Isocyanide-based multicomponent reaction for the formation of 1,3-oxathiolane-2-imine…
3
(1H, t, J = 7.1 Hz, CH), 7.06 (2H, d, J = 7.1 Hz, 2 CH),
3
d = 1.56 (9H, s, 3 Me), 3.42–4.17 (6H, m, 6 CH),
3
7.21 (2H, t, J = 7.1 Hz, 2 CH) ppm;
13
4
.91–5.39 (3H, m, 3 CH), 5.73–5.81 (1H, m, CH) ppm;
C NMR
1
3
C NMR (125.7 MHz, CDCl ): d = 30.2 (3 Me), 35.7
(125.7 MHz, CDCl ): d = 30.1 (3 Me), 34.7 (CH ), 55.1
3
3
2
(
CH ), 58.1 (C), 73.2 (CH ), 79.6 (CH ), 81.1 (CH),
2
(C), 67.1 (CH ), 78.9 (CH), 114.3 (2 CH), 121.9 (CH),
2
2
2
1
19.7(CH ), 136.1(CH), 164.8 (C) ppm; EI-MS (70 eV):
2
129.2 (2 CH), 159.6 (C), 165.2 (C) ppm; EI-MS (70 eV):
?
m/z (%) = 265 (M , 4), 98 (67), 77 (100), 70 (54), 59 (60),
?
m/z (%) = 229 (M , 5), 206 (51), 149 (100), 142 (67), 91
72), 59 (60), 57 (56), 54 (27).
(
54 (20).
N-(tert-Butyl)-5-(chloromethyl)-1,3-oxathiolan-2-imine
4n, C H ClNOS)
The crude product was purified by column chromatography
N-(tert-Butyl)-4-phenyl-1,3-oxathiolan-2-imine
(
(4r, C H NOS)
13 17
8
14
The crude product was purified by column chromatography
(
SiO ; hexane/EtOAc 3/1; R = 0.52) affording 0.15 g
2
(SiO ; hexane/EtOAc 5/1; R = 0.61) affording 0.19 g
2
f
f
(
71%) 4n. Yellow oil; IR (KBr): vꢀ = 3024, 2970, 1641,
(83%) 4r. m.p.: 76–78 °C; IR (KBr): vꢀ = 3040, 2970,
-
1
1
-1 1
1
340, 1136 cm
;
H
NMR (500.1 MHz, CDCl3):
1634, 1310, 1130 cm : H NMR (500 MHz, CDCl ):
3
2
d = 1.47 (9H, s, 3 Me), 3.61–3.92 (4H, m, 4 CH),
d = 1.60 (9H, s, 3 Me), 4.81 (1H, dd, J = 10.1 Hz,
1
.88–4.94 (1H, m, CH) ppm; C NMR (125.7 MHz,
3
3
2
4
J = 5.6 Hz, CH), 5.12 (1H, dd,
J = 10.1 Hz,
3
CDCl ): d = 29.4 (3 Me), 37.1 (CH ), 45.8 (CH ), 56.1
J = 6.9 Hz, CH), 5.32 (1H, m, CH), 7.17–7.42 (5H, m,
1
3
2
2
3
(
C), 83.5 (CH), 165.1 (C) ppm; EI-MS (70 eV): m/
5 CH) ppm; C NMR (125.7 MHz, CDCl ): d = 30.1 (3
3
?
z (%) = 207 (M , 4), 135 (100), 70 (54), 59 (60), 54 (20).
Me), 51.4 (CH ), 56.2 (C), 80.3 (CH), 127.1 (2 CH), 128.5
2
(
(
(
CH), 129.7 (2 CH), 136.1 (C), 166.8 (C) ppm; EI-MS
?
70 eV): m/z (%) = 235 (M , 4), 98 (67), 77 (100), 70
N-(tert-Butyl)hexahydrobenzo[d][1,3]oxathiol-2-imine
(
4o, C H NOS)
11 19
54), 59 (60).
The crude product was purified by column chromatography
(
SiO ; hexane/EtOAc 8/1; R = 0.27) affording 0.20 g
2 f
(
95%) 4o; IR (KBr): vꢀ = 3028, 2976, 1633, 1323,
N-(tert-Butyl)-4,5-diphenyl-1,3-oxathiolan-2-imine
-
1
1
1
109 cm
;
H NMR (500.1 MHz, CDCl ): d = 1.53
(4s, C H NOS)
19 21
3
(
9H, s, 3 Me), 1.44–2.11 (8H, m, 4 CH ), 3.70–3.75 (1H,
2
The crude product was purified by column chromatography
1
3
m, CH), 5.11–5.15 (1H, m, CH) ppm;
C NMR
(SiO ; hexane/EtOAc 3/1; R = 0.51) affording 0.25 g
2
f
(
(
(
125.7 MHz, CDCl ): d = 25.1 (CH ), 25.7 (CH ), 29.1
(79%) 4s. m.p.: 101–103 °C; IR (KBr): vꢀ = 3041, 2938,
3
2
2
-1 1
;
CH ), 31.6 (CH ), 32.9 (3 Me), 40.1 (CH), 57.3 (C), 83.2
2
2231, 1634, 1318, 1134 cm
H NMR (500 MHz,
2
?
CH), 169.2 (C) ppm; EI-MS (70 eV): m/z (%) = 213 (M ,
), 149 (100), 98 (75), 91 (63), 71 (55), 59 (48), 54 (26).
CDCl ): d = 1.46 (9H, s, 3 Me), 4.11 (1H, s, CH), 5.67
3
1
(1H, s, CH), 7.14–7.32 (10H, m, 10 CH) ppm; C NMR
3
5
(
(
(
(
(
125.7 MHz, CDCl ): d = 29.6 (3 Me), 46.3 (CH), 57.1
3
N-(tert-Butyl)hexahydro-4H-cyclohepta[d][1, 3]oxathiol-
-imine (4p, C H NOS)
The crude product was purified by column chromatography
C), 72.2 (CH), 120.1 (C), 126.7 (CH), 127.9 (CH), 128.1
2 CH), 128.4 (2 CH), 128.5 (2 CH), 129.1 (2 CH), 134.2
C), 1383.0 (C), 167.2 (C) ppm; EI-MS: m/z (%) = 311
2
1
2 21
(
SiO ; hexane/EtOAc 7/1; R = 0.37) affording 0.13 g
2 f
?
M , 4), 162 (21), 146 (34), 135 (74), 119 (80), 102 (58),
(
58%) 4p. m.p.: 181–183 °C; IR (KBr): vꢀ = 3051, 2917,
7
7 (100), 43 (32).
-
631, 1312, 1123 cm ; H NMR (500 MHz, CDCl3):
1
1
1
d = 1.41–148 (2H, m, CH ), 1.54 (9H, s, 3 Me), 1.68–2.27
2
N-(tert-Butyl)-4-(4-methoxyphenyl)-1,3-oxathiolan-2-imine
4t, C H NO S)
The crude product was purified by column chromatography
(
8H, m, 4 CH ), 3.72–3.76 (1H, m, CH), 5.04–5.11 (1H, m,
2
(
1
4
19
2
1
3
CH) ppm; C NMR (125.7 MHz, CDCl ): d = 23.1
3
(
CH ), 24.6 (CH ), 29.3 (CH ), 32.2 (3 Me), 32.7 (CH ),
2 2 2 2
(SiO ; hexane/EtOAc 4/1; R = 0.58) affording 0.24 g
2 f
3
5.1 (CH ), 43.5 (CH), 56.1 (C), 86.3 (CH), 165.2 (C) ppm;
2
(
91%) 4t. m.p.: 141–143 °C; IR (KBr): vꢀ = 3025, 2961,
?
EI-MS (70 eV): m/z (%) = 227 (M , 4), 135 (100), 98
67), 77 (85), 70 (54), 59 (60), 54 (20).
-1
648, 1305, 1128 cm ; H NMR (500 MHz, CDCl ):
1
1
3
(
2
d = 1.42 (9H, s, 3 Me), 3.27 (1H, dd, J = 11.1 Hz,
3
2
J = 5.6 Hz, CH), 3.71 (1H, dd,
J = 11.1 Hz,
N-(tert-Butyl)-5-(phenoxymethyl)-1,3-oxathiolan-2-imine
4q, C H NO S)
The crude product was purified by column chromatography
3
J = 4.2 Hz, CH), 3.80 (3H, s, OMe), 4.70 (1H, m, CH),
3
.78 (2H, d, J = 7.1 Hz, 2 CH), 6.90 (2H, d, J = 7.1 Hz,
(
1
4
19
2
3
6
1
3
2
CH) ppm; C NMR (125.7 MHz, CDCl ): d = 29.7 (3
(
SiO ; hexane/EtOAc 5/1; R = 0.48) affording 0.26 g
2
3
f
Me), 49.1 (CH), 55.2 (OMe), 57.0 (C), 76.2 (CH ), 115.1
2
(
98%) 4q. m.p.: 65–67 °C; IR (KBr): vꢀ = 3037, 2922,
-
632, 1324, 1136 cm ; H NMR (500 MHz, CDCl3):
1
1
(
2 CH), 128.6 (2 CH), 137.1 (C), 159.2 (C), 167.3 (C) ppm;
?
1
EI-MS: m/z (%) = 265 (M , 4), 162 (21), 146 (34), 135
74), 107 (100), 102 (58), 43 (32).
d = 1.51 (9H, s, 3 Me), 3.51–3.59 (2H, m, 2 CH),
.23–4.31 (2H, m, 2 CH), 4.87–4.92 (1H, m, CH), 6.83
(
4
123