FULL PAPERS
Jie Guang et al.
determined by chiral stationary phase HPLC analysis using
136.4, 138.1, 143.2, 195.5; IR: nmax(neat): 1156, 1335, 1439,
1491, 1598, 1677, 3313 cmÀ1; [a]2D5: À303.9 (c 0.98, THF, 96%
ee). Enantiomeric excess of the product was determined by
chiral stationary phase HPLC analysis using a ChiralPak IC
column (80:20, hexanes/iPrOH at 1.0 mLminÀ1), major
isomer: tR =9.2 min, minor isomer: tR =11.6 min; HRMS-
ESI (m/z): calcd. for C28H28ClN2O3S2 [M+NH4]+: 539.1224;
found: 539.1240.
a
ChiralPak IB column (90:10, hexanes/iPrOH at
1.0 mLminÀ1), major isomer: tR =14.6 min, minor isomer:
tR =19.4 min; HRMS-ESI (m/z): calcd. for C29H28F3N2O3S2
[M+NH4]+: 573.1488; found: 573.1491.
S-Phenyl (2S,3S)-3-(2-chlorophenyl)-3-[(4-methylphenyl)-
sulfonamido]-2-phenylpropanethioate (3h): White solid;
1
49.5 mg (95% yield); m.p. 138–1408C; H NMR (500 MHz,
CDCl3): d 2.25 (s, 3H), 5.17 (br, 3H), 6.94–7.23 (m, 18H);
13C NMR (125 MHz, CDCl3): d 21.4, 59.4, 65.9, 115.0, 115.2,
126.6, 127.2, 128.8, 129.1, 129.2, 129.6, 129.8, 129.9, 133.2,
133.9, 134.1, 136.3, 143.3, 161.4, 163.3, 195.5; IR: nmax(neat):
1156, 1329, 1440, 1598, 1698, 3261 cmÀ1; [a]D25: À149.3 (c 0.99,
THF, 90% ee). Enantiomeric excess of the product was de-
termined by chiral stationary phase HPLC analysis using
S-Phenyl (2S,3S)-2-(4-bromophenyl)-3-[(4-methylphenyl)-
sulfonamido]-3-phenylpropanethioate (3l): White solid;
52.7 mg (93% yield); m.p. 179–1818C; H NMR (500 MHz,
1
CDCl3): d 2.41 (s, 3H), 4.04 (d, J=10.5 Hz, 1H), 4.84 (dd,
J=3.5, 10.5 Hz, 1H), 5.24 (d, J=7.0 Hz, 1H), 6.93 (d, J=
7.0 Hz, 2H), 7.07 (dd, J=8.0, 16.5 Hz, 4H), 7.22–7.32 (m,
14H); 13C NMR (125 MHz, CDCl3): d 21.5, 60.2, 65.1, 122.8,
126.5, 126.9, 127.8, 128.0, 128.4, 129.1, 129.3, 129.7, 130.4,
132.0, 132.7, 134.2, 136.6, 138.3, 143.2, 195.3; IR: nmax(neat):
1155, 1334, 1440, 1486, 1669, 2920, 3311 cmÀ1; [a]D25: À300.4
(c 0.97, THF, 95% ee). Enantiomeric excess of the product
was determined by chiral stationary phase HPLC analysis
using a ChiralPak IC column (80:20, hexanes/iPrOH at
1.0 mLminÀ1), major isomer: tR =13.9 min, minor isomer:
tR =15.8 min; HRMS-ESI (m/z): calcd. for C28H28BrN2O3S2
[M+NH4]+: 583.0719; found: 583.0731.
a
ChiralPak IC column (80:20, hexanes/iPrOH at
1.0 mLminÀ1), major isomer: tR =14.8 min, minor isomer:
tR =17.5 min; HRMS-ESI (m/z): calcd. for C28H28ClN2O3S2
[M+NH4]+: 539.1224; found: 539.1229.
S-Phenyl (2S,3R,E)-3-[(4-methylphenyl)sulfonamido]-2,5-
diphenylpent-4-enethioate (3i): White solid; 46.7 mg (91%
1
yield); m.p. 178–1808C; H NMR (500 MHz, CDCl3): d 2.30
(s, 3H), 4.21 (d, J=8.0 Hz, 1H), 4.36 (dd, J=7.5, 15.0 Hz,
1H), 4.81 (d, J=6.5 Hz, 1H), 5.97 (dd, J=7.5, 15.5 Hz, 1H),
6.12 (d, J=16.0 Hz, 1H), 7.12 (t, J=8.5 Hz, 4H), 7.22–7.39
(m, 13H), 7.58 (d, J=7.0 Hz, 1H); 13C NMR (125 MHz,
CDCl3): d 21.4, 59.3, 64.5, 125.1, 126.5, 126.9, 127.4, 127.9,
128.4, 128.5, 129.0, 129.2, 129.3, 129.5, 129.7, 133.6, 134.3,
134.4, 136.0, 137.2, 143.4, 197.0; IR: nmax(neat): 1152, 1251,
1325, 1426, 1681, 3304 cmÀ1; [a]2D5: À138.0 (c 0.53, THF, 97%
ee). Enantiomeric excess of the product was determined by
chiral stationary phase HPLC analysis using a ChiralPak IB
column (93:7, hexanes/iPrOH at 1.0 mLminÀ1), major
isomer: tR =22.3 min, minor isomer: tR =26.6 min; HRMS-
ESI (m/z): calcd. for C30H31N2O3S2 [M+NH4]+: 531.1771;
found: 531.1769.
S-Phenyl (2S,3S)-2-(3-chlorophenyl)-3-[(4-methylphenyl)-
sulfonamido]-3-phenylpropanethioate (3m): White solid;
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50.2 mg (96% yield); m.p. 205–2078C; H NMR (500 MHz,
CDCl3): d 2.37 (s, 3H), 4.04 (d, J=10.5 Hz, 1H), 4.78 (dd,
J=4.0, 10.5 Hz, 1H), 5.15 (d, J=6.0 Hz, 1H), 6.93 (d, J=
7.5 Hz, 2H), 7.05 (d, J=8.5 Hz, 2H), 7.17–7.33 (m, 14H);
13C NMR (125 MHz, CDCl3): d 21.5, 60.3, 65.3, 126.5, 126.9,
127.3, 127.8, 128.1, 128.4, 128.7, 129.1, 129.3, 129.7, 130.2,
134.2, 134.9, 135.6, 136.2, 138.1, 143.2, 195.2; IR: nmax(neat):
1156, 1335, 1433, 1572, 1593, 1680, 3334 cmÀ1; [a]D25: À222.5
(c 0.94, THF, 96% ee). Enantiomeric excess of the product
was determined by chiral stationary phase HPLC analysis
using a ChiralPak IC column (85:15, hexanes/iPrOH at
1.0 mLminÀ1), major isomer: tR =13.2 min, minor isomer:
tR =17.2 min; HRMS-ESI (m/z): calcd. for C28H28ClN2O3S2
[M+NH4]+: 539.1224; found: 539.1228.
S-Phenyl (2S,3S)-2-(4-methoxyphenyl)-3-[(4-methylphe-
nyl)sulfonamido]-3-phenylpropanethioate (3j): White solid;
1
51.9 mg (90% yield); m.p. 183–1858C; H NMR (500 MHz,
CDCl3): d 2.29 (s, 3H), 3.75 (s, 3H), 3.94 (d, J=10.5 Hz,
1H), 4.72 (dd, J=5.5, 10.0 Hz, 1H), 4.80 (d, J=4.5 Hz, 1H),
6.71 (d, J=8.5 Hz, 1H), 6.89 (d, J=7.0 Hz, 1H), 6.98 (d, J=
8.0 Hz, 1H), 7.06 (d, J=8.5 Hz, 1H),7.14–7.23 (m, 11H); 13C
NMR (125 MHz, CDCl3): d 21.5, 55.2, 60.1, 65.1, 114.5,
125.1, 126.4, 126.8, 127.2, 127.9, 128.0, 128.2, 129.0, 129.1,
129.5, 129.7, 130.0, 134.2, 136.3, 138.1, 143.0, 159.8, 195.9;
IR: nmax(neat): 1157, 1249, 1331, 1440, 1511, 1681, 2922,
3334 cmÀ1; [a]2D5: À265.8 (c 1.02, THF, 95% ee). Enantiomer-
ic excess of the product was determined by chiral stationary
phase HPLC analysis using a ChiralPak IC column (80:20,
hexanes/iPrOH at 1.0 mLminÀ1), major isomer: tR =
18.7 min, minor isomer: tR =22.3 min; HRMS-ESI (m/z):
calcd. for C29H31N2O4S2 [M+NH4]+: 535.1720; found:
573.1726.
S-Phenyl
(2R,3S)-3-[(4-methylphenyl)sulfonamido]-3-
phenyl-2-(thiophen-2-yl)propanethioate (3n): White solid;
1
46.4 mg (94% yield); m.p. 192–1948C; H NMR (500 MHz,
CDCl3): d 2.37 (s, 3H), 4.37 (d, J=9.5 Hz, 1H), 4.77 (dd, J=
4.5, 9.5 Hz, 1H), 4.94 (d, J=5.0 Hz, 1H), 6.97–6.98 (m, 2H),
7.03 (d, J=7.0 Hz, 2H), 7.09 (d, J=8.0 Hz, 2H), 7.17–7.19
(m, 2H), 7.22–7.37 (m, 9H); 13C NMR (125 MHz, CDCl3): d
21.5, 60.6, 61.1, 126.6, 127.1, 127.2, 127.3, 128.0, 128.1, 128.3,
128.4, 129.1, 129.2, 129.7, 134.2, 134.8, 136.3, 137.5, 143.2,
195.1; IR: nmax(neat): 1153, 1231, 1319, 1597, 1685,
3326 cmÀ1; [a]2D5: À89.5 (c 1.05, THF, 96% ee). Enantiomeric
excess of the product was determined by chiral stationary
phase HPLC analysis using a ChiralPak IC column (80:20,
hexanes/iPrOH at 1.0 mLminÀ1), major isomer: tR =
16.7 min, minor isomer: tR =22.6 min; HRMS-ESI (m/z):
calcd. for C26H27N2O3S3 [M+NH4]+: 511.1178; found:
511.1183.
S-Phenyl (2S,3S)-2-(4-chlorophenyl)-3-[(4-methylphenyl)-
sulfonamido]-3-phenylpropanethioate (3k): White solid;
1
46.9 mg (90% yield); m.p. 178–1808C; H NMR (300 MHz,
CDCl3): d 2.32 (s, 3H), 3.98 (d, J=10.5 Hz, 1H), 4.76 (dd,
J=3.6, 10.5 Hz, 1H), 5.11 (d, J=6.9 Hz, 1H), 6.86 (d, J=
6.9 Hz, 2H), 6.98 (d, J=8.1 Hz, 2H), 7.01–7.25 (m, 14H);
13C NMR (75 MHz, CDCl3): d 21.5, 60.2, 65.0, 126.4, 126.9,
127.7, 128.1, 128.4, 129.1, 129.2, 130.1, 132.1, 134.2, 134.5,
S-Phenyl
(2S,3R)-2-bromo-3-[(4-methylphenyl)-sulfon-
amido]-3-phenylpropanethioate (3o): White solid; 30.0 mg
(61% yield); m.p. 145–1478C; H NMR (500 MHz, CDCl3):
d 2.35 (s, 3H), 4.68 (d, J=6.0 Hz, 1H), 5.00 (t, J=7.5 Hz,
1H), 5.64 (d, J=7.5 Hz, 1H), 7.10 (d, J=7.5 Hz, 2H), 7.15–
1
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ꢁ 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 0000, 000, 0 – 0
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