5
750
H. Liu et al. / Tetrahedron Letters 56 (2015) 5747–5751
stirring at room temperature, the organic layer was decanted and
washed with sodium bicarbonate solution (45 mL). The aqueous
phase was extracted with dichloromethane (3 Â 15 mL). The com-
12. Characterization data for compounds 3, 4, A, and 5. All NMR spectra were
obtained in CDCl unless otherwise indicated. 3b: mp 126.5–128.0 °C. IR: 3245,
3
À1
1
1656, 1390, 1338, 1160, 1092, 566 cm
. H NMR: d 7.27–7.23 (m, 4H), 5.53–
5
.58 (m, 1H), 3.90–4.65 (m, 3H), 3.16, 3.08 (ss, 3H), 2.79, 2.73 (ss, 3H), 2.42 (s,
13
bined organic layers were dried over MgSO
4
and evaporated to
3H), 1.00, 0.96 (ss, 9H). C NMR: d 172.0, 171.5, 143.7, 143.4, 136.9, 129.4,
1
2
5
29.3, 127.3, 127.2, 81.2, 77.8, 59.4, 59.3, 56.1, 55.6, 35.7, 35.6, 34.0, 33.4, 26.5,
6.3, 21.5. Anal. Calcd for C16 S: C, 56.12; H, 7.65; N, 8.18. Found: C,
6.35; H, 7.46; N, 8.16. 3d: mp 111.5–113.0 °C. IR: 3222, 1656, 1510, 1164,
afford the crude product which was purified by column
chromatography on silica gel (petroleum ether/ethyl acetate com-
26 2 4
H N O
-(N-sulfonyl)amino amides 5.12 5k: IR: 3334,
À1
1
bination) to afford
255, 1646, 1450, 1342, 1169, 1089, 690 cm
600 MHz, CDCl ): d 7.21–7.89 (m, 10H), 6.49 (d, J = 14.4 Hz, 1H),
.04 (s, 1H), 5.96, 5.93 (dd, J = 7.8 Hz, 1H), 5.87 (d, J = 4.2 Hz, 1H),
a
1084, 1023, 578 cm . H NMR: d 6.73–7.73 (m, 9H), 6.54, 6.49 (dd, J = 8.4 Hz,
À1
1
1H), 5.28, 5.19 (dd, J = 8.4 Hz, 1H), 4.22–4.66 (m, 2H), 3.73 (s, 3H), 3.03, 2.99
ss, 3H), 2.82, 2.74 (ss, 3H). 13C NMR: d 170.4, 170.0, 159.7, 140.5, 140.3, 132.3,
32.2, 129.1, 129.0, 128.7, 128.1, 127.2, 127.1, 127.0, 114.4, 80.5, 78.1, 57.3,
57.1, 55.8, 55.4, 55.3, 34.3, 32.9. Anal. Calcd for C18 S: C, 57.13; H, 5.86;
N, 7.40. Found: C, 57.34; H, 5.93; N, 7.14. 3e: mp 133.0–134.0 °C. IR: 3264,
3
.
H NMR
(
1
(
3
6
2
1
1
1
6
22 2 5
H N O
1
3
3
.80, 2.79 (ss, 3H). C NMR (151 MHz, CDCl ): d 170.1, 169.9,
À1
1
1652, 1347, 1164, 1098, 681 cm
. H NMR: d 7.04–7.7.64 (m, 8H), 6.34, 6.30
40.6, 140.4, 135.5, 135.3, 135.0, 134.3, 132.6, 132.5, 129.0,
28.9, 128.8, 128.6, 128.5, 128.4, 127.3, 127.2, 126.7, 123.6,
22.6, 80.6, 78.2, 34.5, 33.0. Anal. Calcd for C17
(
dd, J = 8.4 Hz, 1H), 5.27, 5.17 (dd, J = 8.4 Hz, 1H), 4.22–4.66 (m, 2H), 3.05, 3.00
13
(ss, 3H), 2.85, 2.75 (ss, 3H), 2.38, 2.36 (ss, 3H), 2.29 (s, 3H). C NMR: d 170.4,
1
1
2
70.0, 143.1, 143.0, 138.6, 138.5, 137.4, 137.3, 133.2, 132.4, 129.7, 129.3, 129.2,
27.8, 127.6, 127.3, 127.1, 80.5, 78.1, 57.5, 57.3, 55.7, 55.4, 34.3, 32.9, 21.5,
18 2 3
H N O S: C,
1.80; H, 5.49; N, 8.48. Found: C, 61.88; H, 5.56; N, 8.60.
1.4, 21.1. Anal. Calcd for C19
0.52; H, 6.68; N, 7.47. 3f: IR: 3235, 1656, 1450, 1333, 1159, 1093, 723 cm
H
24
N
2
O
4
S: C, 60.61; H, 6.43; N, 7.44. Found: C,
À1
6
.
1
H NMR: d 7.24–7.95 (m, 10H), 6.44, 6.40 (dd, J = 7.8 Hz, 1H), 5.40, 5.25 (dd,
Conclusions
J = 7.8 Hz, 1H), 4.24–4.68 (m, 2H), 3.06, 3.02 (ss, 3H), 2.86, 2.77 (ss, 3H). 13
C
NMR: d 170.2, 169.8, 140.3, 140.2, 136.0, 135.2, 132.6, 132.4, 132.3, 129.1,
We have successfully developed a novel and highly efficient
synthetic method toward -(N-sulfonyl)amino-N-methoxy-
methyl-N-methylamides by the additions of N-methoxymethyl-
N-methylcarbamoyl(trimethyl)silane to N-sulfonylimines. The
reaction in general provides good yields of the products under mild
reaction conditions. This approach is an efficient synthesis method
128.7, 128.6, 127.9, 127.7, 127.2, 127.0, 126.4, 80.5, 78.2, 57.8, 57.6, 55.9, 55.5,
3
4.3, 32.9. Anal. Calcd for C17
H
20
N
2
O
4
S: C, 58.60; H, 5.79; N, 8.04. Found: C,
a
À1
5
8.71; H, 5.74; N, 8.25. 3g: IR: 3231, 1656, 1445, 1333, 1164, 1093, 723 cm
.
1
H NMR: d 7.16–7.73 (m, 9H), 6.75, 6.70 (dd, J = 8.4 Hz, 1H), 5.33, 5.24 (dd,
J = 8.4 Hz, 1H), 4.29–4.66 (m, 2H), 3.05, 3.04, 2.99, 2.98 (ssss, 3H), 2.84, 2.75 (ss,
3
1
5
H). 13C NMR: d 169.9, 169.7, 140.3, 140.2, 134.7, 134.6, 134.5, 133.9, 132.5,
32.4, 129.3, 129.2, 129.1, 128.8, 127.1, 126.9, 126.3, 80.6, 78.2, 57.0, 56.8,
19 2 4
5.9, 55.5, 34.7, 33.0. Anal. Calcd for C17H N O SCl: C, 53.33; H, 5.00; N, 7.32.
of
hydrolysis of
lamides 3 at room temperature leading to corresponding
a
-(N-sulfonyl)amino secondary amides because of the acid
-(N-sulfonyl)amino-N-methoxymethyl-N-methy-
-(N-sul-
Found: C, 53.42; H, 5.11; N, 7.38. 3h: mp 114.5–116.0 °C. IR: 3264, 1652, 1515,
À1
1
a
1352, 1169, 1098, 719 cm
. H NMR: d 7.35–8.07 (m, 9H), 6.74, 6.72 (dd,
J = 7.8 Hz, 1H), 5.47, 5.37 (dd, J = 7.8 Hz, 1H), 4.43–4.66 (m, 2H), 3.10, 3.02 (ss,
a
13
3
1
H), 2.90, 2.80 (ss, 3H). C NMR: d 169.2, 169.1, 150.6, 147.8, 147.7, 143.1,
fonyl)amino secondary amides 5. The mild and no catalyst
42.3, 140.0, 139.9, 132.8, 128.9, 128.8, 128.7, 127.1, 126.9, 124.2, 124.0, 122.9,
conditions, simple procedure, and impressive yield provide a valu-
80.9, 76.4, 56.9, 56.6, 56.0, 55.7, 35.2, 35.1. Anal. Calcd for C17
H
19
N
3
O
6
S: C,
5
1
1.90; H, 4.87; N, 10.68. Found: C, 51.84; H, 4.91; N, 10.74. 3i: IR: 3226, 1665,
able method for the preparation of various
a-(N-sulfonyl)amino
À1
1
450, 1337, 1164, 1089, 752 cm
. H NMR: d 7.19–7.77 (m, 6H), 6.54, 6.52 (dd,
secondary amides. We believe that the current methodology will
find applications in organic and medicinal chemistry.
J = 7.8 Hz, 1H), 6.19–6.23 (m, 2H), 5.47, 5.40 (dd, J = 7.8 Hz, 1H), 4.36–4.72 (m,
2H), 3.03–3.07 (m, 3H), 2.82–2.86 (m, 3H). 13C NMR: d 168.0, 167.7, 148.7,
1
1
48.1, 143.0, 142.9, 140.1, 140.0, 132.5, 128.8, 128.7, 127.1, 127.0, 110.7, 109.4,
09.1, 80.5, 78.2, 55.8, 55.4, 51.7, 51.5, 34.4, 32.8. Anal. Calcd for C15 S:
18 2 5
H N O
Acknowledgments
C, 53.24; H, 5.36; N, 8.28. Found: C, 53.33; H, 5.49; N, 8.33. 3j: IR: 3230, 1660,
À1
1
1
445, 1333, 1164, 1088, 723 cm . H NMR: d 6.84–7.79 (m, 8H), 6.51, 6.46 (dd,
J = 8.4 Hz, 1H), 5.62, 5.54 (dd, J = 8.4 Hz, 1H), 4.36–4.72 (m, 2H), 3.11, 3.06 (ss,
This research was supported by Shanxi Province Foundation for
Returness (No. 0713), the Natural Science Foundation of Shanxi
Province (No. 2012011046-9) and Foundation of Shanxi Normal
University (No. SD2015CXXM-83), China.
3
1
H), 2.87, 2.86 (ss, 3H). 13C NMR: d 169.6, 169.3, 140.3, 140.2, 138.7, 137.9,
32.6, 128.9, 128.8, 127.3, 127.2, 127.0, 126.9, 126.8, 126.7, 80.8, 78.2, 56.0,
55.5, 53.0, 52.8, 34.5, 33.0. Anal. Calcd for C15H18N O S : C, 50.83; H, 5.12; N,
2
4 2
7
1
6
.90. Found: C, 50.97; H, 5.22; N, 7.99. 3k: IR: 3222, 1656, 1445, 1333, 1164,
À1
1
094, 691 cm
. H NMR: d 7.21–7.86 (m, 10H), 6.62, 6.56 (dd, J = 15.6 Hz, 1H),
.27, 5.24 (dd, J = 8.4 Hz, 1H), 6.00, 5.97, 5.93, 5.90 (dddd, J = 7.2 Hz, 1H), 5.03,
Supplementary data
4.95 (tt, J = 7.2 Hz, 1H), 4.52–4.94 (m, 2H), 3.19, 3.09 (ss, 3H), 2.98, 2.90 (ss,
3
1
8
H). 13C NMR: d 170.1, 169.9, 140.6, 140.4, 135.5, 135.3, 135.0, 134.3, 132.6,
32.5, 129.0, 128.9, 128.8, 128.6, 128.5, 128.4, 127.3, 127.2, 126.7, 123.6, 122.6,
0.6, 78.2, 55.9, 55.8, 55.6, 55.5, 34.5, 33.0. Anal. Calcd for C191
H N O S: C,
22 2 4
0
60.94; H, 5.92; N, 7.48. Found: C, 60.83; H, 5.99; N, 7.61. 4: mp 114.0–
1
1
1
1
15.5 °C. H NMR: d 7.28–7.77 (m, 4H), 6.31 (d, J = 9.6 Hz, 1H), 5.81–5.83 (m,
13
H), 2.44 (s, 3H), 1.63 (s, 3H), 1.47 (s, 3H). C NMR: d 143.5, 137.2, 129.7,
26.9, 120.3, 116.7, 22.2, 21.6, 16.2. A: 1H NMR: d 8.14 (s, 1H), 4.72, 4.58 (ss,
13
References and notes
2H), 3.24, 3.20 (ss, 3H), 2.93, 2.87 (ss, 3H). C NMR: d 163.3, 162.7, 81.1, 74.4,
5
1
5
2
3
5.3, 54.2, 32.5, 28.3. 5b: mp 196.0–197.0 °C. IR: 3443, 3204, 1644, 1401, 1333,
À1
1
160, 1072 cm
. H NMR: d 7.77 (d, J = 7.8 Hz, 2H), 7.29 (d, J = 8.4 Hz, 2H),
1
.
.39 (d, J = 9.0 Hz, 1H), 5.28 (s, 1H), 3.29 (d, J = 9.6 Hz, 1H), 2.52, 2.51 (ss, 3H),
.43(s, 3H), 0.96 (s, 9H). 13C NMR: d 170.0, 143.6, 136.6, 129.5, 127.5, 65.4, 53.5,
22 2 3
4.4, 26.5, 26.0, 21.5. Anal. Calcd for C14H N O S: C, 56.35; H, 7.43; N, 9.39.
Found: C, 56.48; H, 7.24; N, 9.52. 5c: mp 218.5–220.0 °C. IR: 3340, 3257, 1644,
À1
1
1327, 1167, 1088 cm
. H NMR: d 7.62 (d, J = 8.4 Hz, 2H), 7.28 (d, J = 8.4 Hz,
2.
3.
4.
2H), 6.70 (d, J = 8.4 Hz, 2H), 6.57 (d, J = 8.4 Hz, 2H), 5.81 (d, J = 3.6 Hz, 1H), 5.75
(
3
6
d, J = 3.6 Hz, 1H), 4.61, 4.60 (ss, 1H), 2.94 (s, 6H), 2.76, 2.75 (ss, 3H), 2.41 (s,
H). 13C NMR: d 170.2, 150.7, 143.2, 136.6, 129.4, 128.7, 127.4, 123.7, 112.5,
0.4, 40.4, 26.7, 21.5. Anal. Calcd for C18 S: C, 59.81; H, 6.41; N, 11.63.
23 3 3
H N O
Found: C, 59.62; H, 6.13; N, 11.45. 5d: mp 113.0–114.0 °C. IR: 3340, 3265,
À1
1
1651, 1509, 1333, 1156, 1088 cm
. H NMR: d 7.72–7.41 (m, 5H), 7.05 (d,
J = 8.4 Hz, 2H), 6.77 (d, J = 8.4 Hz, 2H), 5.98 (s, 1H), 5.67 (s, 1H), 4.72, 4.71 (ss,
1
1
H), 3.86, 3.78 (ss, 3H), 2.76, 2.75 (ss, 3H). 13C NMR: d 169.7, 159.8, 139.7,
32.6, 128.9, 128.4, 127.2, 114.4, 60.1, 55.3, 26.7. Anal. Calcd for C16 S:
18 2 4
H N O
5.
6.
7.
8.
C, 57.47; H, 5.43; N, 8.38. Found: C, 57.50; H, 5.26; N, 8.10. 5e: mp 174.0–
À1
1
175.5 °C. IR: 3423, 3256, 1656, 1401, 1342, 1167, 1088 cm
. H NMR: d 7.62
(
d, J = 8.4 Hz, 2H), 7.22 (d, J = 8.4 Hz, 2H), 7.07 (d, J = 8.4 Hz, 2H), 7.02 (d,
J = 8.4 Hz, 2H), 5.93 (d, J = 3.6 Hz, 1H), 5.79 (d, J = 3.6 Hz, 1H), 4.68, 4.67 (ss, 1H),
2
1
C
.74, 2.73 (ss, 3H), 2.42 (s, 3H), 2.32 (s, 3H). 13C NMR: d 169.6, 143.5, 138.7,
36.5, 133.7, 129.7, 129.5, 127.6, 127.3, 60.4, 26.7, 21.5, 21.1. Anal. Calcd for
9
.
1
17
H N O S: C, 61.42; H, 6.06; N, 8.43. Found: C, 61.15; H, 6.13; N, 8.18. 5f:
20 2 3
À1
1
mp 182.0–183.0 °C. IR: 3434, 3276, 1640, 1401, 1342, 1171, 1076 cm
. H
1