8606 J . Org. Chem., Vol. 62, No. 24, 1997
Notes
To a solution of dibenzylamine (300 mg, 1.52 mmol) and
triethylamine (2.21 mL, 15.2 mmol) in CH2Cl2 (20 mL) was
added dropwise ice-cold tert-butylsulfinyl chloride (428 mg, 3.04
mmol) in CH2Cl2 (15 mL) at 0 °C. After 1 h (TLC monitoring,
EtOAc:MeOH, 9:1 containing 3% NH4OH), the mixture was
diluted with saturated aqueous NaHCO3.7 The aqueous layer
was extracted with CH2Cl2 (20 mL). The organic extracts were
combined, dried over MgSO4, and concentrated under reduced
pressure. The residue was purified by flash column chroma-
tography (EtOAc:hexanes, 1:4) to afford sulfinamide 2a as a
white solid (mp 54-56 °C): 1H NMR (300 MHz, CDCl3) δ 7.33-
7.25 (m, 10 H), 4.30 (d, J ) 15.0 Hz, 2 H), 4.05 (d, J ) 15.0 Hz,
2 H), 1.22 (s, 9 H); 13C NMR (75 MHz, CDCl3) δ 136.7, 128.5,
128.3, 127.3, 58.4, 51.3, 23.1; CIMS m/z (relative intensity) 302
(MH+, 7), 85 (75), 69 (100).
1-In d olin etr im eth ylm eth a n esu lfin a m id e (2b). The gen-
eral procedure was followed using 1-indoline (319 mg, 2.67
mmol), tert-butylsulfinyl chloride (753 mg, 5.35 mmol), trieth-
ylamine (2.98 mL, 21.4 mmol), and CH2Cl2 (15 mL). The crude
product was purified by flash column chromatography (EtOAc:
hexanes, 1:9) to afford sulfinamide 2b (595 mg, 100%) as a
colorless liquid: 1H NMR (300 MHz, CDCl3) δ 7.15-6.88 (m, 4
H), 4.27 (dt, J ) 6.6, 10.5 Hz, 1 H), 3.48 (dt, J ) 6.9, 10.3 Hz, 1
H), 3.27-3.01 (m, 2 H), 1.31 (s, 9 H); 13C NMR (75 MHz, CDCl3)
δ 148.9, 130.9, 127.2, 124.7, 122.2, 112.3, 57.8, 41.7, 29.3, 23.2;
CIMS m/z (relative intensity) 224 (MH+, 90), 167 (MH+ - t-Bu,
75), 150 (100), 120 (MH+ - tert-butylsulfinyl, 88).
tert-butylsulfinyl chloride (588 mg, 4.18 mmol), triethylamine
(1.47 mL, 10.5 mmol), and CH2Cl2 (15 mL). The crude product
was purified by flash column chromatography (EtOAc:hexanes,
1:4) to afford sulfinamide 2g (422 mg, 83%) as a colorless
liquid: 1H NMR (300 MHz, CDCl3) δ 3.22-2.98 (m, 3 H), 1.53
(br tt, J ) 6.9, 6.8 Hz, 2 H), 1.24 (br s, 12 H), 1.18 (s, 9 H), 0.85
(br t, J ) 6.7 Hz, 3 H); 13C NMR (75 MHz, CDCl3) δ 55.4, 45.7,
31.8, 31.0, 29.4, 29.2, 26.7, 22.6 (2C), 14.0; CIMS m/z (relative
intensity) 248 (MH+, 100), 191 (MH+ - t-Bu, 41).
Gen er a l P r oced u r e for F or m a tion of ter t-Bu tylsu lfon a -
m id es. N,N-Diben zyltr im eth ylm eth a n esu lfon a m id e (3a ).
A. To a solution of sulfinamide 2a (100 mg, 0.33 mmol) in
CH2Cl2 (5 mL) was added m-CPBA (55%, 135 mg, 0.43 mmol)
at rt. After 45 min, the reaction mixture was diluted with a
mixture of saturated aqueous NaHSO3 (5 mL) and NaHCO3 (5
mL). The aqueous layer was extracted with CH2Cl2 (2 × 5 mL).
The organic extracts were combined, dried over MgSO4, and
concentrated under reduced pressure. The residue was purified
by flash column chromatography (EtOAc:hexanes, 1:4) to afford
sulfonamide 3a (102 mg, 97%) as a white solid (mp 125-127
°C): 1H NMR (300 MHz, CDCl3) δ 7.30-7.20 (m, 10 H), 4.44 (s,
4 H), 1.52 (s, 9 H); 13C NMR (75 MHz, CDCl3) δ 135.8, 128.4,
128.4, 127.5, 61.8, 51.4, 24.8; CIMS m/z (relative intensity) 318
(MH+, 7), 261 (MH+ - t-Bu, 100), 196 (M+ - tert-butylsulfonyl,
34); HRMS calcd for C18H23NO2S 317.1449, found 317.1454.
B. To a solution of sulfinamide 2a (100 mg, 0.33 mmol) in a
mixture of CH2Cl2 (3 mL), CH3CN (3 mL), and H2O (4.7 mL)
were added RuCl3‚H2O (0.74 mg, 0.0033 mmol)15 and NaIO4 (85
mg, 0.40 mmol) at 0 °C. After 1 h, the mixture was diluted with
CH2Cl2 (5 mL) and the aqueous layer was extracted with 12 mL
of CH2Cl2. The organic extracts were combined, dried over
MgSO4, and concentrated under reduced pressure. The residue
was purified by flash column chromatography as above giving
the sulfonamide 3a (101 mg, 97%) as a white solid.
1-In d olin etr im eth ylm eth a n esu lfon a m id e (3b). A. The
general procedure was followed using sulfinamide 2b (200 mg,
0.90 mmol), m-CPBA (55%, 365 mg, 1.16 mmol), and CH2Cl2
(10 mL). The crude product was purified by flash column
chromatography (EtOAc:hexanes, 1:4) to afford sulfonamide 3b
(180 mg, 84%) as a colorless liquid: 1H NMR (300 MHz, CDCl3)
δ 7.40-6.92 (m, 4 H), 4.12 (t, J ) 8.5 Hz, 2 H), 3.13 (t, J ) 8.5
Hz, 2 H), 1.47 (s, 9 H); 13C NMR (75 MHz, CDCl3) δ 143.4, 130.5,
127.4, 124.9, 122.5, 114.1, 62.6, 51.9, 28.2, 24.6; CIMS m/z
(relative intensity) 240 (MH+, 63), 183 (MH+ - t-Bu, 100), 118
(M+ - tert-butylsulfonyl, 44).
B. The general procedure was followed using sulfinamide 2b
(84 mg, 0.38 mmol), RuCl3‚H2O (0.85 mg, 0.004 mmol), and
NaIO4 (105 mg, 0.49 mmol) in a mixture of CH2Cl2 (7 mL),
CH3CN (7 mL), and H2O (11 mL). The crude product was
purified by flash column chromatography as above to afford
sulfonamide 3b (78 mg, 87%).
1,2,3,4-Tet r a h yd r oisoq u in olin et r im et h ylm et h a n esu l-
fon a m id e (3c). A. The general procedure was followed using
sulfinamide 2c (505 mg, 2.13 mmol), m-CPBA (55%, 868 mg,
2.77 mmol), and CH2Cl2 (20 mL). The crude product was
purified by flash column chromatography (EtOAc:hexanes, 1:4)
to afford sulfonamide 3c (497 mg, 92%) as a white solid (mp
105-106 °C): 1H NMR (300 MHz, CDCl3) δ 7.20-7.04 (m, 4 H),
4.57 (s, 2 H), 3.66 (t, J ) 5.9 Hz, 2 H), 2.96 (t, J ) 5.8 Hz, 2 H),
1.41 (s, 9 H); 13C NMR (75 MHz, CDCl3) δ 133.4, 132.7, 129.1,
126.6, 126.2, 126.0, 61.3, 48.7, 44.9, 29.4, 24.4; CIMS m/z
(relative intensity) 254 (MH+, 49), 197 (MH+ - t-Bu, 100), 132
(MH+ - tert-butylsulfonyl, 75).
1,2,3,4-Tetr a h yd r oisoqu in olin etr im eth ylm eth a n esu lfin -
a m id e (2c). The general procedure was followed using 1,2,3,4-
tetrahydroisoquinoline (319 mg, 2.40 mmol), tert-butylsulfinyl
chloride (471 mg, 3.35 mmol), triethylamine (3.34 mL, 24.0
mmol), and CH2Cl2 (15 mL). The crude product was purified
by flash column chromatography (EtOAc:hexanes, 1:4) to afford
sulfinamide 2c (430 mg, 78%) as a colorless liquid: 1H NMR
(300 MHz, CDCl3) δ 7.15-7.02 (m, 4 H), 4.28 (dd, J ) 24.0, 15.7
Hz, 2 H), 3.47 (dt, J ) 12.8, 6.0 Hz, 1 H), 3.32 (dt, J ) 12.7, 6.2
Hz, 1 H), 2.90 (t, J ) 5.7 Hz, 2 H), 1.21 (s, 9 H); 13C NMR (75
MHz, CDCl3) δ 134.1, 133.4, 128.8, 126.3, 126.1, 125.9, 58.2, 47.2,
45.3, 29.1, 22.9; CIMS m/z (relative intensity) 238 (MH+, 100),
181 (MH+ - t-Bu, 51), 132 (M+ - tert-butylsulfinyl, 20).
1,2,3,4-Tet r a h yd r oq u in olin et r im et h ylm et h a n esu lfin -
a m id e (2d ). The general procedure was followed using 1,2,3,4-
tetrahydroquinoline (318 mg, 2.39 mmol), tert-butylsulfinyl
chloride (583 mg, 4.78 mmol), triethylamine (3.33 mL, 23.9
mmol), and CH2Cl2 (15 mL). The crude product was purified
by flash column chromatography (EtOAc:hexanes, 1:9) to afford
sulfinamide 2d (501 mg, 88%) as a colorless liquid: 1H NMR
(300 MHz, CDCl3) δ 7.11-6.86 (m, 4 H), 4.11 (dt, J ) 12.7, 4.0
Hz, 1 H), 3.09 (ddd, J ) 13.2, 11.0, 2.7 Hz, 1 H), 2.80 (J ) 8.3,
4.7 Hz, 2 H), 2.02-1.92 (m, 1 H), 1.85-1.73 (m, 1 H), 1.31 (s, 9
H); 13C NMR (75 MHz, CDCl3) δ 142.5, 129.6, 126.4, 125.8, 121.2,
117.9, 59.4, 39.1, 27.1, 23.7, 22.5; CIMS m/z (relative intensity)
238 (MH+, 73), 181 (MH+ - t-t-Bu, 83), 164 (100), 134 (MH+
tert-butylsulfinyl, 98).
-
N,N-Dicycloh exyltr im eth ylm eth an esu lfin am ide (2e). The
general procedure was followed using dicyclohexylamine (273
mg, 1.51 mmol), tert-butylsulfinyl chloride (274 mg, 1.95 mmol),
triethylamine (2.09 mL, 15.1 mmol), and CH2Cl2 (15 mL). The
crude product was purified by flash column chromatography
(EtOAc:hexanes, 1:1) to afford sulfinamide 2e (431 mg, 100%)
as a white solid (mp 110-112 °C): 1H NMR (300 MHz, CDCl3)
δ 3.16 (br s, 2 H), 1.91-1.54 (m, 14 H), 1.40-1.19 (m, 4 H), 1.16
(s, 9 H), 1.05 (tt, J ) 12.6, 3.5 Hz, 2 H); 13C NMR (75 MHz,
CDCl3) δ 57.2, 33.6, 26.5, 26.2, 25.4, 24.4; CIMS m/z (relative
intensity) 286 (MH+, 58), 228 (M+ - t-Bu, 46), 85 (88), 69 (100).
N-P h en eth yltr im eth ylm eth an esu lfin am ide (2f). The gen-
eral procedure was followed using phenethylamine (290 mg, 2.39
mmol), tert-butylsulfinyl chloride (506 mg, 3.59 mmol),13 tri-
ethylamine (3.35 mL, 23.9 mmol), and CH2Cl2 (15 mL). The
crude product was purified by flash column chromatography
(EtOAc:hexanes, 1:1) to afford sulfinamide 2f (538 mg, 100%)
as a colorless liquid: 1H NMR (300 MHz, CDCl3) δ 7.31-7.17
(m, 5 H), 3.51-3.22 (m, 3 H), 2.92-2.81 (m, 1 H), 1.15 (s, 9 H);
13C NMR (75 MHz, CDCl3) δ 135.5, 128.8, 128.5, 126.4, 55.6,
46.9, 37.4, 22.5; CIMS m/z (relative intensity) 226 (MH+, 100),
169 (MH+ - t-Bu, 37).
B. The general procedure was followed using sulfinamide 2c
(223 mg, 0.94 mmol), RuCl3‚H2O (2.12 mg, 0009 mmol), and
NaIO4 (241 mg, 1.13 mmol) in a mixture of CH2Cl2 (7 mL),
CH3CN (7 mL), and H2O (11 mL). The crude product was
purified by flash column chromatography as above to afford
sulfonamide 3c (183 mg, 77%).
1,2,3,4-Tetr a h yd r oqu in olin etr im eth ylm eth a n esu lfon a -
m id e (3d ). A. The general procedure was followed using
sulfinamide 2d (73 mg, 0.33 mmol), m-CPBA (55%, 136 mg, 0.43
(14) In this case, 1.5 equiv of tert-butylsulfinyl chloride was used to
minimize formation of the N,N-bis(tert-butylsulfinyl)amine.
(15) The amount of ruthenium catalyst used is crucial. The color of
the upper aqueous layer should be brown, not black. Low yields of
sulfonamide were normally obtained if too much catalyst was used.
N-Non yltr im eth ylm eth a n esu lfin a m id e (2g). The general
procedure was followed using nonylamine (300 mg, 2.09 mmol),