European Journal of Organic Chemistry
10.1002/ejoc.202000915
FULL PAPER
=
8.1 Hz, 1H, NCH), 4.77-4.87 (m, 1H, CHCH
ArH) ppm; 13C NMR (CDCl
) δ : 19.8 (CH
NCH ), 45.9 (CH ), 48.5 (CHCO), 54.2 (CHCO), 61.1 (NCH),
9.2 (NC), 73.6 (CHCH ), 124.8, 126.4, 128.2, 130.5, 134.2,
35.6 (ArC), 173.8 (CO), 174.6 (CO), 175.0 (CO) ppm; IR (ATR)
3
), 7.20-7.35 (m, 4H,
193 (100), 178 (14), 156 (13), 117 (12), 116 (13), 115 (52), 91
3
C
3
), 20.5 (CH ), 25.3
3
(23), 77 (10); HRMS calcd. for C20
352.1423.
20 2 4
H N O : 352.1423; found:
(
3
2
6
1
3
(2R,3S,4R,5S,8R)-3-Benzoyl-8-methyl-2,4-diphenyl-7-oxa-1-
azaspiro[4.4]nonan-6-one (17al). White solid (93.8 mg, 76%
휐푚푎푥: 3022, 2977, 2932, 1773, 1699, 1434, 1285, 1198, 1095 cm-
1;
27.7
MS (EI): m/z 320 (16), 278 (43), 276 (22), 261 (100), 248 (18),
yield, 92:8 dr); Precipitation CHCl
3
/n-Hexane; mp: 194 °C; [훼]퐷
1
2
C
47 (22), 209 (11), 164 (10), 96 (12); HRMS calcd. for
: 328.1423; found: 328.1430.
= 64.6 (c 0.82, CHCl
= 6.2 Hz, 3H, CH
J = 13.0, 6.1 Hz, 1H, CH
3
); H NMR (300 MHz, CDCl
3
) δ
H
: 1.21 (d, J
), 2.71 (dd,
), 4.56 (d, J
18
H
20
N
2
O
4
3
), 2.03 (dd, J = 13.0, 9.7 Hz, 1H, CH
), 2.98-3.07 (m, 1H, CHCH
2
2
3
(
3S,3'R,3a'S,5R,6a'R)-3'-(4-Methoxyphenyl)-5,5'-
= 11.8 Hz, 1H, CCH), 4.94 (dd, J = 11.7, 9.8 Hz, 1H, CHCO), 5.05
(d, J = 9.8 Hz, 1H, NCH), 7.10-7.12 (m, 3H, ArH), 7.24-7.36 (m,
9H, ArH), 7.47-7.51 (m, 1H, ArH), 7.69-7.71 (m, 1H, ArH) ppm;
dimethylhexahydro-2H,4'H-spiro[furan-3,1'-pyrrolo[3,4-
c]pyrrole]-2,4',6'(5'H)-trione (17ai). White solid (87.8 mg, 85%
yield, 89:11 dr); Precipitation CHCl
[
/n-Hexane; mp: 184 °C;
); H NMR (300 MHz, CDCl ) δ : 1.54
), 2.03 (t, J = 11.6 Hz, 1H, CH ), 2.68 (dd,
), 2.86 (s, 3H, NCH ), 3.38 (t, J = 7.7 Hz,
H, CCH), 3.60 (t, J = 7.8 Hz, 1H, NCHCH), 3.81 (s, 3H, OCH ),
.65 (d, J = 8.1 Hz, 1H, NCH), 4.73-4.83 (m, 1H, CHCH ), 6.9 (d,
13C NMR (CDCl
55.0 (CCHPh), 64.6 (NCH), 70.9 (NC), 74.4 (CHCH
3
3
) δ
C
: 21.6 (CH
3
), 41.7 (CH
2
), 54.6 (CHCOPh),
), 127.8,
3
2
4.6
1
훼]
= -151.9 (c 0.5, CHCl
3
3
H
퐷
(
d, J = 6.1 Hz, 3H, CH
3
2
127.9, 128.2, 128.3, 128.7, 129.1, 133.3, 135.2, 137.4, 139.1
J = 12.5, 4.5 Hz, 1H, CH
2
3
(ArC), 179.1 (CO), 196.2 (COPh) ppm; IR (ATR) 휐푚푎푥: 3358, 3082,
-1
1
4
3
3031, 2973, 2935, 1757, 1678, 1664 cm ; MS (EI): m/z 263 (21),
262 (100), 234 (19), 223 (14), 209 (13), 208 (14), 207 (12), 204
(11), 203 (81), 161 (12), 131 (11), 117 (16), 115 (11), 105 (32), 91
3
J = 8.7 Hz, 1H, ArH), 7.26 (d, J = 8.7 Hz, 1H, ArH) ppm; 3C NMR
1
(
5
1
CDCl
3
) δ
4.5 (CHCO), 55.4 (OCH
14.0, 127.0, 128.3, 159.7 (ArC), 174.1 (CO), 174.4 (CO), 174.9
C
: 20.4 (CHCH
3
), 25.4 (NCH
3
), 45.9 (CH
2
), 50.7 (CHCO),
3
(10), 77 (25); HRMS calcd. for C27H25NO : 411.1834; found:
3
), 64.5 (NCH), 69.7 (NC), 73.8 (CHCH
3
), 411.1812.
-1
(
CO) ppm; IR (ATR) 휐
: 2981, 2911, 1774, 1693, 1245 cm ;
Dimethyl (2R,3S,4S,5S,8R)-8-methyl-6-oxo-2-phenyl-7-oxa-1-
azaspiro[4.4]nonane-3,4-dicarboxylate (major
diastereoisomer) (17am). White foam (43.7 mg, 42% yield,
69:31 dr); precipitation CH Cl
/n-Hexane; 1H NMR (300 MHz,
3
CDCl ) δ : major diastereoisomer: 1.47 (d, J = 6.2 Hz, 3H, CHCH ,
푚푎푥
+
MS (EI): m/z 344 (M , 30%), 300 (26), 299 (13), 286 (20), 285
100), 273 (16), 271 (10), 270 (22), 233 (43), 188 (17), 187 (13),
(
1
3
73 (13), 134 (10), 121 (12); HRMS calcd. for C18
44.1372; found: 344.1375.
H
20
N
2
O :
5
2
2
3
H
major diastereoisomer), 1.50 (d, J = 6.3Hz, 1.5H, CH
diastereoisomer), 1.95 (dd, J = 13.5, 8.9 Hz, 1H, CH
3
, minor
, major
(
3S,3'R,3a'S,5R,6a'R)-5,5'-Dimethyl-3'-(thiophen-2-
2
yl)hexahydro-2H,4'H-spiro[furan-3,1'-pyrrolo[3,4-c]pyrrole]-
diastereoisomer), 2.09 (dd, J = 13.0, 9.2 Hz, 0.4 H, CH
2
, minor
2
,4',6'(5'H)-trione (17aj). White solid (89.3 mg, 93% yield, 86:14
diastereoisomer), 2.67 (dd, J = 13.5, 6.7 Hz, 1H, CH
2
diastereoisomer), 2.89 (dd, J = 13.0, 8.0 Hz, 0.4H, CH , minor
2
, major
2
4.6
dr); Precipitation CHCl
3
/n-Hexane; mp: 154 °C; [훼]
= -119.3 (c
: 1.54 (d, J = 6.1 Hz,
), 2.64 (dd, J =
), 3.36 (d, J = 7.6 Hz,
H, CCH), 3.61 (t, J = 7.8 Hz, 1H, NCHCH), 4.73-4.83 (m, 1H,
), 4.91 (d, J = 8.0 Hz, 1H, NCH), 7.03 (dd, J = 5.0, 3.6 Hz,
H, ArH), 7.12 (d, J = 3.6 Hz, 1H, ArH), 7.30 (dd, J = 5.1 Hz, 1.1
Hz) ppm; 13C NMR (CDCl
) δ : 20.4 (CHCH ), 25.5 (NCH ), 46.0
), 51.0 (CHCO), 54.4 (CHCO), 69.6 (NCH), 73.7 (NC), 125.4,
25.7, 127.2, 138.6 (ArC), 173.8 (CO), 174.3 (CO), 174.5(CO)
퐷
1
0
3
1
1
.5, CHCl
H, CH
2.4, 4.6 Hz, 1H, CH
3
); H NMR (300 MHz, CDCl
3
) δ
H
diastereoisomer), 3.20 (s, 3H, CO
3.65 (s, 1.24, 3H, CO CH , minor diastereoisomer), 3.73 (s, 1.70H,
CO CH , CCH, minor diastereoisomer), 3.75 (s, 3H, CO CH
2 3
CH , major diastereoisomer),
3
), 1.99 (dd, J = 12.1, 11.1 Hz, 1H, CH
), 2.93 (s, 3H, NCH
2
2
3
2
3
2
3
2
3
,
major diastereoisomer), 3.79-3.94 (m, 2H, NCHCH, CCH, major
diastereoisomer), 4.31-4.40 (m, 1.4 H, CH2 major
CHCH
1
3
diastereoisomer, CH
2
minor diastereoisomer), 4.69 m (1H, NCH,
3
C
3
3
major diastereoisomer), 4.74-4.89 (m, 1H, NCH, minor
13
(
CH
2
diastereoisomer) 7.29-7.54 (m, 7.2 H, ArH) ppm; C NMR
(CDCl ) δ : major diastereoisomer: 22.0, 41.4, 51.8, 52.6, 52.8,
1
3
C
-1
ppm; IR (ATR) 휐
3
2
: 2981, 1770, 1693, 1203 cm ; MS (EI): m/z
57.6, 63.6, 68.7, 74.7, 127.3, 127.4, 128.4, 128.6, 129.0, 138.9,
170.4, 170.8, 177.4; Minor diastereoisomer: 21.0, 45.4, 52.9, 54.2,
54.7, 67.4, 70.4, 74.4, 139.0, 170.7, 173.1, 176.4 ppm; IR (ATR)
푚푎푥
+
20 (M , 16%), 278 (44), 276 (22), 275 (11), 262 (16), 261 (100),
47 (22), 209 (11), 164 (10), 96 (12); HRMS calcd. for
S: 320.0831; found: 320.0829.
-1
+
C
15
H
16
N
2
O
4
휐푚푎푥: 2950, 1761, 1729, 1201, 1163 cm ; MS (EI): m/z 316 (M -
CH O, 24%), 303 (26), 271 (14), 256 (22), 244 (48), 243 (15), 242
3
(
2S,3S,4S,5S,8R)-8-Methyl-3-nitro-2,4-diphenyl-7-oxa-1-
azaspiro[4.4]nonan-6-one (17ak). White solid (82.4 mg, 92%
yield, 90:10 dr); Precipitation CHCl /n-Hexane; mp: 177 °C;
); H NMR (300 MHz, CDCl ) δ : 1.22
), 1.97 (dd, J = 13.2, 9,3 Hz, 1H, CH ), 2.59
dd, J = 13.2, 6.2 Hz, 1H, CH ), 3.17 (dp, J = 9.3, 6.2 Hz, 1H,
), 4.57 (d, J = 8.8 Hz, 1H, CCH), 4.98 (d, J = 8.3 Hz, 1H,
NCH), 5.84 (t, J = 8.5 Hz, 1H, CHNO ), 7.32-7.48 (m, 10 H, ArH)
ppm; 13C NMR (CDCl
) δ : 21.5 (CH ), 40.2 (CH ), 57.6 CCHPh),
5.5 (NCH), 70.6 (NC), 74.8 (CHCH ), 93.0 (CHNO ), 127.0,
27.8, 129.0, 129.1, 129.2, 129.6, 132.8, 134.8 (ArC), 177.3 (CO)
(14), 216 (24), 212 (40), 203 (20), 196 (15), 187 (57), 178 (12),
177 (100), 170 (14), 157 (16), 156 (41), 143 (21), 141 (97), 115
3
(26) ; HRMS calcd. for C18
288.1237.
6 2 3 2
H21NO –(C H O ): 288.1236; found:
2
8.6
1
[
(
(
훼]
= 65.4 (c 0.7, CHCl
3
3
H
퐷
d, J = 6.2 Hz, 1H, CH
3
2
2
(2R,3S,5R,8R)-8-Methyl-3-(2-oxopyrrolidine-1-carbonyl)-2-
phenyl-7-oxa-1-azaspiro[4.4] nonan-6-one (17an). White solid
CHCH
3
2
(61.6 mg, 60% yield, 93:7 dr); Precipitation CHCl
3
/n-Hexane;
); H NMR (300 MHz, CDCl
3
), 1.69-1.84 (m, 1H), 1.93 (m, 1H),
30.4
1
3
C
3
2
mp: °C; [훼]퐷 = 45.34 (c, 0.6 CHCl
: 1.48 (d, J = 6.1 Hz, 3H, CH
3
3
)
6
1
3
2
δ
H
2.09-2.26 (m, 2H), 2.35-2.44 (m, 1H), 2.49-2.56 (m, 1H), 2.65 (bs,
1H), 2.71-2.78 (m, 1H), 2.84-2.92 (m, 1H), 3.45-3.54 (m, 1H),
4.50-4.61 (m, 1H), 4.70-4.74 (m, 2H), 7.24-7.29 (m, 5H) ppm; 13
C
-1
+
ppm; IR (ATR) 휐푚푎푥: 2979, 1769, 1551 cm ;MS (EI): m/z 306 (M
-
(
NO
2
, 23%), 263 (17), 262 (72), 261 (18), 260 (18), 246 (35), 233
14), 232 (56), 220 (11), 219 (32), 203 (12), 202 (12), 194 (16),
3 C 2 3 2 2
NMR (CDCl ) δ : 16.9 (CH ), 20.8 (CH ), 33.6 (CH ), 37.5 (CH ),
8
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