The Journal of Organic Chemistry
Article
.2 Hz, 3H). 13C NMR (400 MHz, CDCl ) δ 161.8, 148.8, 137.6,
32.6, 130.5, 124.3, 121.7, 79.2, 63.5, 54.5, 31.4, 14.0. IR (film) v cm
973, 1720, 1637, 1533, 1453, 1374, 1307, 1261, 1150, 1091, 1050,
789, 731, 674. HRMS (ESI) calcd for C H Br N NaO S (M + Na )
20 22 2 2 4
m/z 566.9559, found 566.9561.
+
7
1
2
8
3
−1
Ethyl rel(3S,5S,6R)-2,4-Dimethyl-3,5-di(naphthalen-2-yl)-1,2,4-
thiadiazinane-6-carboxylate 1,1-dioxide (4m). Colorless crystals.
81, 801, 757, 680, 666. HRMS (ESI) calcd for C H N O S (M +
12
15
2
6
+
1
H ) m/z 315.0645, found 315.0647.
Mp 80−82 °C. Yield 41 mg (16%). H NMR (400 MHz, CDCl
3
) δ
Ethyl cis- and trans-2-Methyl-3-(2-nitrophenyl)-1,2-thiazetidine-
-carboxylate 1,1-dioxide (Two Inseparable Diastereomers, cis- and
8.00 (s, 1H), 7.97−7.85 (m, 7H), 7.72 (d, J = 8.3 Hz, 2H), 7.60−7.52
(m, 4H), 5.69 (s, 1H), 4.50 (d, J = 11.1 Hz, 1H), 4.45 (d, J = 11.1 Hz,
1H), 4.09−4.02 (m, 1H), 4.02−3.95 (m, 1H), 2.87 (s, 3H), 1.99 (s,
3H), 0.96 (t, J = 7.1 Hz, 3H). C NMR (400 MHz, CDCl ) δ 162.9,
135.8, 133.6, 133.4, 133.1, 133.03, 133.00, 129.2, 129.1, 128.3, 128.2,
128.1, 128.0, 127.72, 127.68, 126.9, 126.6, 126.55, 126.52, 126.1,
125.0, 82.5, 69.6, 65.1, 62.3, 39.5, 31.6, 13.7. IR (film) v cm 2979,
1739, 1600, 1509, 1465, 1363, 1344, 1303, 1202, 1163, 1123, 1119,
937, 865, 749, 639. HRMS (ESI) calcd for C H N NaO S (M +
4
trans-3q). Yellow oil. Total yield: 103 mg (66%).
1
13
trans-Isomer: H NMR (400 MHz, CDCl ) δ 8.11−8.08 (m, 2H),
3
3
7
.83−7.79 (m, 1H), 7.63−7.59 (m, 1H), 5.02 (d, J = 5.0 Hz, 1H), 4.87
(
d, J = 5.0 Hz, 1H), 4.40 (q, J = 7.2 Hz, 2H), 2.90 (s, 3H), 1.37 (t, J =
.2 Hz, 3H). 13C NMR (400 MHz, CDCl ) δ 162.3, 148.3, 134.7,
−1
7
1
3
31.7, 130.1, 129.6, 128.3, 125.4, 80.8, 63.3, 51.6, 31.8, 14.0. IR (film)
−1
v cm 2917, 1746, 1660, 1632, 1610, 1579, 1529, 1447, 1370, 1336,
266, 1196, 1038, 857, 792, 759, 724, 697. HRMS (ESI) calcd for
28
28
2
4
+
1
Na ) m/z 511.1662, found 511.1657.
+
C H N NaO S (M + Na ) m/z 337.0465, found 337.0463.
Ethyl rel(3S,5S,6R)-2,4-Dimethyl-3,5-di(naphthalen-1-yl)-1,2,4-
thiadiazinane-6-carboxylate 1,1-dioxide (4n, two rotamers). Color-
12
14
2
6
1
cis-Isomer: H NMR (400 MHz, CDCl ) δ 8.23 (dd, J = 8.2, 1.1 Hz,
3
1
1
2
H), 8.02 (d, J = 7.4 Hz, 1 H), 7.83−7.79 (m, 1H), 7.63−7.59 (m,
H), 5.67 (d, J = 8.4 Hz, 1H), 4.94 (d, J = 8.4 Hz, 1H), 4.08−3.97 (m,
H), 2.87 (s, 3H), 1.09 (t, J = 7.2 Hz, 3H). 13C NMR (400 MHz,
less solids. Mp 167−169 °C. Total yield 3 mg (1%).
1
Rotamer 1. H NMR (400 MHz, CDCl ) δ 9.22 (d, J = 8.3 Hz,
3
1H), 8.33 (d, J = 7.4 Hz, 1H), 7.80−7.50 (m, 11H), 6.46 (s, 1H), 5.36
(s, 1H), 4.97 (d, J = 11.6 Hz, 1H), 4.80 (d, J = 11.6 Hz, 1H), 3.89 (q, J
= 7.1 Hz, 2H), 2.76 (s, 3H), 1.94 (s, 3H), 0.71 (t, J = 7.1 Hz, 3H).
CDCl ) δ 161.5, 147.7, 134.4, 133.4, 129.65, 129.64, 125.5, 76.9, 62.5,
5
3
−1
13
3.1, 29.7, 13.7. IR (film) v cm 2917, 1746, 1660, 1632, 1610, 1579,
C
1
529, 1447, 1370, 1336, 1266, 1196, 1038, 857, 792, 759, 724, 697.
NMR (400 MHz, CDCl ) δ 162.9, 135.4, 134.1, 133.6, 131.7, 131.2,
130.0, 130.07, 129.96, 129.75, 129.1, 129.8, 128.8, 127.2, 126.5, 126.1,
3
+
HRMS (ESI) calcd for C H N NaO S (M + Na ) m/z 337.0465,
12
14
2
6
found 337.0463.
126.0, 125.6, 125.0, 124.4, 123.2, 77.8, 73.3, 63.3, 62.2, 39.0, 32.0, 13.6.
IR (film) v cm 2980, 1740, 1597, 1511, 1462, 1364, 1348, 1304,
−1
Ethyl rel(3S,5S,6R)-2,4-Dimethyl-3,5-diphenyl-1,2,4-thiadiazi-
nane-6-carboxylate 1,1-dioxide (4a). Colorless oil. Yield 31 mg
1260, 1201, 1160, 1137, 1119, 1039, 1023, 939, 910, 799, 777, 732,
1
+
(
16%). H NMR (400 MHz, CDCl ) δ 7.55−7.34 (m, 10H), 5.47 (s,
683, 648. HRMS (ESI) calcd for C H N NaO S (M + Na ) m/z
3
28 28
2
4
1
7
H), 4.29 (d, J = 11.2 Hz, 1H), 4.25 (d, J = 11.2 Hz, 1H), 4.07 (qd, J =
.1, 0.6 Hz, 2H), 2.78 (s, 3H), 1.91 (s, 3H), 1.06 (t, J = 7.1 Hz, 3H).
C NMR (400 MHz, CDCl ) δ 162.9, 138.6, 135.5, 129.2, 129.1,
511.1662, found 511.1656.
1
Rotamer 2. H NMR (400 MHz, CDCl ) δ 8.33 (d, J = 8.6 Hz,
3
1
3
3
1H), 7.80−7.50 (m, 12H), 6.37 (s, 1H), 5.37 (s, 1H), 4.54 (d, J = 10.6
1
28.8, 128.7, 128.6, 128.2, 82.2, 69.4, 65.1, 62.2, 39.2, 31.5, 13.8. IR
Hz, 1H), 3.73 (d, J = 10.6 Hz, 1H), 3.82−3.67 (m, 2H), 2.81 (s, 3H),
−1
13
(film) v cm 2917, 1740, 1456, 1384, 1364, 1270, 1280, 1142, 1075,
2.08 (s, 3H), 0.83 (t, J = 7.1 Hz, 3H). C NMR (400 MHz, CDCl ) δ
3
+
1
013, 758, 702, 662. HRMS (ESI) calcd for C H N O S (M + H )
162.7, 134.6, 134.1,132.1, 131.2, 130.8, 130.2, 130.02, 129.67, 129.4,
129.8, 128.8, 128.7, 127.2, 126.3, 126.2, 126.0, 125.7, 124.4, 124.2,
123.1, 77.6, 65.7, 63.0, 62.0, 40.1, 32.0, 13.3. IR (film) v cm− 2980,
1740, 1597, 1511, 1462, 1364, 1348, 1304, 1260, 1201, 1160, 1137,
1119, 1039, 1023, 939, 910, 799, 777, 732, 683, 648. HRMS (ESI)
2
0
25
2
4
m/z 389.1530, found 389.1529.
1
Ethyl rel(3S,5S,6R)-3,5-Di(4-methoxyphenyl)-2,4-dimethyl-1,2,4-
thiadiazinane-6-carboxylate 1,1-dioxide (4j). Colorless oil. Yield
1
4
3 mg (19%). H NMR (400 MHz, CDCl ) δ 7.41 (d, J = 8.7 Hz,
3
+
2H), 7.35 (d, J = 8.7 Hz, 2H), 6.92 (d, J = 8.7 Hz, 2H), 6.88 (d, J = 8.7
calcd for C H N NaO S (M + Na ) m/z 511.1662, found 511.1656.
28
28
2
4
Hz, 2H), 5.37 (s, 1H), 4.22 (d, J = 11.1 Hz, 1H), 4.15 (d, J = 11.1 Hz,
Ethyl rel(3S,5S,6R)-3,5-Bis(4-nitrophenyl)-2,4-dimethyl-1,2,4-thia-
1
1
1
6
2
1
4
H), 4.05 (q, J = 7.1 Hz, 2H), 3.83 (s, 3H), 3.80 (s, 3H), 2.74 (s, 3H),
.86 (s, 3H), 1.07 (t, J = 7.1 Hz, 2H). C NMR (400 MHz, CDCl ) δ
63.0, 159.9, 159.6, 130.6, 130.4, 129.3, 127.6, 114.1, 113.8, 81.8, 68.7,
5.2, 62.1, 55.3, 55.2, 39.1, 31.3, 13.8. IR (film) v cm 3064, 3032,
981, 2923, 2841, 1736, 1603, 1513, 1464, 1400, 1367, 1334, 1259,
160, 1028, 834. HRMS (ESI) calcd for C H N O S (M + H )
49.1741, found 449.1741.
Ethyl rel(3S,5S,6R)-3,5-Di([1,1′-biphenyl]-4-yl)-2,4-dimethyl-1,2,4-
thiadiazinane-6-carboxylate 1,1-dioxide (4k). Colorless crystals. Mp
diazinane-6-carboxylate 1,1-dioxide (4o). Colorless crystals. Mp
13
1
192−193 °C. Yield 7 mg (3%). H NMR (400 MHz, CDCl ) δ 8.32
3
3
(d, J = 8.6 Hz, 2H), 8.27 (d, J = 8.6 Hz, 2H), 7.73 (d, J = 8.6 Hz, 2H),
7.69 (d, J = 8.6 Hz, 2H), 5.61 (s, 1H), 4.45 (d, J = 11.1 Hz, 1H), 4.25
(d, J = 11.1 Hz, 1H), 4.14 (dq, J = 10.8, 7.2 Hz, 1H), 4.06 (dq, J =
10.8, 7.2 Hz, 1H), 2.77 (s, 3H), 1.90 (s, 3H), 1.11 (t, J = 7.2 Hz, 3H).
−
1
+
2
2
29
2
6
13
C NMR (400 MHz, CDCl ) δ 162.3, 148.4, 148.2, 145.2, 141.8,
3
130.2, 129.3, 124.3, 124.1, 81.1, 68.6, 64.3, 62.9, 39.4, 31.7, 13.8. IR
−1
(
film) v cm 3112, 3081, 2982, 2923, 1739, 1608, 1524, 1491, 1367,
1
1
7
7
71−172 °C. Yield 81 mg (30%). H NMR (400 MHz, CDCl ) δ
3
1349, 1301, 1270, 1202, 1164, 1012, 860. HRMS (ESI) calcd for
.66−7.57 (m, 10H), 7.53 (d, J = 8.2 Hz, 2H), 7.49−7.43 (m, 4H),
.40−7.34 (m, 2H), 5.52 (s, 1H), 4.33 (d, J = 11.4 Hz, 1H), 4.30 (d, J
+
C H N O S (M + H ) m/z 479.1231, found 479.1237.
20
23
4
8
Ethyl rel(3S,5S,6R)-2,4-Dimethyl-3,5-bis(3-nitrophenyl)-1,2,4-
=
11.4 Hz, 1H), 4.07 (qd, J = 7.1, 1.8 Hz, 2H), 2.83 (s, 3H), 1.98 (s,
thiadiazinane-6-carboxylate 1,1-dioxide (4p). Yellow oil. Yield 33
H), 1.05 (t, J = 7.1 Hz, 3H). 13C NMR (400 MHz, CDCl ) δ 163.0,
1
3
1
1
3
1
mg (13%). H NMR (400 MHz, CDCl ) δ 8.39 (d, J = 10.4 Hz, 2H),
3
3
42.0, 141.6, 140.3, 140.2, 137.5, 134.4, 129.7, 128.86, 128.85, 128.7,
27.7, 127.6, 127.5, 127.2, 127.1, 127.0, 82.0, 69.1, 65.0, 62.3, 39.3,
8.32 (dd, J = 8.2, 1.2 Hz, 1H), 8.27 (dd, J = 8.2, 1.2 Hz, 1H), 7.91 (d, J
= 7.7 Hz, 1H), 7.87 (d, J = 7.7 Hz, 1H), 7.70 (t, J = 8.0 Hz, 1H), 7.64
(t, J = 7.9 Hz, 1H), 5.65 (s, 1H), 4.48 (d, J = 11.2 Hz, 1H), 4.30 (d, J =
−
1
1.6, 13.8. IR (film) v cm 2981, 1739, 1603, 1487, 1450, 1408, 1363,
338, 1302, 1201, 1162, 1138, 1120, 1007, 938, 851, 764, 698, 655.
11.2 Hz, 1H), 4.19−4.12 (m, 1H), 4.12−4.05 (m, 1H), 2.82 (s, 3H),
+
13
HRMS (ESI) calcd for C H N O S (M + H ) m/z 541.2156, found
1.95 (s, 3H), 1.12 (t, J = 7.1 Hz, 3H). C NMR (400 MHz, CDCl ) δ
32
33
2
4
3
5
41.2152.
Ethyl rel(3S,5S,6R)-3,5-Di(4-bromophenyl)-2,4-dimethyl-1,2,4-
thiadiazinane-6-carboxylate 1,1-dioxide (4l). Colorless oil. Yield
162.3, 148.7, 148.5, 140.3, 137.2, 135.1, 134.6, 130.2, 130.1, 124.5,
124.1, 123.0, 81.2, 68.6, 64.5, 62.9, 39.5, 31.7, 13.8. IR (film) v cm−
1
2
983, 1738, 1584, 1532, 1464, 1352, 1305, 1204, 1164, 1139, 1120,
1
1
7
2
4
7
1
3
1
1 mg (4%). H NMR (400 MHz, CDCl ) δ 7.56 (d, J = 8.4 Hz, 2H),
3
1017, 906, 810, 795, 733, 693. HRMS (ESI) calcd for C H N NaO S
2
0
22
4
8
.51 (d, J = 8.4 Hz, 2H), 7.37 (d, J = 8.4 Hz, 2H), 7.33 (d, J = 8.4 Hz,
H), 5.40 (s, 1H), 4.22 (d, J = 11.2 Hz, 1H), 4.18 (d, J = 11.2 Hz, 1H),
.07 (qd, J = 7.1, 2.8 Hz, 2H), 2.73 (s, 3H), 1.86 (s, 3H), 1.09 (t, J =
+
(
M + Na ) m/z 501.1051, found 501.1052.
Ethyl rel(4bR,5R,13bR)-4b,5,9,13b,15,16-Hexahydro-8H-[1,2,4]-
thiadiazino[3,2-a:5,4-a′]diisoquinoline-5-carboxylate 6,6-dioxide
.1 Hz, 3H). 13C NMR (400 MHz, CDCl ) δ 162.6, 137.5, 134.3,
(6a). Colorless crystals. Mp 134−135 °C. Yield 42 mg (20%). H
1
3
32.4, 132.1, 131.9, 130.8, 129.9, 128.4, 81.5, 68.7, 64.8, 62.5, 39.3,
1.4, 13.8. IR (film) v cm 2925, 1740, 1591, 1487, 1460, 1406, 1366,
338, 1299, 1262, 1202, 1162, 1137, 1119, 1096, 1072, 1008, 939, 843,
NMR (400 MHz, CDCl ) δ 7.48−7.44 (m, 1H), 7.31−7.25 (m, 2H),
3
−1
7.25−7.18 (m, 3H), 7.11 (dd, J = 12.4, 7.5 Hz, 2H), 5.97 (s, 1H), 5.18
(d, J = 10.4 Hz, 1H), 4.32 (d, J = 10.4 Hz, 1H), 4.28−4.23 (m, 1H),
H
J. Org. Chem. XXXX, XXX, XXX−XXX