The Journal of Organic Chemistry
Article
chromatography (30% EtOAc/hexane) afforded N-Boc-sulfoximine 2e
(168 mg, 78%) as a white solid. Rf = 0.5 (30% EtOAc/hexane); mp
=125−129 °C; IR (film) νmax (cm−1): 2979, 1651, 1274, 1143, 893,
985, 835, 817, 786, 753, 1H NMR (400 MHz, CDCl3): δ 7.65 (app d, J
= 8 Hz, 2H), 7.32 (app d, J = 8 Hz, 2H), 2.77 (s, 3H), 2.41 (s, 3H),
1.46 (s, 9H); 13C{1H} NMR (101 MHz, CDCl3): δ 164.6, 143.0,
133.8, 130.6 (2C), 126.3 (2C), 79.0, 36.0, 28.5 (3C), 21.5; HRMS
(ESI-TOF) m/z: calcd for C13H20NO2S [M + H]+ 254.1215, found
254.1225.
1
855, 762, 726; H NMR (400 MHz, CDCl3): δ 7.87 (app d, J = 8.3
Hz, 2H), 7.41 (app d, J = 8.3 Hz, 2H), 7.31−7.19 (m, 3H), 7.15−7.06
(m, 2H), 3.67 (ddd, J = 13.8, 12.2, 5.0 Hz, 1H), 3.51 (ddd, J = 13.8,
12.2, 5.0 Hz, 1H), 3.13 (app. td, J = 13, 5.0 Hz, 1H), 2.97 (app. td, J =
13, 5.0 Hz, 1H), 2.49 (s, 3H), 1.42 (s, 9H); 13C{1H} NMR (101 MHz,
CDCl3): δ 158.0, 144.9, 137.1, 134.2, 130.4 (2C), 128.9 (2C), 128.5
(2C), 128.1 (2C), 127.1, 80.6, 57.5, 28.4, 28.1 (3C), 21.7; HRMS
(ESI-TOF) m/z: calcd for C20H26NO3S+ [M + H]+ 360.1633, found
360.1639.
Methyl[methyl(4-methylphenyl)oxido-λ6-sulfanylidene]-
carbamate (3a). Prepared according to General Procedure 1 using
sulfoxide 1a (98 mg, 0.64 mmol) and methyl carbamate (72 mg, 0.96
mmol). Purification by flash chromatography (30% hexane/EtOAc)
afforded sulfoximine 3a (142 mg, 98%) as a white solid. Rf = 0.5 (30%
hexane/EtOAc); mp =92−96 °C; IR (film) νmax (cm−1): 2952, 1672,
1251, 1226, 1089, 982, 873, 790; 1H NMR (400 MHz, CDCl3): δ 7.84
(app d, J = 8.3 Hz, 2H), 7.37 (app d, J = 8.3 Hz, 2H), 3.63 (s, 3H),
3.27 (s, 3H), 2.43 (s, 3H); 13C{1H} NMR (101 MHz, CDCl3): δ
159.5, 145.2, 135.2, 130.4 (2C), 127.4 (2C), 53.2, 44.6, 21.7; HRMS
(ESI-TOF) m/z: calcd for C10H14NO3S+ [M + H]+ 228.0694, found
228.0703.
tert-Butyl[oxido(diphenyl)-λ6-sulfanylidene]carbamate (2f). Pre-
pared according to General Procedure 1 using sulfoxide 1f (127 mg,
0.63 mmol) and tert-butylcarbamate (110 mg, 0.940 mmol).
Purification by flash chromatography (30% EtOAc/hexane) afforded
N-Boc-sulfoximine 2f (139 mg, 70%) as a white solid. Rf = 0.3 (30%
EtOAc/hexane); mp =97−102 °C; IR (film) νmax (cm−1): 2985, 1687,
1446, 1365, 1237, 1092, 913, 780, 763, 726, 684; 1H NMR (400 MHz,
CDCl3): δ 8.03−8.00 (m, 4H), 7.58−7.49 (m, 6H), 1.33 (s, 9H);
13C{1H} NMR (101 MHz, CDCl3): δ 157.3, 140.1 (2C), 133.3 (2C),
Methyl[(chloromethyl)(4-methylphenyl)oxido-λ6-sulfanylidene]-
carbamate (3d). Prepared according to General Procedure 1 using
sulfoxide 1d (123 mg, 0.65 mmol) and methyl carbamate (73 mg, 0.97
mmol). Purification by flash chromatography (50% EtOAc/hexane)
afforded sulfoximine 3d (113 mg, 66%) as a white solid. Rf = 0.5 (50%
ethyl acetate/hexane); mp =80−84 °C; IR (film) νmax (cm−1): 3017,
2955, 1670, 1439, 1263, 1234, 1192, 1148, 1090, 961, 894, 814, 737;
1H NMR (400 MHz, CDCl3): δ 7.90 (app d, J = 8.3 Hz, 2H), 7.41
(app d, J = 8.3 Hz, 2H), 5.18 (d, J = 11.9 Hz, 1H), 4.84 (d, J = 11.9
Hz, 1H), 3.73 (s, 3H), 2.47 (s, 3H); 13C{1H} NMR (101 MHz,
CDCl3): δ 159.2, 146.5, 130.4 (2C), 130.0, 129.5 (2C), 58.6, 53.7,
21.9; HRMS (ESI-TOF) m/z: calcd for C10H13ClNO3S+ [M + H]+
262.0305, found 262.0308.
129.5 (4C), 127.9 (4C), 80.8, 28.1 (3C); HRMS (ESI-TOF) m/z:
calcd for C17H20NO3S [M + H ]+ 318.1164, found 318.1164.
tert-Butyl[ethenyl(oxido)phenyl-λ6-sulfanylidene]carbamate
(2g). Prepared according to General Procedure 1 using sulfoxide 1g
(94 mg, 0.62 mmol) and tert-butylcarbamate (109 mg, 0.930 mmol).
Purification by flash chromatography (50% EtOAC/hexane) afforded
N-Boc-sulfoximine 2g (147 mg, 89%) as a white solid. Rf = 0.5 (50%
EtOAc/hexane); mp =83−87 °C; IR (film) νmax (cm−1): 3062, 2973,
1655, 1271, 1232, 1151, 1085, 979, 894, 867, 755, 690; 1H NMR (400
MHz, CDCl3): δ 7.95 (app d, J = 7.6 Hz, 2H), 7.64 (t, J = 7.6 Hz, 1H),
7.56 (app t, J = 7.6 Hz, 2H), 6.73 (dd, J = 16.4, 9.6 Hz, 1H), 6.47 (d, J
= 16.4 Hz, 1H), 6.12 (d, J = 9.6 Hz, 1H), 1.38 (s, 9H); 13C{1H} NMR
(101 MHz, CDCl3): δ 157.5, 138.1, 137.3, 133.7, 129.7 (2C), 128.8,
128.0 (2C), 80.9, 28.1 (3C); HRMS (ESI-TOF) m/z: calcd for
C13H18NO3S+ [M + H]+ 268.1007, found 268.1010.
Methyl[ethenyl(oxido)phenyl-λ6-sulfanylidene]carbamate (3g).
Prepared according to General Procedure 1 using sulfoxide 1g (91
mg, 0.60 mmol) and methyl carbamate (67 mg, 0.90 mmol).
Purification by flash chromatography (50% EtOAc/hexane) afforded
sulfoximine 3g (106 mg, 78%) as a white solid. Rf = 0.4 (50% EtOAc/
hexane); mp =59−63 °C; IR (film) νmax (cm−1): 3062, 2957, 1647,
1438, 1252, 1218, 955, 888, 792, 770, 699, 685; 1H NMR (400 MHz,
CDCl3): δ 7.96 (app d, J = 8.0 Hz, 2H), 7.66 (t, J = 8.0 Hz, 1H), 7.58
(app t, J = 8.0 Hz, 2H), 6.74 (dd, J = 16.3, 9.6 Hz, 1H), 6.51 (d, J =
16.3 Hz, 1H), 6.18 (d, J = 9.6 Hz, 1H), 3.67 (s, 3H); 13C{1H} NMR
(101 MHz, CDCl3): δ 159.3, 137.5, 136.9, 134.0, 129.8 (2C), 129.3,
128.0 (2C), 53.4; HRMS (ESI-TOF) m/z: calcd for C10H12NO3S+ [M
+ H]+ 226.0538, found 226.0542.
tert-Butyl[dibenzyl(oxido)-λ6-sulfanylidene]carbamate (2h). Pre-
pared according to General Procedure 1 using sulfoxide 1h (138 mg,
0.60 mmol) and tert-butylcarbamate (105 mg, 0.900 mmol).
Purification by flash chromatography (40% hexane/EtOAc) and
recrystallization (Et2O) afforded N-Boc-sulfoximine 2h (137 mg,
66%) as a white solid. Rf = 0.3 (40% hexane/EtOAc); mp =129−131
°C; IR (film) νmax (cm−1): 2984, 1657, 1457, 1365, 1287, 1247, 1146,
1
912, 771, 697; H NMR (400 MHz, CDCl3): δ 7.42−7.38 (m, 10H),
4.55 (d, J = 14 Hz, 2H), 4.48 (d, J = 14 Hz, 2H), 1.52 (s, 9H);
Ethyl[methyl(4-methylphenyl)oxido-λ6-sulfanylidene]carbamate
(4a). Prepared according to General Procedure 1 using sulfoxide 1a
(101 mg, 0.657 mmol) and ethyl carbamate (87.7 mg, 0.985 mmol).
Purification by flash chromatography (30% hexane/EtOAc) afforded
sulfoximine 4a (122 mg, 77%) as a white solid. Rf = 0.4 (30% hexane/
EtOAc); mp =57−61 °C; IR (film) νmax (cm−1): 3018, 2988, 2930,
1664, 1592, 1467, 1412, 1368, 1244, 1219, 1085, 986, 872, 790, 766;
1H NMR (400 MHz, CDCl3): δ 7.86 (app d, J = 8.2 Hz, 2H), 7.38
13C{1H} NMR (101 MHz, CDCl3): δ 158.6, 131.4 (4C), 129.5 (2C),
129.2 (4C), 126.9 (2C), 80.5, 56.4 (2C), 28.3 (3C); HRMS (ESI-
TOF) m/z: calcd for C19H24NO3S+ [M + H]+ 346.1479, found
346.1477.
tert-Butyl(1-oxidotetrahydro-1H-1λ4-thiophen-1-ylidene)-
carbamate (2i). Prepared according to General Procedure 1 using
sulfoxide 1i (70 mg, 0.67 mmol) and tert-butylcarbamate (118 mg,
1.00 mmol). Purification by flash chromatography (30% hexane/
EtOAc) afforded N-Boc-sulfoximine 2i (115 mg, 78%) as a yellow oil.
Rf = 0.3 (30% hexane/ethyl acetate); IR (film) νmax (cm−1): 2975,
1651, 1287, 1155, 727; 1H NMR (400 MHz, CDCl3): δ 3.55−3.48 (m,
2H), 3.20 (app. dt, J = 12.6, 6.1 Hz, 2H), 2.16−2.28 (m, 4H), 1.41 (s,
9H); 13C{1H} NMR (101 MHz, CDCl3): δ 159.1, 80.5, 52.8 (2C),
28.1 (3C), 23.5 (2C); HRMS (ESI-TOF) m/z: calcd for
C11H20N2O3NaS+ [M + CH3CN + Na]+ 283.1092, found 283.1080.
tert-Butyl[(Z)-methyl(phenyl)-λ4-sulfanylidene]carbamate (2j).
To a suspension of the methyl 4-methylphenyl sulfide (98 mg, 0.71
mmol), tert-butylcarbamate (125 mg, 1.06 mmol), MgO (97 mg, 2.4
mmol) and Rh2(OAc)4 (7.0 mg, 2.5 mol %) in CH2Cl2 (6 mL) was
added PhI(OAc)4 (290 mg, 0.900 mmol) at rt. The resulting mixture
was stirred for 8 h at 40 °C. The reaction mixture was filtered through
a pad of diatomaceous earth and concentrated in vacuo. Purification by
flash chromatography (EtOAc) afforded N-Boc-sulfilimine 2j (61 mg,
34%) as a white solid. Rf = 0.3 (EtOAc); mp =152−155 °C; IR (film)
νmax (cm−1): 3013, 2975, 2925, 1626, 1361, 1277, 1246, 1158, 1079,
(app d, J = 8.2 Hz, 2H), 4.14−4.02 (m, 2H), 3.28 (s, 3H), 2.45 (s,
3H), 1.22 (t, J = 7.2 Hz, 3H); 13C{1H} NMR (101 MHz, CDCl3): δ
159.1, 145.2, 135.4, 130.4 (2C), 127.5 (2C), 62.0, 44.8, 21.7, 14.4;
HRMS (ESI-TOF) m/z: calcd for C11H16NO3S+ [M + H]+ 242.0851,
found 242.0850. Compound previously reported.46
Ethyl[dibenzyl(oxido)-λ6-sulfanylidene]carbamate (4h). Prepared
according to General Procedure 1 using sulfoxide 1h (139 mg, 0.604
mmol) and ethyl carbamate (80.7 mg, 0.906 mmol). Purification by
flash chromatography (30% EtOAc/hexane) afforded sulfoximine 4h
(145 mg, 76%) as a white solid. Rf = 0.3 (30% EtOAc/hexane); mp
=98−102 °C; IR (film) νmax (cm−1): 3065, 2974, 2940, 1646, 1456,
1
1365, 1273, 1233, 1109, 1003, 905, 785, 695; H NMR (400 MHz,
CDCl3): δ 7.46−7.33 (m, 10H), 4.56 (d, J = 14.0 Hz, 2H), 4.51 (d, J =
14.0 Hz, 2H), 4.17 (q, J = 7.1 Hz, 2H), 1.30 (t, J = 7.1 Hz, 3H);
13C{1H} NMR (101 MHz, CDCl3): δ 159.4, 131.4 (4C), 129.6 (2C),
129.2 (4C), 126.6 (2C), 62.3, 56.6 (2C), 14.6; HRMS (ESI-TOF) m/
z: calcd for C17H20NO3S+ [M + H]+ 318.1164, found 318.1172.
E
J. Org. Chem. XXXX, XXX, XXX−XXX