H, Ha), 6.70 (broad s, 1H, Hb), 7.23–7.35 (m, 5H); 13C NMR (CDCl3) δ 29.1, 33.5, 36.0, 36.5, 51.7, 60.1, 61.0, 66.4, 76.0, 127.0, 128.2, 128.5, 133.1, 138.4, 166.1. 4g′: 1H NMR (CDCl3) δ 1.15 (s, 9H), 1.29 (s, 9H), 2.42 (dd, 1H, J = 7.4, 9.9 Hz), 2.53 (d, 1H, J = 9.9 Hz), 2.79 (d, 1H, J = 9.9 Hz), 3.11 (t, 1H, J = 9.2 Hz, Ha), 3.47–3.54 (m, 3H), 6.50 (s, 1H, Hb), 7.23–7.31 (m, 5H)
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