1384
E. Selva et al. / Tetrahedron 75 (2019) 1378e1386
13C NMR (75 MHz, CDCl
d
: 172.6, 168.2, 152.7, 138.5, 130.2, 130.0,
1H), 3.88 (s, 3H), 3.54 (t, J ¼ 8.2 Hz, 1H), 3.28 (d, J ¼ 7.0 Hz, 1H),
2.88e2.61 (m, 9H), 2.18e1.84 (m, 5H), 1.51e1.11 (m, 8H), 0.99e0.70
3
)
1
4
2
29.9, 128.5, 128.4, 128.0, 127.9, 127.3, 127.1, 71.2, 66.0, 61.8, 47.2,
2.4, 39.5, 31.9, 31.5, 29.8, 29.7, 29.5, 29.3, 29.1, 27.2, 25.62, 25.2,
2.7, 22.6, 14.3, 14.1. LRMS (EI): m/z ¼ 552 (M , <1%), 481 (97), 479
13
(m, 3H). C NMR (75 MHz, CDCl
3
)
d
: 175.4, 174.4, 171.8, 141.2, 130.4
þ
2
(d,
J
C-F ¼ 32.9 Hz, CHCF
3
), 129.4, 128.7, 128.5, 127.9, 127.7, 127.6,
3
(
(
100), 392 (26), 331 (58), 198 (16), 170 (20), 156 (36), 91 (25), 55
32). HRMS (EI): calcd. for C33
127.45, 127.4, 125.4 (d,
52.6, 50.0, 34.7, 31.5, 29.3, 27.2, 25.6, 25.5, 24.9, 22.5, 21.9, 14.1.
J
C-F ¼ 4.1 Hz, CHCHCF
3
), 70.7, 60.9, 55.3,
19
H
48
N
2
O
5
552.3563; found 552.3557.
F
þ
NMR
d
: ꢁ63.0. LRMS (EI): m/z ¼ 600 (M , <1%), 541 (27), 395 (23),
4
1
.5.13. Ethyl (1SR,3RS,3aSR,6aRS)-1-[(7Z,10Z)-hexadeca-7,10-dien-
-yl]-5-methyl-4,6-dioxo-3-(4-(trifluoromethyl)phenyl)
355 (100), 322 (25), 210 (25), 91 (18), 67 (23). HRMS (EI): calcd. for
600.3175; found 600.3167.
34 43 3 2 4
C H F N O
octahydropyrrolo[3,4-c]pyrrole-1-carboxylate 6bd
Yellow oil, (255 mg, 86% yield). R 0.43 (hexane/ethyl acetate: 7/
). IR (neat) ʋmax: 1127, 1165, 1325, 1706, 2856, 2927, 3341,
f
3
3
4.5.17. Ethyl (1SR,3SR,3aSR,6aRS)-1-[(2Z,5Z,8Z,11Z,14Z,17Z)-icosa-
2,5,8,11,14,17-hexaen-1-yl]-5-methyl-4,6-dioxo-3-
phenyloctahydropyrrolo[3,4-c]pyrrole-1-carboxylate 6da
ꢁ
1 1
464 cm . H NMR (300 MHz, CDCl
3
)
d
: 7.61 (d, J ¼ 8.7 Hz, 2H), 7.48
(
(
d, J ¼ 8.1 Hz, 2H), 5.53e5.20 (m, 4H), 4.69 (d, J ¼ 9.1 Hz, 1H), 4.36
dd, J ¼ 7.2, 4.6 Hz, 2H), 3.56 (dd, J ¼ 9.1, 7.5 Hz, 1H), 3.29 (d,
f
Yellow oil, (210 mg, 74% yield). R 0.40 (hexane/ethyl acetate: 7/
J ¼ 7.5 Hz, 1H), 2.81 (s, 3H), 2.77 (t, J ¼ 6.1 Hz, 1H), 2.06 (dd, J ¼ 8.2,
3). IR (neat) ʋmax: 1130, 1288, 1382, 1438, 1702, 2965, 3060,
ꢁ
1
1
5
.2 Hz, 4H), 1.95e1.65 (m, 1H), 1.52e1.14 (m, 19H), 0.96e0.86 (m,
3454 cm
.
3
H NMR (300 MHz, CDCl ) d: 7.36e7.34 (m, 5H),
1
3
3
H). C NMR (75 MHz, CDCl
3
)
d
: 175.4, 174.4, 171.4, 141.4, 132.5 (d,
5.62e5.31 (m, 12H), 4.68 (d, J ¼ 9.1 Hz, 1H), 4.35 (qd, J ¼ 7.1, 0.9 Hz,
2H), 3.54 (dd, J ¼ 9.2, 7.5 Hz, 1H), 3.33 (d, J ¼ 7.4 Hz, 1H), 3.06e2.76
(m, 13H), 2.66 (dd, J ¼ 14.5, 7.8 Hz, 1H), 2.09 (tt, J ¼ 8.2, 1.2 Hz, 3H),
1
2
J
1
C-F ¼ 271.7 Hz, CF
3
), 130.5 (d,
J
C-F ¼ 32.7 Hz, CHCF
3
), 130.3129.8,
3
28.2, 127.8, 127.5, 125.4 (d, JC-F ¼ 3.7 Hz, CHCHCF
3
), 70.6, 61.7, 60.7,
13
5
5.0, 49.9, 34.9, 31.5, 29.4, 29.3, 29.0, 27.2, 27.1, 25.6, 24.9, 23.6, 22.5,
1.40 (t, J ¼ 7.2 Hz, 3H), 0.99 (t, J ¼ 7.5 Hz, 3H). C NMR (75 MHz,
1
9
þ
1
4.1. F NMR
d: ꢁ62.5. LRMS (EI): m/z ¼ 590 (M , <1%), 519 (47),
3
CDCl ) d: 175.6, 174.7, 171.3, 137.3, 132.8, 132.1, 130.2, 129.8, 129.1,
517 (100), 369 (83), 323 (22), 212 (26). HRMS (EI): calcd. for
128.8,128.6,128.4,128.4,127.9,127.8,127.8,127.5,127.1,127.0,122.5,
C
33
H
45
F
3
N
2
O
4
590.3331; found 590.3333.
70.2, 61.8, 61.6, 54.5, 50.1, 33.1, 26.0, 25.7, 25.6, 25.5, 24.8, 20.6, 14.3,
þ
14.1, 13.9. LRMS (EI): m/z ¼ 570 (M , <1%), 370 (17), 369 (89), 301
4
1
.5.14. Ethyl (1SR,3RS,3aSR,6aRS)-1-[(7Z,10Z)-hexadeca-7,10-dien-
-yl]-5-methyl-4,6-dioxo-3-(thiazol-2-yl)octahydropyrrolo[3,4-c]
(100), 211 (14), 144 (11). HRMS (EI): calcd. for C36
570.3458; found 570.3435.
46 2 4
H N O
pyrrole-1-carboxylate 6be
f
Yellow oil, (190 mg, 72% yield). R 0.13 (hexane/ethyl acetate: 7/
3
3
1
1
). IR (neat) ʋmax: 1287, 1436, 1705, 1736, 2254, 2855, 2927, 3007,
4.5.18. Ethyl (1SR,3RS,3aSR,6aRS)-5-(4-fluorobenzyl)-1-
[(2Z,5Z,8Z,11Z,14Z,17Z)-icosa-2,5,8,11,14,17-hexaen-1-yl]-4,6-dioxo-
3-phenyloctahydropyrrolo[3,4-c]pyrrole-1-carboxylate 6 db
ꢁ
1 1
314, 3464 cm . H NMR (300 MHz, CDCl
3
)
d
: 7.81 (d, J ¼ 3.2 Hz,
H), 7.35 (d, J ¼ 3.2 Hz, 1H), 5.44e5.29 (m, 4H), 5.05 (d, J ¼ 9.0 Hz,
H), 4.36 (dq, J ¼ 7.1, 3.8 Hz, 2H), 3.69 (t, J ¼ 8.3 Hz, 1H), 3.32 (d,
f
Yellow oil, (220 mg, 66% yield). R 0.54 (hexane/ethyl acetate: 7/
J ¼ 7.5 Hz, 1H), 2.84 (s, 3H), 2.77 (t, J ¼ 6.0 Hz, 1H), 2.04 (q, J ¼ 6.9,
3). IR (neat) ʋmax: 1224, 1396, 1510, 1707, 2932, 2964, 3012, 3345,
ꢁ1 1
5
5
.0 Hz, 4H), 1.86e1.57 (m, 1H), 1.48e1.16 (m, 19H), 0.90 (td, J ¼ 6.9,
3467 cm . H NMR (300 MHz, CDCl ) d: 7.34e7.07 (m, 7H), 6.99 (t,
3
.9, 3.3 Hz, 3H). 13C NMR (75 MHz, CDCl
)
d: 175.2, 174.4, 170.8,
J ¼ 8.7 Hz, 2H), 5.52e5.22 (m, 12H), 4.63 (d, J ¼ 9.2 Hz, 1H), 4.44 (d,
J ¼ 7.1 Hz, 2H), 4.39e4.32 (m, 2H), 3.47 (dt, J ¼ 8.7, 6.2 Hz, 1H), 3.31
(d, J ¼ 7.6 Hz, 1H), 3.10e2.63 (m, 10H), 2.64 (dd, J ¼ 14.5, 7.8 Hz, 1H),
2.17e1.97 (m, 3H) 2.20e1.92 (m, 3H), 1.39 (t, J ¼ 7.2 Hz, 3H), 0.99 (t,
3
167.4, 142.8, 130.2, 129.9, 128.1, 127.8, 119.6, 71.1, 61.7, 59.4, 55.7,
5
0.3, 35.6, 31.5, 29.5, 29.4, 29.3, 29.0, 27.2, 27.1, 25.6, 25.0, 23.7, 22.6,
þ
1
2
4.1. LRMS (EI): m/z ¼ 529 (M , <1%), 558 (48), 556 (100), 308 (47),
1
3
62 [15], 86 (26). HRMS (EI): calcd. for C29
H
43
N
3
O
4
S 529.2974;
J ¼ 7.5 Hz, 3H). C NMR (75 MHz, CDCl
3
) d: 175.1, 174.2, 171.1, 162.44
1
4
found 529.2979.
(d, JC-F ¼ 246.5 Hz, CF), 136.8, 132.8, 132.1, 131.5 (d,
J
C-F ¼ 3.3 Hz,
3
CCHCHCF), 131.0 (d,
J
C-F ¼ 8.2 Hz, CHCHCF), 129.7, 129.0, 128.8,
4.5.15. Methyl (1SR,3RS,3aSR,6aRS)-5-methyl-1-[(3Z,6Z,9Z,12Z)-
128.6,128.4,128.4,128.3,128.2,127.9,127.8,127.8,127.5,127.1,127.0,
2
octadeca-3,6,9,12-tetraen-1-yl]-4,6-dioxo-3-
phenyloctahydropyrrolo[3,4-c]pyrrole-1-carboxylate 6ca
122.5,115.3 (d, JC-F ¼ 21.4 Hz, CHCF), 70.4, 61.8, 61.7, 54.6, 49.8, 41.7,
19
33.0, 26.0, 25.7, 25.6, 25.5, 20.5, 14.3, 14.1. F NMR
d: ꢁ114.2. LRMS
þ
Yellow oil, (160 mg, 60% yield). R
f
0.28 (hexane/ethyl acetate: 8/
(EI): m/z ¼ 664 (M , <1%), 396 (24), 395 (100), 144 (15), 109 (41), 91
2
2
5
). IR (neat) ʋmax: 1098, 1288, 1436, 1484, 1642, 1703, 1736,
[15], 79 [13]. HRMS (EI): calcd. for C42
664.3666.
2 4
H49FN O 664.3676; found
ꢁ
1
1
959 cm
.
3
H NMR (300 MHz, CDCl ) d: 7.38e7.30 (m, 5H),
.43e5.34 (m, 8H), 4.67 (d, J ¼ 9.1 Hz, 1H), 3.91 (s, 3H), 3.52 (dd,
J ¼ 9.2, 7.4 Hz, 1H), 3.27 (d, J ¼ 7.4 Hz, 1H), 2.82e2.77 (m, 9H),
.19e2.16 (m,1H), 2.11e1.99 (m, 3H), 2.08e1.25 (m,10H), 0.92e0.88
m, 3H). 13C NMR (75 MHz, CDCl
: 175.8, 174.8, 172.1, 130.6, 129.3,
28.8, 128.6, 128.6, 128.5, 128.2, 127.9, 127.8, 127.6, 127.0, 70.8, 61.9,
2
(
1
5
4.5.19. Ethyl (1SR,3RS,3aSR,6aRS)-1-[(2Z,5Z,8Z,11Z,14Z,17Z)-icosa-
2,5,8,11,14,17-hexaen-1-yl]-5-methyl-4,6-dioxo-3-(thiazol-2-yl)
octahydropyrrolo[3,4-c]pyrrole-1-carboxylate 6dc
3
) d
5.8, 52.6, 50.6, 35.0, 31.6, 29.4, 27.3, 25.7, 25.6, 24.9, 22.7, 22.0, 14.2.
f
Yellow oil, (200 mg, 69% yield). R 0.17 (hexane/ethyl acetate: 7/
þ
LRMS (EI): m/z ¼ 532 (M , <1%), 473 (35), 341 (28), 327 (22), 287
3). IR (neat) ʋmax: 1098, 1288, 1381, 1435, 1705, 2934, 2967,
ꢁ
1 1
(
100), 254 (26), 241 (21), 193 (23), 130 (29), 91 (21). HRMS (EI):
3401 cm . H NMR (300 MHz, CDCl
(d, J ¼ 3.2 Hz, 1H), 5.59e5.19 (m, 12H), 5.02 (d, J ¼ 9.1 Hz, 1H), 4.31
qd, J ¼ 7.2, 1.2 Hz, 2H), 3.76e3.57 (m, 1H), 3.35 (d, J ¼ 7.5 Hz, 1H),
3.30 (dd, J ¼ 7.6, 3.0 Hz, 1H), 3.02e2.59 (m, 13H), 2.52 (dd, J ¼ 14.4,
3
)
d
7.76 (d, J ¼ 3.2 Hz, 1H), 7.31
calcd. for C33 532.3301; found 532.3289.
44 2 4
H N O
(
4.5.16. Methyl (1SR,3RS,3aSR,6aRS)-5-methyl-1-[(3Z,6Z,9Z,12Z)-
13
octadeca-3,6,9,12-tetraen-1-yl]-4,6-dioxo-3-(4-(trifluoromethyl)
phenyl)octahydropyrrolo[3,4-c]pyrrole-1-carboxylate 6 cb
7.5 Hz, 1H), 1.36 (t, J ¼ 7.2 Hz, 3H), 0.96 (t, J ¼ 7.5 Hz, 3H). C NMR
(75 MHz, CDCl : 175.1, 174.3, 170.5, 167.8, 143.0, 133.0, 132.1,
3
) d
Yellow oil, (168 mg, 56% yield). R
f
0.45 (hexane/ethyl acetate: 8/
128.9, 128.7, 128.5, 128.4, 128.1, 128.0, 127.9, 127.5, 127.1, 122.5, 119.7,
70.9, 62.0, 59.6, 54.9, 50.2, 33.7, 26.1, 25.8, 25.7, 25.6, 25.2, 20.7, 14.4,
2
3
2
). IR (neat) ʋmax: 1128, 1436, 1620, 1701, 1779, 2858, 2929, 3012,
ꢁ
1
1
þ
349, 3460 cm
.
H NMR (300 MHz, CDCl
3
)
d
7.61 (d, J ¼ 8.0 Hz,
14.2. LRMS (EI): m/z ¼ 577 (M , <1%), 308 (100), 262 (6), 177 (7), 91
H), 7.47 (d, J ¼ 8.0 Hz, 2H), 5.57e5.19 (m, 8H), 4.69 (d, J ¼ 8.6 Hz,
43 3 4
(5). HRMS (EI): calcd. for C33H N O S 577.2974; found 577.2963.