N. Chen, J. Xu / Tetrahedron 68 (2012) 2513e2522
2521
ArH); 13C NMR (D2OeHCOOH, 75.5 MHz)
130.9, 134.9.
d
: 41.1, 61.9, 129.2, 129.4,
4.4.11. syn-2-Amino-1-phenylpropane-1-sulfonic
acid
(syn-4j).
Colorless crystals, yield: 88%. Mp >310 ꢁC. 1H NMR (300 MHz, D2O)
d
: 7.34 (s, 5H, ArH), 4.12e4.01 (m, 2H, CHN and CHS), 1.06 (d,
4.4.3. 1-Amino-3-methylbutane-2-sulfonic acid (4c).25a Colorless
crystals, yield: 94%. Mp >330 ꢁC (dec). 1H NMR (D2O, 300 MHz)
J¼6.3 Hz, 3H, CH3); 13C NMR (125 MHz, D2OeHCOOH)
d: 133.1,
d:
130.2, 129.52, 129.47, 68.5, 48.8, 17.4. HRMS (ESI) calcd for
3.26 (dd, J¼13.8, 2.9 Hz, 1H in CH2N), 3.18 (dd, J¼13.8, 10.1 Hz, 1H in
CH2N), 2.87 (ddd, J¼10.1, 3.3, 2.9 Hz, 1H, CHS), 2.22 (dhept, J¼3.3,
7.0 Hz, 1H, CH), 0.97 (d, J¼7.0 Hz, 3H, CH3), 0.89 (d, J¼7.0 Hz, 3H,
C9H14NO3S [MþH]þ m/z: 216.0689; found: 216.0690.
4.4.12. anti-2-Amino-1-phenylbutane-1-sulfonic acid (anti-4k).
Colorless crystals, yield: 87%. Mp >310 ꢁC. 1H NMR (300 MHz, D2O)
CH3); 13C NMR (75 MHz, D2OeHCOOH)
d: 62.8, 37.4, 28.0, 21.1, 17.2.
d
: 7.42e7.27 (m, 5H, ArH), 4.25 (d, J¼4.4 Hz, 1H, CHN), 3.89e3.83
4.4.4. 1-Amino-2-phenylpropane-2-sulfonic acid (4d).25a Colorless
crystals, yield: 97%. Mp 288e289 ꢁC (MeOH), lit.21 mp 285e287 ꢁC.
(m, 1H, CHN),1.75e1.43 (m, 2H, CH2), 0.92 (t, J¼7.4 Hz, 3H, CH3); 13
C
NMR (75 MHz, DMSO-d6) d: 133.5, 130.0, 128.1, 127.4, 63.6, 53.5,
1H NMR (D2O, 200 MHz)
d: 7.38e7.45 (m, 2H, Ar), 7.23e7.31 (m, 3H,
24.1, 10.2. HRMS (ESI) calcd for C10H15NO3SNaþ [MþNa]þ m/z:
ArH), 3.68 (d, J¼13.4 Hz, 1H in CH2), 3.51 (d, J¼13.4 Hz, 1H in CH2),
252.0665; found: 252.0667.
1.67 (s, 3H, CH3); 13C NMR (D2O, 75 MHz)
d: 134.8, 128.9, 128.8,
129.9, 61.6, 44.7, 18.2. HRMS (ESI) calcd for C9H14NO3Sþ [MþH]þ m/
z: 216.0689; found 216.0693.
4.4.13. syn-2-Amino-1-phenylbutane-1-sulfonic
Colorless crystals, yield: 87%. Mp >310 ꢁC. 1H NMR (400 MHz,
DMSO-d6) : 8.17 (br s, 3H), 7.33e7.27 (m, 5H, ArH), 3.75 (d,
acid
(syn-4k).
d
4.4.5. 1-Amino-2-methylbutane-2-sulfonic acid (4e).25a Colorless
J¼10.9 Hz, 1H, CHS), 3.68e3.62 (m, 1H, CHN), 1.45e1.16 (m, 2H,
crystals, yield: 91%. Mp 324e327 ꢁC. 1H NMR (300 MHz, D2O)
d:
CH2), 0.76 (t, J¼7.3 Hz, 3H, CH3); 13C NMR (101 MHz, DMSO-d6)
d:
3.21 (d, J¼15.1 Hz, 1H in CH2N), 3.15 (d, J¼15.1 Hz, 1H in CH2N), 1.78
(dq, J¼14.4, 7.6 Hz, 1H in CH2), 1.69 (dq, J¼14.4, 7.6 Hz, 1H in CH2),
1.25 (s, 3H, CH3), 0.89 (t, J¼7.6 Hz, 3H, CH3); 13C NMR (125 MHz,
135.4, 129.6, 127.9, 127.2, 66.0, 53.1, 23.9, 8.7. HRMS (ESI) calcd for
C10H15NO3SNaþ [MþNa]þ m/z: 252.0665; found, 252.0659.
D2OeHCOOH)
d
: 58.0, 42.8, 25.6, 16.6, 7.1. HRMS (ESI) calcd for
4.4.14. anti-2-Amino-1-(4-chlorophenyl)propane-1-sulfonic
(anti-4l). Colorless crystals, yield: 82% (PtO2 as the catalyst.). Mp
>10 ꢁC. 1H NMR (300 MHz, D2O)
: 7.43e7.35 (m, 4H, ArH), 4.18 (d,
acid
C5H14NO3S [MþH]þ m/z: 168.0689; found 168.0690.
d
4.4.6. 1-Amino-2,4,4-trimethylpentane-2-sulfonic acid (4f). Colorless
J¼6.3 Hz, 1H, CHS), 4.06 (dq, J¼6.3, 6.6 Hz, 1H, CHN), 1.39 (d,
crystals, yield: 98%. Mp 329 ꢁC (dec). 1H NMR (300 MHz, D2O)
d:
J¼6.6 Hz, 3H, CH3); 13C NMR (75 MHz, DMSO-d6)
d: 134.0, 132.5,
3.37 (d, J¼14.2 Hz, 1H in CH2N), 3.25 (d, J¼14.2 Hz, 1H in CH2N), 1.76
131.7, 127.9, 66.4, 47.9, 17.2. HRMS (ESI) calcd for C9H13ClNO3Sþ
(d, J¼15.0 Hz, 1H in CH2), 1.63 (d, J¼15.0 Hz, 1H in CH2), 1.40 (s, 3H,
[MþH]þ m/z: 250.0299; found: 250.0311.
CH3), 0.91 (s, 9H, 3CH3 in t-Bu); 13C NMR (101 MHz, DMSO-d6)
d:
56.8, 43.9, 43.8, 31.6, 31.5, 18.2. HRMS (ESI) calcd for C8H19NNaO3Sþ
4.4.15. syn-2-Amino-1-(4-chlorophenyl)propane-1-sulfonic
(syn-4l). Colorless crystals, yield: 92% (PtO2 as the catalyst). Mp
>310 ꢁC. 1H NMR (300 MHz, DMSO-d6)
: 8.05 (br s, 3H, NH3), 7.38
acid
[MþNa]þ m/z: 232.0978; found: 232.0984.
d
4.4.7. 2-Amino-1,1-diphenylethanesulfonic acid (4g).22 Colorless
crystals, yield 90%. Mp 196e198 ꢁC (dec). 1H NMR (300 MHz,
(d, J¼8.6 Hz, 2H, ArH), 7.35 (d, J¼8.6 Hz, 2H, ArH), 4.05 (dq, J¼10.4,
5.6 Hz, 1H, CHN), 3.97 (d, J¼10.4 Hz, 1H, CHS), 0.92 (d, J¼5.6 Hz, 3H,
DMSO-d6)
d
: 7.28e7.11 (m, 10H, ArH), 3.69 (s, 2H, CH2); 13C NMR
CH3); 13C NMR (75 MHz, DMSO-d6)
d: 134.6, 132.0, 131.4, 127.9, 66.7,
(75.5 MHz, HCO2H)
d
: 143.1, 128.9, 128.5, 126.0, 75.9, 49.5. IR,
n
48.0, 17.4. HRMS (ESI) calcd for C9H13ClNO3Sþ [MþH]þ m/z:
(cmꢀ1): 3424.2 (br, NH and OH), 1178.6 (SO2). MS (ESI) m/z: 276
[MꢀH]ꢀ. HRMS (ESI) calcd for C14H16NO3S [MþH]þ m/z: 278.0845;
found: 278.0835.
250.0299; found: 250.0303.
4.4.16. anti-2-Amino-1-(4-chlorophenyl)butane-1-sulfonic
(anti-4m). Colorless crystals, yield: 83% (PtO2 as the catalyst).
Mp 307e310 ꢁC (dec). 1H NMR (300 MHz, DMSO-d6)
: 7.88 (s,
acid
4.4.8. 2-Aminopropane-1-sulfonic acid (4h).25b Colorless crystals,
yield: 75%. Mp >330 ꢁC, lit.25b mp 318e320 ꢁC. 1H NMR (300 MHz,
d
3H, NH3), 7.50 (d, J¼8.6 Hz, 2H, ArH), 7.42 (d, J¼8.6 Hz, 2H,
ArH), 4.07 (d, J¼2.8 Hz, 1H, CHS), 3.63 (m, 1H, CHN), 1.42e1.35
(m, 2H, CH2), 0.91 (t, J¼7.4 Hz, 3H, CH3); 13C NMR (75 MHz,
D2O)
d
: 5.56 (ddq, J¼3.0, 8.1, 6.5 Hz, 1H, CHN), 3.12 (dd, J¼3.6,
13.7 Hz, 1H in CH2S), 2.96 (dd, J¼8.1, 13.7 Hz, 1H in CH2S), 1.24
(d, J¼6.5 Hz, 3H, CH3); 13C NMR (75.5 MHz, D2OeHCO2H)
d
: 73.5,
DMSO-d6) d: 132.6, 132.3, 131.9, 128.1, 62.8, 53.4, 24.1, 10.1.
44.3, 18.0.
HRMS (ESI) calcd for C10H14ClNO3SNaþ [MþNa]þ m/z: 286.0275;
found: 286.0278.
4.4.9. 2-Aminobutane-1-sulfonic acid (4i).41 Colorless crystals,
yield: 78%. Mp 306e307 ꢁC (dec), lit.41 mp 303e306 ꢁC. 1H NMR
4.4.17. syn-2-Amino-1-(4-chlorophenyl)butane-1-sulfonic acid (syn-
(300 MHz, D2O)
d
: 3.50 (ddt, J¼9.4, 3.1, 6.7 Hz, 1H, CHN), 3.15 (dd,
4m). Colorless crystals, yield: 80% (PtO2 as the catalyst.). Mp
J¼15.0, 3.1 Hz, 1H in CH2S), 3.00 (dd, J¼15.0, 9.4 Hz, 1H in CH2S),
>310 ꢁC (dec). 1H NMR (300 MHz, DMSO-d6)
d: 8.25 (br s, 3H,
1.67 (dq, J¼6.7, 7.5 Hz, 2H, CH2), 0.88 (t, J¼7.5 Hz, 3H, CH3); 13C NMR
NHþ3 ), 7.45 (d, J¼8.6 Hz, 2H, ArH), 7.33 (d, J¼8.6 Hz, 2H, ArH),
3.75 (d, J¼10.6 Hz, 1H, CHS), 3.74e3.71 (m, 1H, CHN), 1.44e1.13
(m, 2H, CH2), 0.77 (d, J¼7.4 Hz, 3H, CH3); 13C NMR (75 MHz,
(300 MHz, D2OeHCOOH) d: 51.9, 50.5, 25.9, 9.2. HRMS (ESI) calcd
for C4H11NO3SNaþ [MþNa]þ m/z: 176.0352; found: 176.0357.
DMSO-d6)
d: 134.6, 132.8, 130.9, 128.2, 63.5, 53.1, 24.0, 10.2.
4.4.10. anti-2-Amino-1-phenylpropane-1-sulfonic acid (anti-4j).
Colorless crystals, yield: 83%. Mp 291e293 ꢁC. 1H NMR
HRMS (ESI) calcd for C10H14ClNO3SNaþ [MþH]þ m/z: 286.0275;
found: 286.0265.
(300 MHz, D2O)
d
: 7.40e7.34 (m, 5H, ArH), 4.16 (d, J¼6.3 Hz, 1H,
CHS), 4.06 (dq, J¼6.3, 6.6, 1H, CHN), 1.40 (d, J¼6.6 Hz, 3H, CH3);
4.4.18. anti-2-Amino-1,2-diphenylethanesulfonic acid (anti-4n).20
Colorless crystals, yield, 88%. Mp 288e290 ꢁC, lit.20 mp 306e308 ꢁC.
13C NMR (75 MHz, D2OeHCOOH)
d: 132.0, 130.03, 129.99, 68.2,
49.5, 17.7. HRMS (ESI) calcd for C9H14NO3S [MþH]þ m/z:
216.0689; found: 216.0680. Anal. Calcd for C9H14NO3S$1/4H2O:
C, 50.21; H, 6.09; N, 6.51; S, 14.90; Found: C, 49.08; H, 6.14; N,
6.50; S, 14.47.
1H NMR (300 M)
d: 8.01 (br s, 3H), 7.24e7.07 (m, 10H, ArH), 4.99 (d,
J¼3.1 Hz, 1H, CHN), 4.09 (d, J¼3.1 Hz, 1H, CHS); 13C NMR (75 MHz,
DMSO)
56.09.
d: 135.87,132.84,130.38,128.13,128.07,127.73,127.41, 67.38,