J.L. García Ruano et al. / Tetrahedron 67 (2011) 2905e2910
2909
The sulfonamide was purified by column chromatography using
hexaneeethyl acetate 4:1 as eluent.
4.3.8. N-Phenethylbenzenesulfonamide 9a26. This sulfonamide was
obtained following the general procedure using methyl sulfinate 1a
and phenethylamine as starting material. Colorless solid; mp:
59e60 ꢀC [lit.26 mp: 65e66 ꢀC]. 1H NMR (300 MHz, CDCl3):
4.3.1. 1N-Butylbenzenesulfinamide 60a23. This sulfinamide was
obtained following the general procedure using methyl sulfinate 1a
and n-butylamine as starting material. Colorless oil. 1H NMR
d
7.85e7.78 (m, 2H), 7.61e7.46 (m, 3H), 7.31e7.18 (m, 3H), 7.12e7.04
(m, 2H), 4.52 (t, J¼5.7 Hz, 1H, NH), 3.24 (q, J¼6.9 Hz, 2H), 2.76
(300 MHz, CDCl3):
d
7.75e7.79 (m, 2H), 7.54e7.48 (m, 3H), 4.08 (t,
(t, J¼6.9 Hz, 2H). 13C NMR (75 MHz, CDCl3):
d 139.9, 137.5, 132.6,
J¼7.2 Hz, 1H, NH), 3.18e3.06 (m, 1H), 2.88e2.76 (m, 1H), 1.54e1.44
129.1, 128.8, 128.7, 127.0, 126.9, 44.2, 35.8. MS (EI): m/z 261 (Mþ, 2),
(m, 2H), 1.38e1.25 (m, 2H), 0.86 (t, J¼7.2 Hz, 3H). 13C NMR (75 MHz,
170 (100), 141 (68), 91 (33), 77 (66).
CDCl3):
d 144.4, 130.7, 128.7, 125.9, 40.9, 32.5, 19.9, 13.6. MS (EI):
m/z 197 (Mþ, 1), 180 (24), 149 (15), 125 (100), 106 (14), 97 (16),
Acknowledgements
77 (39).
We thank Ministerio de Ciencia y Tecnología, Spain (CTQ2009-
12168) and CAM (S2009/PPQ-1634) for financial support. A.P.
4.3.2. N-Benzylbenzenesulfinamide 70a24. This sulfinamide was
obtained following the general procedure using methyl sulfinate 1a
and benzylamine as starting material. Colorless oil. 1H NMR
ꢀ
thanks the Ministerio de Educacion y Ciencia for postdoctoral
fellowships. We also thank Dr. J.M. Muchowski for the critical
reviewing of the manuscript.
(300 MHz, CDCl3):
d 7.80e7.74 (m, 2H), 7.55e7.47 (m, 3H),
7.34e7.22 (m, 5H), 4.40 (m, 1H, NH), 4.24 (dd, J¼5.1 and 13.5 Hz,
1H), 3.89 (dd, J¼6.6 and 13.5 Hz, 1H). 13C NMR (75 MHz, CDCl3):
References and notes
d
144.0, 137.7, 130.9, 128.9, 128.6, 128.3, 127.7, 126.0, 44.7. MS (EI):
m/z 231 (Mþ, 2), 183 (13), 126 (32), 106 (100), 91 (77), 77 (37).
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sulfinate 1a and 4-methoxyaniline as starting material. White solid;
mp: 104e106 ꢀC [lit.6o mp: 105e106 ꢀC]. 1H NMR (300 MHz, CDCl3):
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d
7.79e7.72 (m, 2H), 7.52e7.47 (m, 3H), 7.02 and 6.80 (AA0BB0 sys-
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tem, 4H), 6.05 (s, 1H, NH), 3.76 (s, 3H). 13C NMR (75 MHz, CDCl3):
156.9, 144.7, 132.8, 131.2, 128.9, 125.6, 123.0, 114.6, 55.5.
d
4.3.4. N-Phenethylbenzenesulfinamide 90a6o. This sulfinamide was
obtained following the general procedure using methyl sulfinate 1a
and phenethylamine as starting material. Yellow oil. 1H NMR
(300 MHz, CDCl3):
d 7.68e7.61 (m, 2H), 7.52e7.44 (m, 3H),
7.33e7.20 (m, 3H), 7.17e7.12 (m, 2H), 4.14 (t, J¼5.7 Hz, 1H, NH),
3.45e3.32 (m, 1H), 3.15e3.02 (m, 1H), 2.81 (t, J¼6.9 Hz, 2H).
13C NMR (75 MHz, CDCl3):
d 144.1, 138.3, 130.8, 128.8 (2C), 128.6,
126.6, 126.0, 42.2, 36.8. MS (EI): m/z 245 (Mþ, 6), 216 (11), 154 (40),
125 (87), 91 (100), 77 (9).
4.3.5. N-Butylbenzenesulfonamide 6a6m. This sulfonamide was
obtained following the general procedure using methyl sulfinate 1a
and n-butylamine as starting material. Colorless oil. 1H NMR
(300 MHz, CDCl3):
d 7.90e7.86 (m, 2H), 7.60e7.48 (m, 3H), 4.66
(t, J¼5.4 Hz, 1H, NH), 2.95 (q, J¼6.9 Hz, 2H), 1.50e1.39 (m, 2H),
1.35e1.22 (m, 2H), 0.84 (t, J¼6.9 Hz, 3H). 13C NMR (75 MHz, CDCl3):
d
140.0, 132.5, 129.0, 127.0, 42.9, 31.6, 19.6, 13.5. MS (EI): m/z 213
(Mþ, 3), 170 (100), 141 (97), 77 (84).
4.3.6. N-Benzylbenzenesulfonamide 7a6q. This sulfonamide was
obtained following the general procedure using methyl sulfinate 1a
and benzylamine as starting material. White solid; mp: 89e90 ꢀC
[lit.6q mp: 84e87 ꢀC]. 1H NMR (300 MHz, CDCl3):
d 7.89e7.84 (m,
2H), 7.60e7.46 (m, 3H), 7.28e7.22 (m, 3H), 7.20e7.15 (m, 2H), 4.83
(t, J¼5.7 Hz, 1H, NH), 4.14 (d, J¼5.7 Hz, 2H). 13C NMR (75 MHz,
CDCl3): d 140.0, 136.2, 132.7, 129.1, 128.7, 127.9, 127.8, 127.1, 47.3. MS
(EI): m/z 247 (Mþ, 1), 143 (9), 125 (10), 106 (100), 91 (21), 77 (58).
4.3.7. N-(4-Methoxyphenyl)benzenesulfonamide 8a25. This sulfon-
amide was obtained following the general procedure using methyl
sulfinate 1a and 4-methoxyaniline as starting material. White solid;
mp: 91e92 ꢀC [lit.25 mp: 88e89 ꢀC]. 1H NMR (300 MHz, CDCl3):
7. Bahrami, K.; Khodaei, M. M.; Soheilizad, M. Tetrahedron Lett. 2010, 51, 4843.
8. García Ruano, J. L.; Parra, A.; Yuste, F.; Mastranzo, V. M. Synthesis 2008, 311.
9. When our methodology was published, we were unaware of a seminal publi-
cation of Colonna et al. (see below) describing the synthesis of optically active
sulfinamides by the reaction of lithium or bromomagnesium dialkylamides
d
7.73e7.69 (m, 2H), 7.55e7.50 (m, 1H), 7.45e7.39 (m, 2H), 6.97 and
6.75 (AA0BB0 system, 4H), 6.64 (s, 1H, NH), 3.75 (s, 3H). 13C NMR
(75 MHz, CDCl3):
114.4, 55.4.
d 158.0, 139.0, 132.8, 128.9, 128.7, 127.3, 125.6,