Iminations of Sulfoxides and Sulfides
FULL PAPER
General procedures for the silver-catalyzed iminations
N-(4-Nitrobenzenesulfonyl) (2-benzothiazolyl) methyl sulfoximine (6):
Chromatography: gradient of CH2Cl2 to ethyl acetate/CH2Cl2 1:20; white
solid; m.p. 202–2048C; 1H NMR (400 MHz, [D6]DMSO): d=8.36–8.30
(m, 1H, HAr), 8.25 (d, J=8.8 Hz, 2H, HAr), 8.19–8.13 (m, 1H, HAr), 7.97
(d, J=8.8 Hz, 2H, HAr), 7.72–7.66 (m, 2H, HAr), 3.91 ppm (s, 3H, CH3);
13C NMR (100 MHz, [D6]DMSO): d=165.1 (C), 152.2 (C), 149.9 (C),
147.9 (C), 137.5 (C), 128.9 (CH), 128.5 (CH), 128.3 (2CH), 125.2 (CH),
124.8 (2CH), 124.0 (CH), 40.7 ppm (CH3); IR (KBr): n˜ =3099, 3015,
2926, 1602, 1529, 1311, 1155, 1068, 764, 620 cmÀ1; MS (CI): m/z (%): 398
(100) [M+H+], 136 (55); elemental analysis calcd (%) for C14H11N3O5S3
(397.45): C 42.31, H 2.79, N 10.57; found: C 42.40, H 3.14, N 10.46.
Method A: A mixture of the sulfur compound (0.20 mmol), AgNO3
(2.7 mg, 0.016 mmol), tBu3tpy (6.4 mg, 0.016 mmol), sulfonyl amide
(0.24 mmol) and PhI(OAc)2 (96.6 mg, 0.30 mmol) in CH3CN (2.0 mL)
G
was stirred at room temperature. The reaction mixture was concentrated
under reduced pressure and the residue was purified by flash column
chromatography.
Method B: As described in method A but using the corresponding pre-
formed iminoiodinane PhI=NR (0.30 mmol) instead of the sulfonyl
amide/PhI(OAc)2 mixture.
E
General procedures for the iron-catalyzed iminations
N-(4-Nitrobenzenesulfonyl) methyl [2-(N-methylimidazolyl)] sulfoximine
(7): Chromatography: gradient of ethyl acetate/pentane 2:1 to ethyl ace-
tate; white solid; m.p. 126–1298C; 1H NMR (400 MHz, CD2Cl2): d=8.20
(d, J=8.8 Hz, 2H, HAr), 7.89 (d, J=8.8 Hz, 2H, HAr), 7.06 (brs, 1H,
HAr), 7.03 (brs, 1H, HAr), 3.89 (s, 3H, CH3), 3.56 ppm (s, 3H, CH3);
13C NMR (100 MHz, CD2Cl2): d=149.7 (C), 148.2 (C), 138.2 (C), 129.6
(CH), 127.8 (2CH), 127.2 (CH), 123.9 (2CH), 44.8 (CH3), 35.8 ppm
(CH3); IR (KBr): n˜ =3119, 3021, 2924, 1609, 1533, 1316, 1244, 1157, 1057,
745; MS (CI): m/z (%): 345 (100) [M+H+]; elemental analysis calcd (%)
for C11H12N4O5S2 (344.37): C 38.37, H 3.51, N 16.27; found: C 38.51, H
3.60, N 16.01.
Method A: A mixture of sulfur compound (0.20 mmol), [Fe(acac)3]
A
(7.1 mg, 0.020 mmol), sulfonyl amide (0.30 mmol) and PhI=O (70.4 mg,
0.32 mmol) in CH3CN (2.0 mL) was stirred at room temperature. The re-
action mixture was concentrated under reduced pressure and the residue
was purified by flash column chromatography.
Method B: As described in method A but using the corresponding pre-
formed iminoiodinane PhI=NR (0.30 mmol) instead of the sulfonyl
amide/PhI=O mixture.
General procedure for the copper-catalyzed iminations
Method B:
A
mixture of sulfur compound (0.20 mmol), Cu(OTf)2
A
(7.2 mg, 0.020 mmol) and the corresponding iminoiodinane PhI=NR
(0.30 mmol) in CH3CN (2.0 mL) was stirred at room temperature. The re-
action mixture was concentrated under reduced pressure and the residue
was purified by flash column chromatography.
N-(4-Nitrobenzenesulfonyl) methyl phenyl sulfoximine (2):[12, 14–17] Chro-
matography: gradient of ethyl acetate/pentane 1:2 to 1:1; pale yellow
solid; m.p. 148–1508C (lit.:[14] 148–1518C); 1H NMR (400 MHz, CDCl3):
d=8.32 (d, J=9.2 Hz, 2H, HAr), 8.16 (d, J=9.2 Hz, 2H, HAr), 8.03 (d, J=
N-(4-Nitrobenzenesulfonyl) methyl [2-(5-phenyl-1,3,4-oxadiazolyl)] sul-
foximine (8): Chromatography: CH2Cl2; white solid; m.p. 182–1838C;
1H NMR (400 MHz, [D6]DMSO): d=8.33 (d, J=8.8 Hz, 2H, HAr), 8.04
(d, J=8.8 Hz, 2H, HAr), 8.03 (d, J=7.4 Hz, 2H, HAr), 7.73 (t, J=7.4 Hz,
2H, HAr), 7.64 (t, J=7.4 Hz, 2H, HAr), 4.04 ppm (s, 3H, CH3); 13C NMR
(100 MHz, [D6]DMSO): d=167.0 (C), 160.7 (C), 150.2 (C), 147.1 (C),
134.1 (CH), 130.2 (2CH), 128.4 (2CH), 127.8 (2CH), 125.1 (2
CH), 122.0 (C), 43.7 ppm (CH3); IR (KBr): n˜ =3015, 2922, 1778, 1607,
1533, 1344, 1279, 1088, 750; MS (CI): m/z (%): 409 (12) [M+H+], 307
(32), 163 (100); elemental analysis calcd (%) for C15H12N4O6S2 (408.41):
C 44.11, H 2.96, N 13.72; found: C 43.97, H 3.34, N 13.70.
cis-10-Monoxy-5-[N-(p-toluenesulfonyl)]imino thianthrene (cis-12):[21]
Chromatography: gradient of ethyl acetate/pentane 1:2 to ethyl acetate;
white solid; m.p. 211–2128C (lit.:[21] 215–2218C); 1H NMR (400 MHz,
CDCl3): d=7.99 (d, J=7.7 Hz, 2H, HAr), 7.96 (d, J=8.2 Hz, 2H, HAr),
7.90 (d, J=8.2 Hz, 2H, HAr), 7.69 (t, J=7.6 Hz, 2H, HAr), 7.61 (t, J=
7.7 Hz, 2H, HAr), 7.26 (d, J=8.2 Hz, 2H, HAr), 2.36 ppm (s, 3H, CH3);
13C NMR (100 MHz, CDCl3): d=142.8 (C), 140.3 (C), 139.2 (C), 131.9
(2CH), 131.4 (2CH), 129.7 (2CH), 129.2 (2CH), 126.4 (2CH),
124.9 (2CH), 124.3 (2CH), 21.7 ppm (CH3); MS (CI): m/z (%): 402
(47) [M+H+], 233 (100) [(M+H)+ÀNTs], 172 (42); elemental analysis
calcd (%) for C19H15NO3S3 (401.53): C 56.83, H 3.77, N 3.49; found: C
56.69, H 4.89, N 3.61.
7.9 Hz, 2H,
HAr), 7.80–7.72 (m, 1H, HAr), 7.68–7.62 (m, 2H, HAr),
3.47 ppm (s, 3H, CH3); 13C NMR (100 MHz, CDCl3): d=149.7 (C), 149.0
(C), 137.8 (C), 134.9 (CH), 130.0 (2CH), 128.1 (2CH), 127.4 (2CH),
124.0 (2CH), 46.9 ppm (CH3).
N-(4-Nitrobenzenesulfonyl) methyl (2-pyridyl) sulfoximine (3): Chroma-
tography: gradient of ethyl acetate/pentane 1:1 to ethyl acetate; white
solid; m.p. 132–1348C; 1H NMR (400 MHz, CD2Cl2): d=8.63 (d, J=
4.7 Hz, 1H, HAr), 8.20 (d, J=8.8 Hz, 2H, HAr), 8.11 (d, J=7.7 Hz, 1H,
HAr), 8.01–7.94 (m, 3H, HAr), 7.57 (dd, J=7.7, 4.7 Hz, 1H, HAr),
3.44 ppm (s, 3H, CH3); 13C NMR (100 MHz, CD2Cl2): d=155.6 (C),
150.3 (CH), 149.6 (C), 140.8 (C), 138.7 (CH), 128.3 (CH), 127.8 (2CH),
123.9 (2CH), 123.0 (CH), 41.8 ppm (CH3); IR (KBr): n˜ =3104, 3029,
2936, 1603, 1526, 1466, 1312, 1256, 1159, 1094, 961, 720 cmÀ1; MS (CI):
m/z (%): 342 (100) [M+H+], 326 (5) [(M+H)+ÀO]; elemental analysis
calcd (%) for C12H11N3O5S2 (341.36): C 42.22, H 3.25, N 12.31; found: C
42.34, H 3.47, N 12.27.
trans-10-Monoxy-5-[N-(p-toluenesulfonyl)]imino thianthrene (trans-
12):[21] Chromatography: gradient of ethyl acetate/pentane 1:2 to ethyl
acetate; white solid; m.p. 210–2128C (lit.:[21] 210–2158C); 1H NMR
(400 MHz, CDCl3): d=8.00 (dd, J=7.4, 1.4 Hz, 2H, HAr), 7.97 (dd, J=
7.4, 1.4 Hz, 2H, HAr), 7.70 (d, J=8.2 Hz, 2H, HAr), 7.63 (td, J=7.4,
1.4 Hz, 2H, HAr), 7.56 (td, J=7.3, 1.4 Hz, 2H, HAr), 7.12 (d, J=8.2 Hz,
2H, HAr), 2.30 ppm (s, 3H, CH3); 13C NMR (100 MHz, CDCl3): d=143.8
(C), 142.2 (C), 140.5 (C), 133.0 (C), 132.4 (C), 131.9 (CH), 129.4 (2
CH), 129.0 (2CH), 128.3 (2CH), 126.3 (2CH), 21.6 ppm (CH3); MS
(CI): m/z (%): 402 [(M+H)+, 22], 233 [(M+H)+-NTs, 100], 172 (35); ele-
mental analysis calcd (%) for C19H15NO3S3 (401.53): C 56.83, H 3.77, N
3.49; found: C 56.89, H 3.80, N 3.65.
N-(4-Nitrobenzenesulfonyl) methyl (2-pyrazinyl) sulfoximine (4): Chro-
matography: gradient of ethyl acetate/pentane 1:1 to ethyl acetate; white
solid; m.p. 166–1678C; 1H NMR (400 MHz, CD2Cl2): d=9.39 (brs, 1H,
HAr), 8.95 (brs, 1H, HAr), 8.75 (brs, 1H, HAr), 8.31 (brd, J=9.1 Hz, 2H,
HAr), 8.08 (brd, J=9.1 Hz, 2H, HAr), 3.53 ppm (s, 3H, CH3); 13C NMR
(100 MHz, CD2Cl2): d=152.1 (C), 149.8 (C), 149.0 (CH), 148.4 (C), 144.5
(CH), 143.8 (CH), 127.9 (2CH), 124.0 (2CH), 41.9 ppm (CH3); IR
(KBr): n˜ =3075, 3027, 1730, 1603, 1522, 1312, 1158, 1073, 779, 713,
620 cmÀ1; MS (CI): m/z (%): 343 (100) [M+H+], 327 (7) [(M+H)+ÀO];
elemental analysis calcd (%) for C11H10N4O5S2 (342.35): C 38.59, H 2.94,
N 16.37; found: C 38.72, H 3.20, N 16.34.
N-(4-Nitrobenzenesulfonyl) methyl (2-pyrimidinyl) sulfoximine (5):
10-Monoxy-5,10-bis[N-(p-toluenesulfonyl)imino] thianthrene (cis- and
trans-13): Chromatography: gradient of ethyl acetate/pentane 1:2 to
ethyl acetate; white solid; major isomer: 1H NMR (400 MHz, CDCl3):
d=8.19 (dd, J=7.4, 1.7 Hz, 2H, HAr), 7.89 (dd, J=7.7, 1.4 Hz, 2H, HAr),
7.82 (d, J=8.2 Hz, 2H, HAr), 7.75–7.65 (m, 4H, HAr), 7.42 (d, J=8.2 Hz,
2H, HAr), 7.27 (d, J=8.0 Hz, 2H, HAr), 7.12 (d, J=8.0 Hz, 2H, HAr), 2.38
(s, 3H, CH3), 2.33 ppm (s, 3H, CH3); major isomer: 13C NMR (75 MHz,
CDCl3): d=144.1 (C), 143.1 (C), 140.1 (C), 138.2 (C), 137.9 (C), 134.0
(2CH), 132.4 (C), 131.9 (2CH), 129.9 (2CH), 129.6 (2CH), 128.1
(2CH), 126.7 (2CH), 126.5 (2CH), 126.4 (2CH), 21.6 (CH3),
21.5 ppm (CH3); IR (KBr): n˜ =3073, 2956, 1594, 1444, 1329, 1273, 1152,
Chromatography: gradient of ethyl acetate/pentane 1:1 to ethyl acetate
and then acetone; white solid; m.p.
>
2058C (decomp); 1H NMR
(300 MHz, [D6]DMSO): d=9.13 (d, J=5.0 Hz, 2H, HAr), 8.35 (d, J=
9.0 Hz, 2H, HAr), 7.99 (d, J=9.0 Hz, 2H, HAr), 7.91 (t, J=5.0 Hz, 1H,
HAr), 3.73 ppm (s, 3H, CH3); 13C NMR (75 MHz, [D6]DMSO): d=164.1
(C), 160.0 (2CH), 149.9 (C), 148.7 (C), 128.2 (2CH), 125.6 (CH),
124.8 (2CH), 41.1 ppm (CH3); IR (KBr): n˜ =3013, 2922, 1572, 1531,
1383, 1307, 1163, 1073, 614 cmÀ1; MS (CI): m/z (%): 343 (100) [M+H+];
elemental analysis calcd (%) for C11H10N4O5S2 (342.35): C 38.59, H 2.94,
N 16.37; found: C 38.21, H 3.28, N 16.51.
Chem. Eur. J. 2007, 13, 6674 – 6681
ꢀ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
6679