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T. V. Kumar et al. / Tetrahedron Letters 54 (2013) 1397–1400
1.48 (m, 2H), 1.44–1.21 (m, 4H), 0.91 (t, J = 6.7 Hz, 3H); 13C NMR (CDCl3,
81.5, 73.6, 72.9, 72.6, 71.9, 70.5, 55.2, 37.7, 26.7, 22.7, 17.38, 14.07, 12.6; MS
(ESI): m/z = 577.5 [M+Na]+; HRMS (ESI): calcd for C33H50O5NaSi (M+Na)+
577.33044; found 577.33197.
75 MHz): d = 141.2, 114.3, 73.2, 36.6, 27.4, 22.4, 13.8; MS (EI): m/z = 96
[MꢀH2O]+.
(S)-2-(4-Methoxybenzyloxy)-1-((4R,40R,5R)-2,2,20,20-tetramethyl-4,40-bi(1,3-
(2S,3S)-2-(Benzyloxy)-3-((S)-hept-1-en-3-yloxy)diisopropylsilyloxy)pent-4-en-1-
dioxolan)-5-yl)ethanol (18): ½a D20
ꢁ
= +12.5 (c 1.6, CHCl3); IR (KBr): mmax 3484,
ol (22): ½a 2D0
ꢁ
= ꢀ43 (c 1, CHCl3); IR (KBr): mmax 3465, 2925, 2866, 1498, 1463,
2986, 2924, 1612, 1513, 1459, 1248, 1071, 513 cmꢀ1
;
1H NMR (CDCl3,
1347, 1301, 1247, 1092, 917, 878, 694 cmꢀ1 1H NMR (CDCl3, 400 MHz):
;
300 MHz): d = 7.28–7.22 (m, 2H), 6.89–6.83 (m, 2H), 4.50 (q, J = 18.8 Hz, 2H),
4.14–4.08 (m, 2H), 4.03–3.88 (m, 5H), 3.8 (s, 3H), 3.53 (d, J = 6.04 Hz, 2H) 1.39
(s, 3H), 1.38 (s, 3H), 1.36 (s, 3H), 1.32 (s, 3H); 13C NMR (CDCl3, 75 MHz):
d = 159, 129.3, 113.7, 109.7, 109.5, 80.2, 77.4, 76.9, 76.5, 72.9, 71.7, 69.02, 67.7,
55.2, 27.1, 26.8, 26.5, 25.2. MS (ESI): m/z = 405.4 [M+Na]+; HRMS (ESI): calcd
for C20H30O7Na (M+Na)+ 405.18840; found 405.18837.
d = 7.42–7.26 (m, 5H), 6.02–5.95 (m, 1H), 5.83–5.76 (m, 1H), 5.28 (dd, J = 17.8,
9.8 Hz, 2H), 5.09 (dd, J = 17.8, 9.8 Hz, 2H), 4.74–4.62 (m, 3H)), 4.32–4.27 (m,
1H), 3.86–3.75 (m, 1H), 3.68–3.60 (m, 2H), 1.67–1.47 (m, 2H), 1.39–1.23 (m,
4H), 1.14–0.94 (m, 14H), 0.90 (t, J = 6.9 Hz, 3H); 13C NMR (CDCl3, 75 MHz):
d = 141.1, 138.3, 136.7, 128.4, 127.7, 115.8, 114.1, 81.6, 74.0, 72.6, 72.4, 61.4,
37.8, 26.8, 22.7, 17.3, 14.07, 12.7; MS (ESI): m/z = 457.5 [M+Na]+; HRMS (ESI):
calcd for C25H42NaO4Si (M+Na)+ 457.27546; found 457. 27524.
(4R,40R,5R)-5-(S)-1-((Benzyloxy)-2-(4-methoxybenzyloxy)ethyl)-2,2,20,20-
tetramethyl-4,40-bi(1,3-dioxolane) (19): ½a 2D0
ꢁ
= +13.2 (c 2.6, CHCl3); IR (KBr):
mmax 3064, 2987, 2925, 1613, 1515, 1455, 1371, 1249, 1075, 848, 698,
(S)-2-(Benzyloxy)-2-((4S,7S)-7-butyl-2,2-diisopropyl-4,7-dihydro-1,3,2-
dioxasilepin-4-yl)ethanol (23): ½a D20
ꢁ
= ꢀ73 (c 0.9, CHCl3); IR (KBr): mmax 3443,
513 cmꢀ1
;
1H NMR (CDCl3, 400 MHz): d = 7.33–7.28 (m, 4H), 7.24 (t,
3030, 2934, 2866, 1495, 1462, 1357, 1249, 1208, 1097, 885, 736, 697 cmꢀ1 1H
;
J = 7.99 Hz, 3H), 6.84 (d, J = 8.9 Hz, 2H), 4.81 (d, J = 11.9 Hz, 1H), 4.60 (d,
J = 10.9 Hz, 1H), 4.47 (q, J = 14.9 Hz, 2H), 4.11–4.07 (m, 1H), 4.04–3.98 (m, 3H),
3.87–3.84 (m, 1H), 3.8 (s, 3H), 3.78–3.74 (m, 1H), 3.69 (dd, J = 3.9, 2.0 Hz, 2H),
1.38 (s, 3H), 1.35 (s, 3H), 1.34 (s, 3H), 1.32 (s, 3H); 13C NMR (CDCl3, 75 MHz):
d = 159.1, 138.6, 130.3, 129.2, 128.2, 127.5, 127.4, 113.7, 109.5, 80.6, 77.4, 77.0,
76.5, 73.3, 73.08, 71.2, 67.6, 55.2, 27.2, 26.7, 26.5, 24.2; MS (ESI): m/z = 495.4
[M+Na]+; HRMS (ESI): calcd for C27H36O7Na (M+Na)+ 495.23458; found 495.
23532.
NMR (CDCl3, 400 MHz): d = 7.34–7.25 (m, 5H), 5.68 (dt, J = 11.6, 2.8 Hz, 1H),
5.58 (dt, J = 11.6, 2.8 Hz, 1H), 4.92–4.89 (m, 1H), 4.72–4.62 (m, 3H), 3.85–3.78
(m, 1H), 3.68–3.61 (m, 2H), 1.60–1.40 (m, 2H), 1.39–1.24 (m, 4H), 1.10–0.98
(m, 14H), 0.92 (t, J = 6.7 Hz, 3H); 13C NMR (CDCl3, 75 MHz): d = 138.3, 136.9,
129.6, 128.4, 127.7, 81.4, 72.83, 71.6, 62.0, 38.4, 28.0, 22.5, 17.4, 17.2, 17.19,
17.10, 14.1, 12.7; MS (ESI): m/z = 429.5 [M+Na]+; HRMS (ESI): calcd for
C
23H38NaO4Si (M+Na)+ 429.24316; found 429. 24316.
(S,Z)-Methyl 4-(benzyloxy)-4-((4S,7S)-7-butyl-2,2-diisopropyl-4,7-dihydro-1,3,2-
(4R,5R)-5-(S)-1-(Benzyloxy)-2-(4-methoxybenzyloxy)ethyl)-2,2-dimethyl-1,3-
ioxasilepin-4-yl)but-2-enoate (10): ½a D20
ꢁ
= ꢀ27.5 (c 0.5, CHCl3); IR (KBr): mmax
dioxolan-4-yl)methanol (20): ½a D20
ꢁ
= ꢀ23.3 (c 1.2, CHCl3); IR (KBr): mmax 3463,
2926, 2863, 1726, 1652, 1463, 1437, 1219, 1196, 1094, 885, 696 cmꢀ1 1H NMR
;
3063, 2985, 2925, 1612, 1514, 1457, 1373, 1240, 1080, 851, 742, 699 cmꢀ1
;
1H
(CDCl3, 400 MHz): d = 7.35–7.24 (m, 5H), 6.26 (dd, J = 11.2, 9.5 Hz, 1H), 6.0 (d,
J = 12.1 Hz, 1H), 5.78 (dd, J = 12.1, 2.5 Hz, 1H), 5.72 (dd, J = 12.1, 2.5 Hz, 1H),
5.18 (dd, J = 8.6, 4.3 Hz, 1H)), 4.85–4.82 (m, 1H), 4.64–4.51 (m, 3H), 3.7 (s, 3H),
1.67–1.47 (m, 2H), 1.39–1.23 (m, 4H), 1.14–0.94 (m, 14H), 0.90 (t, J = 6.9 Hz,
3H); 13C NMR (CDCl3, 75 MHz): d = 166.2, 146.9, 138.5, 136.8, 130.7, 128.1,
127.6, 127.4, 122.5, 76.8, 73.0, 71.5, 71.1, 51.3, 38.3, 27.9, 22.5, 17.3, 17.2, 17.1,
17.0, 14.0, 12.9, 12.8; MS (ESI): m/z = 483.3 [M+Na]+; HRMS (ESI): calcd for
NMR (CDCl3, 400 MHz): d = 7.41–7.33 (m, 5H), 7.30 (d, J = 8.7 Hz, 2H), 6.93 (d,
J = 8.7 Hz, 2H), 4.86 (d, J = 12.05 Hz, 1H), 4.71 (d, J = 10.9 Hz, 1H), 4.54 (q,
J = 13.1 Hz, 2H)), 4.11–4.04 (m, 2H), 3.88 (s, 3H), 3.79–3.68 (m, 4H), 3.66–3.57
(m, 1H), 1.45 (s, 6H); 13C NMR (CDCl3, 75 MHz): d = 159.2, 138.0, 130.0, 129.2,
128.3, 128.0, 127.6, 113.7, 108.9, 77.9, 77.1, 76.4, 73.1, 73.0, 70.1, 62.3, 55.2,
27.0, 26.8; MS (ESI): m/z = 425.4 [M+Na]+; HRMS (ESI): calcd for C23H30O6Na
(M+Na)+ 425.19211; found 425.19346.
C
26H40NaO5Si (M+Na)+ 483.25296; found 483. 25372.
(4R,5S)-4-(S)-1-(Benzyloxy)-2-(4-methoxybenzyloxy)ethyl)-5-(iodomethyl)-2,2-
(5S,6S)-5-(Benzyloxy)-6-((S,Z)-3-hydroxyhept-1-enyl)-5,6-dihydro-2H-pyran-2-
dimethyl-1,3-dioxolane (21): ½a D20
ꢁ
= ꢀ3.08 (c 1.2, CHCl3); IR (KBr): mmax 3014,
one (24): ½a 2D0
ꢁ
= +117 (c 0.5, CHCl3); IR (KBr): mmax 2923, 2853, 1725, 1463,
2987, 2962, 1615, 1514, 1457, 1378, 1240, 1080, 851, 712 cmꢀ1
;
1H NMR
1459, 1219, 1052, 772 cmꢀ1 1H NMR (CDCl3, 400 MHz): d = 7.36–7.28 (m, 5H),
;
(CDCl3, 400 MHz): d = 7.36–7.23 (m, 7H), 6.91–6.85 (m, 2H), 4.79 (d,
J = 11.8 Hz, 1H), 4.64 (d, J = 11.8 Hz, 1H), 4.48 (s, 2H), 3.97–3.87 (m, 2H), 3.81
(s, 3H) 3.74–3.66 (m, 3H), 3.25–3.19 (m, 1H), 3.15–3.09 (m, 1H), 1.44 (s, 3H),
1.39 (s, 3H); 13C NMR (CDCl3, 75 MHz): d = 159.1, 138, 129.9, 129.3, 128.3, 128,
127.7, 113.7, 109.3, 81.3, 76.0, 75.5, 73.1, 72.8, 69.9, 55.2, 27.4, 27, 6.8; MS
(ESI): m/z = 535.1 [M+Na]+; HRMS (ESI): calcd for C23H29O5INa (M+Na)+
535.09424; found 535.09424.
6.86 (dd, J = 9.9, 4.7 Hz, 1H), 6.1 (d, J = 9.9 Hz, 1H), 5.88 (dd, J = 11.2, 8.6 Hz, 1H),
5.78 (dd, J = 11.25, 8.6 Hz, 1H), 5.35 (dd, J = 8.2, 3.8 Hz, 1H)), 4.62 (q, J = 16.6 Hz,
2H), 4.42 (q, J = 13.4 Hz, 1H), 4.06 (t, J = 4.3 Hz, 1H), 1.39–1.24 (m, 6H), 0.90 (t,
J = 6.9 Hz, 3H); 13C NMR (CDCl3, 75 MHz): d = 162.6, 143.2, 138.9, 137.0, 128.6,
128.2, 127.8, 124.0, 123.2, 122.5, 75.8, 71.8, 68.8, 68.2, 36.7, 27.4, 22.6, 13.9;
MS (ESI): m/z = 339.2 [M+Na]+; HRMS (ESI): calcd for C19H24NaO4 (M+Na)+
339.15677; found 339.15668.
(3S,4S)-4-(Benzyloxy)-5-(4-methoxybenzyloxy)pent-1-en-3-ol (13): ½a D20
ꢁ
= ꢀ10.5
(S,Z)-1-((2S,3S)-3-(Benzyloxy)-6-oxo-3,6-dihydro-2H-pyran-2-yl)hept-1-en-3-yl
(c 1, CHCl3); IR (KBr): mmax 3459, 3063, 2922, 2855, 1612, 1513, 1455, 1248,
acetate (25): ½a D20
ꢁ
= +107 (c 0.5, CHCl3); IR (KBr): mmax 2924, 2853, 1725, 1463,
1219, 1089, 771, 699 cmꢀ1
;
1H NMR (CDCl3, 400 MHz): d = 7.38–7.28 (m, 5H),
1459, 1317, 1239, 1054, 772 cmꢀ1 1H NMR (CDCl3, 400 MHz): d = 7.37–7.25
;
7.25 (td, J = 9.06, 3.02, 2.26 Hz, 2H), 6.88 (td, J = 9.06, 3.02, 2.26 Hz, 2H), 5.95–
5.83 (m, 1H), 5.36 (td, J = 17.37, 1.51 Hz, 1H), 5.21 (td, J = 10.57, 1.5 Hz, 1H)),
4.74 (d, J = 11.33 Hz, 1H), 4.59 (d, J = 11.33 Hz, 1H), 4.45 (q, J = 15.1 Hz, 2H),
4.27–4.21 (m, 1H), 3.81 (s, 3H), 3.69–3.62 (m, 1H), 3.59–3.53 (m, 2H); 13C NMR
(CDCl3, 75 MHz): d = 159.1, 138.06, 137.2, 129.9, 129.2, 128.3, 127.8, 127.7,
116.5, 113.7, 80.2, 73.1, 72.9, 72.5, 69.4, 55.1; MS (ESI): m/z = 351.3 [M+Na]+;
HRMS (ESI): calcd for C20H24O4Na (M+Na)+ 351.15703; found 351.15668.
(4S,5S,9S)-4-(Benzyloxy)-7,7-diisopropyl-1-(4-methoxyphenyl)-5,9-divinyl-2,6,8-
(m, 5H), 6.86 (dd, J = 9.8, 4.9 Hz, 1H), 6.15 (d, J = 9.8 Hz, 1H), 5.93 (dd, J = 10.8,
8.8 Hz, 1H), 5.66 (dd, J = 10.8, 9.8 Hz, 1H), 5.43–5.36 (m, 2H)), 4.59 (q,
J = 1.8 Hz, 2H), 3.97–3.94 (m, 1H), 2.02 (s, 3H), 1.69–1.38 (m, 6H), 0.90 (t,
J = 6.8 Hz, 3H); 13C NMR (CDCl3, 75 MHz): d = 170.2, 162.4, 142.5, 137.0, 132.5,
128.5, 128.2, 127.7, 127.3, 123.6, 122.5, 76.1, 71.6, 69.2, 69.1, 34.2, 29.6, 22.4,
21.1, 13.8; MS (ESI): m/z = 381.1 [M+Na]+; HRMS (ESI): calcd for C21H26NaO5
(M+Na)+ 381.16682; found 381.16720.
(S,Z)-1-((2S,3S)-3-Hydroxy-6-oxo-3,6-dihydro-2H-pyran-2-yl)hept-1-en-3-yl
trioxa-7-silatridecane (11): ½a D20
ꢁ
= ꢀ62 (c 2, CHCl3); IR (KBr): mmax 2927, 2865,
acetate (3): ½a 2D0
ꢁ
= +72 (c 0.5, MeOH); IR (KBr): mmax 3410, 2924, 2853, 1730,
1613, 1513, 1463, 1363, 1301, 1248, 1095, 1036, 921, 821, 696 cmꢀ1
;
1H NMR
1462, 1374, 1245, 1239, 1087, 1042, 962, 825, 771 cmꢀ1 1H NMR (CDCl3,
;
(CDCl3, 400 MHz): d = 7.39–7.22 (m, 7H), 6.86 (d, J = 8.49 Hz, 2H), 5.94 (ddd,
J = 6.42, 5.47, 5.09 Hz, 1H), 5.76 (ddd, J = 6.6, 6.42, 3.9 Hz, 1H), 5.29 (td,
J = 17.37, 1.70 Hz, 1H), 5.16–4.97 (m, 3H), 4.79 (d, J = 11.8 Hz, 2H), 4.68 (d,
J = 11.8 Hz, 2H), 4.57–4.51 (m, 1H), 4.45 (q, J = 14.1 Hz, 2H), 4.25 (q, J = 12.0 Hz,
2H), 3.8 (s, 3H), 3.76–3.70 (m, 1H), 3.51–3.44 (m, 1H), 1.59–1.51 (m, 3H), 1.32–
1.21 (m, 3H), 0.92–1.06 (m, 14H), 0.87 (t, J = 6.79 Hz, 3H); 13C NMR (CDCl3,
75 MHz): d = 159, 141.2, 139, 136.7, 130.7, 127.6, 127.3, 115.1, 113.9, 113.5,
400 MHz): 7.06 (dd, J = 9.9, 5.9 Hz, 1H), 6.14 (d, J = 9.9 Hz, 1H), 5.75–5.66 (m,
2H), 5.51 (dd, J = 7.9, 5.9 Hz, 1H), 5.29 (d, J = 5.9 Hz, 1H)), 4.18–4.12 (m, 1H),
2.04 (s, 3H), 1.74–1.32 (m, 6H), 0.90 (t, J = 6.9 Hz, 3H); 13C NMR (CDCl3,
75 MHz): d = 171.0, 162.5, 144.0, 134.3, 125.3, 122.9, 77.9, 71.0, 63.1, 34.2,
27.2, 22.4, 21.9, 13.9; MS (ESI): m/z = 291.1 [M+Na]+; HRMS (ESI): calcd for
C
21H26NaO5 (M+Na)+ 291.12030; found 291.12029.