Paper
Organic & Biomolecular Chemistry
1
27.4, 127.6 (o-C), 129.5, 129.7 (p-C), 131.1 (C-7), 132.4 (C-8), tion of 8b (38.0 mg, 0.11 mmol) in CH
2 2 3
Cl (1 mL) NEt
1
33.9, 134.7 (i-C), 135.9, 136.0 (m-C), 147.9 (C-3), 166.6 (COEt). (0.03 mL, 0.20 mmol) was added and the mixture stirred for
1
Diastereomer 2: R
f
= 0.45 (hexanes/EtOAc, 3 : 1). H NMR 15 min. Then a solution 13a (50 mg, 0.10 mmol) in CH
) δ 0.68 (d, J = 6.9 Hz, 3H, 4-CH ), 0.98 (d, J = (1 mL) was added and the reaction mixture heated at reflux for
.1 Hz, 3H, 1′-CH ), 1.04 [s, 9H, C(CH ) ], 1.30 (t, J = 7.2 Hz, 23 h. The solvent was removed under reduced pressure and
2 2
Cl
(500 MHz, CDCl
3
3
6
3
1
1
3
3 3
H, CH
.5 Hz, 1H, H
H, H-4), 3.79 (dq, J = 7.6, 6.1 Hz, 1H, H-1′), 4.06–4.10 (m, 2H, a colorless liquid (dr 60 : 33 : 7 : 0 by H NMR). R = 0.24. FT-IR
2
CH
3
), 1.58 (br, 1H, OH), 1.93 (dddd, J = 14.5, 7.4, 7.4, the residue was purified by chromatography on SiO
2
with
a
-3), 2.03–2.12 (m, 2H, H -3, H-5), 2.16–2.26 (m, hexanes/EtOAc (10 : 1) to give 12a (20 mg, 0.04 mmol, 38%) as
b
1
f
2 3
CH
), 5.35 (ddt, J = 15.4, 10.2, (ATR) ( ˜ν cm− ) 3071 (w), 2960 (m), 2930 (m), 2893 (w),
1
H-8), 4.20 (q, J = 7.2 Hz, 2H, CH
.4 Hz, 1H, H-6), 5.61 (dt, J = 15.4, 5.7 Hz, 1H, H-7), 5.77 (dt, 2857 (w), 1717 (s), 1870 (w), 1668 (s), 1630 (w), 1593 (m), 1473
J = 15.5, 1.5 Hz, 1H, H-1), 6.91 (dt, J = 15.5, 7.4 Hz, 1H, H-2), (w), 1427 (m), 1364 (m), 1312 (w), 1251 (s), 1222 (w), 1176 (w),
1
13
7
.34–7.46 (m, 6H, o-H, p-H), 7.65–7.72 (m, 4H, m-H). C NMR 1107 (vs), 1043 (w), 999 (s), 980 (w), 938 (w), 909 (w), 822 (m),
1
3 2 3 3
(125 MHz, CDCl ) δ 14.3 (CH CH ), 15.1 (4-CH ), 19.4 770 (w), 735 (s), 702 (vs), 686 (w), 646 (w), 608 (m). H NMR
[
C(CH ) ], 22.1 (1′-CH ), 27.1 [C(CH ) ], 31.6 (C-4), 38.4 (C-3), (500 MHz, CDCl ) δ 0.70 (d, J = 6.8 Hz, 3H, 4-CH ), 0.77 (d, J =
3
3
3
3 3
3
3
5
1
1
4.9 (C-5), 60.2 (CH
2
CH
3
), 63.6 (C-8), 69.8 (C-1′), 122.4 (C-1), 6.9 Hz, 3H, 4-CH
3
*), 0.99 (d, J = 6.1 Hz, 3H, 1′-CH
*), 1.03–1.06 (m, 18H, C(CH
3
), 1.02 (d, J =
, C(CH *),
27.4, 127.6 (o-C), 129.4 (p-C), 129.7 (C-6), 132.8 (C-7), 133.8, 6.5 Hz, 3H, 1′-CH
34.7 (i-C), 135.95, 136.00 (m-C), 148.3 (C-2), 166.7 (COEt).
3
3
)
3
3 3
)
1.30 (t, J = 7.1 Hz, 3H, CH CH ), 1.31 (t, J = 7.1 Hz, 3H,
2
3
Ethyl (2E,6R,7E)-6-(1-{[tert-butyl(diphenyl)silyl]oxy}ethyl)-5- CH
2
CH
3
*), 1.80–2.00 (m, 4H, H
a
a
-3, H *-3, H*-4, H-5), 2.00–2.10
methyl-9-oxonona-2,7-dienoate (13a). To a solution of 32 (m, 1H, H
b
-3), 2.11–2.24 (m, 3H, H
b
*-3, H-4, H*-5), 2.26 (s, 3H,
(
(
443 mg, 0.90 mmol) in dry CH Cl (10 mL) at 0 °C DMP H-11), 2.28–2.32 (m, 3H, H*-11), 3.83–3.90 (m, 1H, H-1′),
2
2
496 mg, 1.17 mmol) was added and the reaction mixture 3.96–4.02 (m, 1H, H*-1′), 4.19 (q, J = 7.1 Hz, CH
CH *), 5.66 (dt, J = 15.8, 1.5 Hz, H*-1), 5.76 (dt,
pressure. The crude product was purified by chromatography J = 15.6, 1.4 Hz, 1H, H-1), 5.89 (dd, J = 15.5, 9.9 Hz, 1H, H-6),
2 3
CH ), 4.20 (q,
stirred for 3 h. The solution was concentrated under reduced J = 7.1 Hz, CH
2
3
on SiO
CH Cl
2
with hexanes/EtOAc (10 : 1) and a small quantity of 6.05–6.12 (m, 4H, H-6, H*-7, H-9, H*-9), 6.15 (dd, J = 15.3,
2
2
to dissolve the remaining DMP to give 13a (356 mg, 10.8 Hz, 1H, H-7), 6.79 (ddd, J = 15.1, 8.4, 6.6 Hz, 1H, H*-2),
1
0
.72 mmol, 80%) as colorless oil (dr 56 : 39 : 5 : 0 by H NMR, 6.87 (dt, J = 15.6, 7.4 Hz, 1H, H-2), 7.05 (dd, J = 15.6, 10.8 Hz,
2
0
CHO). R
f
= 0.33 (hexanes/EtOAc, 10 : 1). [α]
D
−190 (c 1.0 in 1H, H-8), 7.08–7.21 (m, 1H, H*-8), 7.33–7.47 (m, 12H, o-H,
−
1
13
3 3
CHCl ). FT-IR (ATR) ( ˜ν cm ) 2962 (w), 2931 (w), 2857 (w), 2253 p-H), 7.60–7.73 (m, 8H, m-H). C NMR (125 MHz, CDCl )
(
w), 1716 (m), 1689 (m), 1653 (w), 1473 (w), 1427 (w), 1390 (w), δ 14.4 (CH CH , CH CH *), 15.6 (4-CH ), 17.5 (4-CH *), 19.4,
2
3
2
3
3
3
1
367 (w), 1314 (w), 1265 (w), 1225 (w), 1178 (w), 1110 (m), 1043 19.5 [C(CH ], 22.0 (1′-CH
3
)
3
3 3
), 22.6 (1′-CH *), 27.2, 27.5, 27.49,
(
w), 979 (m), 906 (s), 821 (w), 729 (vs), 702 (vs), 648 (m), 610 27.52 [C(CH ) ], 32.2 (C-4), 32.6 (C-4*), 37.7 (C-3), 38.4 (C-3*),
3 3
1
(m). H NMR (500 MHz, CDCl ) δ 0.74 (d, J = 6.9 Hz, 3H, 56.0 (C-5), 56.2 (C-5*), 60.4 (CH CH , CH CH *), 69.7 (C-11,
3
2
3
2
3
4
-CH
3
3
), 0.79 (d, J = 6.3 Hz, 3H, 4-CH *), 1.00–1.06 [m, 24H, C-11*), 122.9 (C-1*), 123.0 (C-1), 127.5, 127.6, 127.80, 127.83
3 3 3 3 3 3
C(CH ) , C(CH ) *, 1′-CH , 1′-CH *], 1.30 (t, J = 7.1 Hz, 6H, (o-C), 129.3 (C-9, C-9*), 129.5, 129.7, 129.9, 130.0 (m-C), 131.9,
CH CH , CH CH *), 1.81–1.88 (m, 1H, H *-3), 1.88–1.95 (m, 132.2 (C-7, C-7*), 133.7, 133.8, 134.6, 134.7, 136.06, 136.1,
2
3
2
3
a
1
3
H, H
a
-3), 1.99–2.05 (m, 2H, H*-4, H*-5), 2.05–2.10 (m, 1H, H
b
-
136.13 (p-C), 142.6 (C-6, C-6*), 143.2 (C-8), 143.6 (C-8*), 147.4
Et), 198.8, 199.0 (C-10).
), 2.13–2.19 (m, 1H, H
b
*-3), 2.19–2.27 (m, 1H, H-4), 2.31–2.38 (C-2*), 147.8 (C-2), 166.6, 166.7 (CO
2
+
(m, 1H, H-5), 3.90–3.97 (m, 1H, H*-1′), 4.03–4.09 (m, 1H, H-1′), MS (ESI) m/z 283.15 [M − C H OSi] , 265.14, 231.14, 105.08.
1
8
23
+
4
.15–4.23 (m, 4H, CH
2
CH
3
, CH
2
CH
3
*), 5.67 (d, J = 15.5 Hz, 1H, HRMS (ESI) obsd 555.2890, calc. for C33
Ethyl (2R,3aS,4R,5S,7aR)-5-acetyl-1-(1-{[tert-butyl(diphenyl)-
), 6.57 (dd, J = 15.7, 10.4 Hz, 1H, H-6), 6.72–6.80 (m, 1H, H*- silyl]oxy}ethyl)-2-methyl-2,3,3a,4,5,7a-hexahydro-1H-indene-4-
44 4
H O SiNa : 555.2901.
H*-1), 5.77 (d, J = 15.7 Hz, 1H, H-1), 6.00–6.10 (m, 2H, H-7, H*-
7
6
7
), 6.80–6.88 (m, 2H, H-2, H*-2), 7.33–7.49 (m, 12H, o-H, p-H), carboxylate (11a). To a solution of 12a (80 mg, 0.15 mmol) in
.59–7.72 (m, 8H, m-H), 9.47 (d, J = 7.8 Hz, 1H, CHO), 9.54 (d, toluene (2 mL) BHT (3.31 mg, 0.02 mmol) was added and the
1
3
J = 8.1 Hz, 1H, CHO). C NMR (125 MHz, CDCl ) δ 14.4 reaction mixture heated at reflux for 93 h. The solvent was
3
(
2
3
CH
2
CH
1.7 (1′-CH
2.4 (C-4*), 37.4 (C-3*), 38.1 (C-3), 55.4 (C-5), 55.9 (C-5*), 60.4 11a (25 mg, 0.05 mmol, 33%) as a colorless oil (dr 55 : 42 : 3 : 0
3
), 15.8 (4-CH
3
), 17.3 (4-CH
3
*), 19.45, 19.48 [C(CH
3
)
3
], removed under reduced pressure and the residue was purified
3
), 22.7 (1′-CH
3
*), 27.15, 27.17 [C(CH
3
)
3
], 32.2 (C-4), by chromatography on SiO
2
with hexanes/EtOAC (10 : 1) to give
1
−1
(
CH
2
3 f
CH ), 69.26, 69.30 (C-1′, C-1′*), 123.2 (C-1*), 123.4 (C-1), by H NMR, H-1′). R = 0.39. FT-IR (ATR) ( ˜ν cm ) 3072 (w),
1
27.59, 127.63, 127.90, 127.96 (o-C), 129.81, 129.84, 130.04 2959 (m), 2930 (m), 2856 (m), 2359 (w), 2255 (w), 1729 (s), 1713
(
m-C), 133.3, 133.5, 134.3, 134.4 (p-C), 136.06, 136.08 (C-7, (s), 1589 (w), 1473 (m), 1461 (m), 1427 (m), 1392 (w), 1375 (m),
C-7*), 146.6 (C-6*), 145.0 (C-2, C-2*), 156.1 (C-6), 157.8 (COO*), 1354 (m), 1308 (w), 1277 (br), 1206 (m), 1178 (m), 1155 (m),
66.5 (COO), 193.5, 193.8 (CHO, CHO*). MS (ESI) m/z 515.26 1109 (s), 1054 (w), 1030 (w), 1007 (w), 975 (w), 939 (w), 908 (s),
1
+
+
1
[M + Na] , 284.15 [M − C H OSi + H] , 259.13, 233.11. HRMS 861 (w), 821 (m), 731 (vs), 702 (vs), 648 (w), 609 (m). H NMR
1
8
23
+
(
ESI) obsd 515.2582, calc. for C30
Ethyl (2E,6R,7E,9E)-6-(1-{[tert-butyl(diphenyl)silyl]oxy}- 7.3 Hz, 3H, 2-CH
ethyl)-5-methyl-11-oxododeca-2,7,9-trienoate (12a). To a solu- (m, 20H, C(CH ) , H -3, H *-3), 1.12 (d, J = 6.3 Hz, 3H, 1′-CH ),
H
40
O
4
SiNa : 515.2588.
(500 MHz, CDCl
3
) δ 0.94 (d, J = 7.2 Hz, 3H, 2-CH
3
*), 0.98 (d, J =
), 1.03–1.05
3
), 1.02 (d, J = 6.4 Hz, 3H, 1′-CH
3
3
3
a
a
3
892 | Org. Biomol. Chem., 2016, 14, 884–894
This journal is © The Royal Society of Chemistry 2016