The Journal of Organic Chemistry
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3H), 2.86−2.78 (m, 2H), 1.85−1.73 (m, 4H), 1.29 (t, J = 7.0 Hz, 3H),
0.96 (s, 9H) ppm; 13C NMR (CDCl3, 100 MHz) δ 172.6, 138.3, 128.4,
127.6, 72.9, 69.4, 66.5, 61.3, 56.2, 34.9, 28.7, 26.3, 20.2, 14.1 ppm; MS
(ESI) m/z 370 (M + H+); HRMS (MALDI/TOF) m/z calcd for
[C19H31NO4S + H+] 370.2052, found 370.2061.
−112.91 (m) ppm; 13C NMR (CDCl3, 100 MHz) δ 172.2, 162.8 (d, J
= 245.7 Hz), 131.7 (d, J = 7.9 Hz), 130.3 (d, J = 8.3 Hz), 126.1 (d, J =
2.9 Hz), 117.4 (d, J = 21.7 Hz), 115.3 (d, J = 20.9 Hz), 66.5, 61.6, 61.3,
35.0, 26.2, 14.1 ppm; MS (ESI) m/z 316 (M + H+), 338 (M + Na+);
HRMS (MALDI/TOF) m/z calcd for [C15H22FNO3S + H+]
316.1383, found 316.1375.
Data for (S)-ethyl 2-[(S)-decanesulfinamido]-3,3-dimethyl-
butanoate [(2S,sS)-3e]: colorless oil (149 mg, 43%); [α]2D5 −54.9 (c
0.84 in CHCl3); IR (KBr) 3211, 2958, 2925, 2855, 1735, 1466, 1369,
Data for (S)-ethyl 2-[(S)-(4-fluorophenyl)methane-
sulfinamido]-3,3-dimethylbutanoate (5d): white solid (214 mg,
68%); mp 146−147 °C; [α]D25 +123.6 (c 0.82 in CHCl3); IR (KBr)
3161, 2966, 1736, 1602, 1510, 1368, 1325, 1220, 1160, 1067, 1052,
843 cm−1; 1H NMR (CDCl3, 300 MHz) δ 7.33−7.28 (m, 2H), 7.11−
7.05 (m, 2H), 4.30 (d, J = 9.6 Hz, 1H), 4.21−4.13 (m, 2H), 4.05 (d, J
= 13.1 Hz, 1H), 3.96 (d, J = 13.1 Hz, 1H), 3.49 (d, J = 9.3 Hz, 1H),
1.25 (t, J = 6.9 Hz, 3H), 0.85 (s, 9H) ppm; 19F NMR (CDCl3, 282.4
MHz) δ −113.82 to −113.92 (m) ppm; 13C NMR (CDCl3, 100 MHz)
δ 172.2, 162.8 (d, J = 247.5 Hz), 132.2 (d, J = 8.2 Hz), 125.3 (d, J =
2.7 Hz), 115.8 (d, J = 21.7 Hz), 66.5, 61.3, 61.1, 35.0, 26.2, 14.1 ppm;
MS (ESI) m/z 316 (M + H+), 338 (M + Na+); HRMS (MALDI/
TOF) m/z calcd for [C15H22FNO3S + H+] 316.1383, found 316.1373.
Data for (S)-ethyl 2-[(S)-(2-chlorophenyl)methane-
sulfinamido]-3,3-dimethylbutanoate (5e): white solid (183 mg,
55%); mp 118−120 °C; [α]D25 +157.1 (c 0.92 in CHCl3); IR (KBr)
3178, 2956, 1732, 1474, 1366, 1323, 1216, 1158, 1067, 1049, 922, 770
cm−1; 1H NMR (CDCl3, 400 MHz) δ 7.43−7.37 (m, 2H), 7.29−7.24
(m, 2H), 4.53 (d, J = 9.4 Hz, 1H), 4.30−4.23 (m, 2H), 4.21−4.16 (m,
2H), 3.43 (d, J = 9.4 Hz, 1H), 1.26 (t, J = 7.0 Hz, 3H), 0.76 (s, 9H);
ppm 13C NMR (CDCl3, 100 MHz) δ 172.2, 134.6, 132.4, 129.7, 129.6,
128.7, 127.1, 66.8, 61.3, 60.0, 35.0, 26.0, 14.1 ppm; MS (ESI) m/z 354
(M + Na+); HRMS (MALDI/TOF) m/z calcd for [C15H22ClNO3S +
H+] 332.1087, found 332.1079.
1
1318, 1214, 1156, 1095, 1069, 1024 cm−1; H NMR (CDCl3, 300
MHz) δ 4.66 (d, J = 10.8 Hz, 1H), 4.27−4.17 (m, 2H), 3.63 (d, J =
10.8 Hz, 1H), 2.75−2.64 (m, 2H), 1.68−1.59 (m, 2H), 1.43−1.26 (m,
17H), 1.01 (s, 9H), 0.88 (t, J = 6.6 Hz, 3H) ppm; 13C NMR (CDCl3,
100 MHz) δ 173.0, 61.2, 60.8, 54.5, 34.0, 31.8, 29.4, 29.3, 29.2, 28.7,
26.7, 23.2, 22.6, 14.1 ppm; MS (ESI) m/z 370 (M + Na+); HRMS
(MALDI/TOF) m/z calcd for [C18H37NO3S + H+] 348.2572, found
348.2561.
Data for (S)-ethyl 2-[(R)-decanesulfinamido]-3,3-dimethyl-
butanoate [(2S,sR)-3e]: colorless oil (80 mg, 23%); [α]2D5 +41.3 (c
1.19 in CHCl3); IR (KBr) 3213, 2959, 2927, 1737, 1465, 1366, 1214,
1162, 1092 cm−1; 1H NMR (CDCl3, 300 MHz) δ 4.42 (d, J = 9.3 Hz,
1H), 4.26−4.19 (m, 2H), 3.53 (d, J = 9.3 Hz, 1H), 2.85−2.75 (m,
2H), 1.76−1.66 (m, 2H), 1.43−1.26 (m, 17H), 0.97 (s, 9H), 0.88 (t, J
= 6.6 Hz, 3H) ppm; 13C NMR (CDCl3, 100 MHz) δ 172.6, 66.5, 61.3,
56.5, 34.9, 31.8, 29.4, 29.3, 29.2, 29.2, 28.6, 26.7, 26.3, 23.1, 22.6, 14.1
ppm; MS (ESI) m/z 370 (M + Na+); HRMS (MALDI/TOF) m/z
calcd for [C18H37NO3S + H+] 348.2572, found 348.2569.
General Procedure for the 1,3-Migration−Addition of
Benzylzinc Reagent with (R,E)-Ethyl 2-[(tert-butylsulfinyl)-
imino]acetate (1a). To a solution of 1a (205 mg, 1 mmol) in
anhydrous THF (5 mL) was added dropwise freshly prepared
substituted benzylzinc bromide reagents 4 (2.5 mL, 1 M in THF) at
−20 °C under an argon atmosphere, and then the mixture was stirred
for 12 h while being warmed to room temperature. The reaction was
quenched with saturated NH4Cl aqueous solution (10 mL) and
diluted with EtOAc (30 mL). The organic layer was separated, and the
aqueous phase was extracted with EtOAc three times. The combined
organic layers were washed with brine, dried over anhydrous Na2SO4,
filtered, and concentrated under reduced pressure. The residue was
purified by chromatography on silica gel to give the title compound.
Data for (S)-ethyl 3,3-dimethyl-2-[(S)-phenylmethane-
sulfinamido]butanoate (5a): white solid (223 mg, 75%); mp
148−150 °C; [α]2D5 +132.2 (c 0.60 in CHCl3); IR (KBr) 3166, 2959,
1733, 1454, 1366, 1325, 1216, 1160, 1104, 1073, 1052, 1029, 776, 703
cm−1; 1H NMR (CDCl3, 300 MHz) δ 7.42−7.32 (m, 5H), 4.33 (d, J =
9.3 Hz, 1H), 4.20−4.12 (m, 2H), 4.03 (s, 2H), 3.48 (d, J = 9.3 Hz,
1H), 1.24 (t, J = 7.2 Hz, 3H), 0.83 (s, 9H) ppm; 13C NMR (CDCl3, 75
MHz) δ 172.2, 130.5, 129.3, 128.7, 128.3, 66.4, 62.1, 61.2, 35.0, 26.2,
14.1 ppm; MS (ESI) m/z 298 (M + H+); HRMS (MALDI/TOF) m/z
calcd for [C15H23NO3S + H+] 298.1477, found 298.1469.
Data for (S)-ethyl 2-[(S)-(3-chlorophenyl)methane-
sulfinamido]-3,3-dimethylbutanoate (5f): white solid (176 mg,
53%); mp 116−117 °C; [α]D25 +71.6 (c 0.90 in CHCl3); IR (KBr)
3170, 2960, 1732, 1594, 1477, 1366, 1323, 1215, 1157, 1065, 1048,
1
921, 789 cm−1; H NMR (CDCl3, 400 MHz) δ 7.32−7.28 (m, 2H),
7.22−7.19 (m, 2H), 4.37 (d, J = 9.5 Hz, 1H), 4.21−4.14 (m, 2H),
4.03−3.96 (m, 2H), 3.48 (d, J = 9.5 Hz, 1H), 1.25 (t, J = 7.0 Hz, 3H),
0.84 (s, 9H) ppm; 13C NMR (CDCl3, 100 MHz) δ 172.2, 134.6, 131.5,
130.5, 130.0, 128.6, 128.5, 66.5, 61.6, 61.3, 35.0, 26.2, 14.1 ppm; MS
(ESI) m/z 354 (M + Na+); HRMS (MALDI/TOF) m/z calcd for
[C15H22ClNO3S + H+] 332.1087, found 332.1075.
Data for (S)-ethyl 2-[(S)-(4-chlorophenyl)methane-
sulfinamido]-3,3-dimethylbutanoate (5g): white solid (212 mg,
64%); mp 139−140 °C; [α]D25 +110.4 (c 0.90 in CHCl3); IR (KBr)
3169, 2957, 1736, 1492, 1368, 1326, 1215, 1154, 1065, 1050, 841
1
cm−1; H NMR (CDCl3, 300 MHz) δ 7.37 (d, J = 8.4 Hz, 2H), 7.26
(d, J = 8.1 Hz, 2H), 4.29 (d, J = 9.3 Hz, 1H), 4.23−4.12 (m, 2H),
4.04−3.94 (m, 2H), 3.49 (d, J = 9.3 Hz, 1H), 1.25 (t, J = 6.9 Hz, 3H),
0.86 (s, 9H) ppm; 13C NMR (CDCl3, 75 MHz) δ 172.2, 134.4, 131.7,
128.9, 127.8, 66.5, 61.3, 61.2, 35.0, 26.2, 14.1 ppm; MS (ESI) m/z 354
(M + Na+); HRMS (MALDI/TOF) m/z calcd for [C15H22ClNO3S +
H+] 332.1087, found 332.1101.
Data for (S)-ethyl 2-[(S)-(2-fluorophenyl)methane-
sulfinamido]-3,3-dimethylbutanoate (5b): white solid (145 mg,
46%); mp 153−154 °C; [α]2D5 +183.4 (c 0.80, CHCl3); IR (KBr) 3171,
2958, 1732, 1491, 1325, 1158, 1084, 1068, 762 cm−1; 1H NMR
(CDCl3, 400 MHz) δ 7.34−7.30 (m, 2H), 7.16−7.08 (m, 2H), 4.49
(d, J = 9.4 Hz, 1H), 4.21−4.15 (m, 2H), 4.16−4.06 (m, 2H), 3.43 (d, J
= 9.4 Hz, 1H), 1.26 (t, J = 7.0 Hz, 3H), 0.77 (s, 9H) ppm; 19F NMR
(CDCl3, 282.4 MHz) δ −116.77 to −116.88 (m) ppm; 13C NMR
(CDCl3, 100 MHz) δ 172.2, 161.2 (d, J = 246.1 Hz), 132.2 (d, J = 3.0
Hz), 130.1 (d, J = 7.6 Hz), 124.4 (d, J = 3.8 Hz), 117.7 (d, J = 15.3
Hz), 115.6 (d, J = 21.3 Hz), 66.7, 61.3, 55.7, 35.0, 26.0, 14.1 ppm; MS
(ESI) m/z 316 (M + H+), 338 (M + Na+); HRMS (MALDI/TOF)
m/z calcd for (C15H22FNO3S + H+) 316.1383, found 316.1381.
Data for (S)-ethyl 2-[(S)-(3-fluorophenyl)methane-
sulfinamido]-3,3-dimethylbutanoate (5c): white solid (161 mg,
51%); mp 157−159 °C; [α]D25 +118.5 (c 0.74 in CHCl3); IR (KBr)
3172, 2959, 1735, 1614, 1591, 1487, 1450, 1326, 1159, 1104, 1068,
Data for (S)-ethyl 2-[(S)-(4-bromophenyl)methane-
sulfinamido]-3,3-dimethylbutanoate (5h): white solid (252 mg,
67%); mp 147−149 °C; [α]D25 +102.2 (c 0.94 in CHCl3); IR (KBr)
1
3173, 2955, 1732, 1488, 1368, 1326, 1214, 1155, 1065, 838 cm−1; H
NMR (CDCl3, 300 MHz) δ 7.52 (d, J = 8.1 Hz, 2H), 7.20 (d, J = 8.4
Hz, 2H), 4.32 (d, J = 9.0 Hz, 1H), 4.23−4.12 (m, 2H), 4.03−3.93 (m,
2H), 3.49 (d, J = 9.3 Hz, 1H), 1.25 (t, J = 6.9 Hz, 3H), 0.86 (s, 9H)
ppm; 13C NMR (CDCl3, 100 MHz) δ 172.1, 132.0, 131.9, 128.3,
122.6, 66.4, 61.3, 35.0, 26.2, 14.1 ppm; MS (ESI) m/z 398 (M + Na+);
400 (M + 2 + Na+); HRMS (MALDI/TOF) m/z calcd for
[C15H22BrNO3S + H+] 376.0582, found 376.0573. Single crystals of
5h suitable for X-ray diffraction were obtained from ethyl acetate. See
the Supporting Information for full crystallographic data.
Data for (S)-ethyl 2-[(S)-(3-cyanophenyl)methane-
sulfinamido]-3,3-dimethylbutanoate (5i): white solid (132 mg,
41%); mp 99−101 °C; [α]2D5 +103.4 (c 1.0 in CHCl3); IR (KBr) 3230,
3058, 2958, 2242, 1738, 1369, 1322, 1212, 1155, 1070, 941, 808 cm−1;
1H NMR (CDCl3, 400 MHz) δ 7.67−7.63 (m, 2H), 7.60−7.58 (m,
1
1050, 948, 793 cm−1; H NMR (CDCl3, 300 MHz) δ 7.38−7.32 (m,
1H), 7.12−7.05 (m, 3H), 4.38 (d, J = 9.3 Hz, 1H), 4.21−4.15 (m,
2H), 4.07−3.98 (m, 2H), 3.49 (d, J = 9.3 Hz, 1H), 1.25 (t, J = 6.6 Hz,
3H), 0.85 (s, 9H) ppm; 19F NMR (CDCl3, 282.4 MHz) δ −112.80 to
G
dx.doi.org/10.1021/jo401640c | J. Org. Chem. XXXX, XXX, XXX−XXX