C x1, CH x1), 34.8 (CH), 33.0 (CH2), 29.9 (CH2), 29.5 (CH2),
28.6 (CH3), 27.0 (CH2), 18.2 (CH3), 18.1 (CH2), 12.3 (CH),
CHCl3); IR (film) 2926, 2865, 1750, 1695, 1463, 1440, 1366,
1266, 1252, 1175, 1131, 945, 838, 682 cm-1; 1H NMR (500
MHz, CDCl3, 60 °C) δ 5.40 (t, J = 6.9 Hz, 1H), 5.22‒4.90 (m,
2H), 4.78‒4.46 (m, 1H), 4.25‒4.12 (m, 2H), 4.09‒3.94 (m, 1H),
3.90‒3.79 (m, 1H), 3.77 (s, 3H), 3.74‒3.56 (m, 3H), 3.07 (d, J
= 14.4 Hz, 1H), 2.85 (d, J = 12.3 Hz, 1H), 2.63 (d, J = 12.6 Hz,
1H), 2.63‒2.50 (m, 1H), 2.32 (dd, J = 16.3, 6.3 Hz, 1H), 2.16
(ddd, J = 13.5, 3.4, 3.4 Hz, 1H), 2.02‒1.91 (m, 1H), 1.72‒1.66
(m, 1H), 1.60‒1.35 (m, 14H), 1.12‒1.04 (m, 21H), 1.01 (t, J =
8.3 Hz, 2H), 0.06 (s, 9H); 13C NMR (125 MHz, CDCl3, 1:1
mixture of rotamers) δ 156.8 (C), 156.8 (C), 155.8 (C), 155.8
(C), 155.3 (C), 155.2 (C), 143.6 (C), 142.9 (C), 119.7 (CH),
118.6 (CH), 80.4 (C), 79.8 (C), 64.2 (CH2), 64.1 (CH2), 63.9
(CH2), 63.8 (CH2), 63.8 (CH2), 63.7 (CH2), 54.8 (CH3), 54.7
(CH3), 50.8 (CH2), 50.7 (CH2), 48.8 (CH2), 48.6 (CH2), 47.3
(CH2), 47.1 (CH2), 45.1 (CH), 43.9 (CH), 35.6 (CH), 35.5 (CH),
35.4 (CH), 35.1 (CH2), 35.1 (CH2), 34.9 (C), 34.8 (CH), 34.7
(C), 32.8 (CH2), 32.7 (CH2), 29.8 (CH2), 29.3 (CH2), 28.6
(CH3), 28.5 (CH3), 26.8 (CH2), 26.8 (CH2), 18.1 (CH3), 18.1
(CH3), 17.9 (CH2), 17.9 (CH2), 12.0 (CH), 12.0 (CH), ‒1.3
(CH3), ‒1.3 (CH3); HRMS (ESI), calcd for C37H68N2O8Si2Na+
(M+Na)+ 747.4412, found 747.4404.
+
‒1.3 (CH3); HRMS (ESI), calcd for C35H65N2O5Si2 (M+H)+
649.4432, found 649.4434.
Z-Allylic alcohol ((Z)-47): 2-Methyl-2-butene (1.7 mL, 16
mmol) was added to borane THF complex (0.92 M in THF, 8.0
mL, 7.4 mmol) at 0 °C. The solution was maintained at this
temperature for 1 h to give disiamylborane (calculated as 0.76
M in THF).
Disiamylborane (0.76 M, 6.0 mL, 4.6 mmol) was added to a
solution of allene 8 (1.48 g, 2.28 mmol) and THF (23 mL) at
room temperature. The solution was maintained for 10 min at
room temperature, and quenched with NaOH aq (3 M, 10 mL)
and 30% H2O2 aq (10 mL) at 0 °C. The resulting mixture was
maintained for 1 h at 0 °C, and extracted with EtOAc (2x 30
mL). The combined organic extracts were washed with brine
(30 mL), dried over Na2SO4, and concentrated. The residue was
purified by silica gel column chromatography (EtOAc/hexane
1:4) to give Z-allylic alcohol (Z)-47 (1.34 g, 88%) and E-allylic
alcohol (E)-47 (65.7 mg, 4.3%). (Z)-47: a colorless oil; [α]27
D
+4.3 (c 1.00, CHCl3); IR (film) 3450, 2945, 2866, 1688, 1463,
1
1437, 1415, 1250, 1175, 1132, 1105, 838, 765, 681 cm-1; H
NMR (500 MHz, CDCl3, 60 °C) δ 5.68‒5.38 (m, 1H),
5.18‒4.90 (m, 1H), 4.46‒4.33 (m, 1H), 4.30‒4.12 (m, 2H), 4.01
(d, J = 12.3 Hz, 1H), 3.92‒3.76 (m, 2H), 3.74‒3.63 (m, 2H),
3.58 (d, J = 14.1 Hz, 1H), 3.38 (brs, 1H), 3.10 (d, J = 14.1 Hz,
1H), 2.86 (d, J = 12.3 Hz, 1H), 2.63 (d, J = 13.5 Hz, 1H), 2.51
(dd, J = 13.2, 13.2 Hz, 1H), 2.28 (dd, J = 16.3, 6.9 Hz, 1H),
2.15 (ddd, J = 13.5, 3.5, 3.5 Hz, 1H), 1.99‒1.91 (m, 1H),
1.70‒1.65 (m, 1H), 1.58‒1.35 (m, 14H), 1.12‒1.04 (m, 21H),
1.01 (t, J = 8.3 Hz, 2H), 0.06 (s, 9H); 13C NMR (125 MHz,
CDCl3, 60 °C) δ 156.8 (C), 156.7 (C), 140.4 (C), 125.2 (CH),
80.7 (C), 63.9 (CH2), 63.9 (CH2), 57.1 (CH2), 51.1 (CH2), 49.1
(CH2), 48.1 (CH2), 44.3 (CH), 35.9 (CH), 35.6 (CH), 35.4
(CH2), 35.0 (C), 33.4 (CH2), 29.5 (CH2), 28.7 (CH3), 27.0
(CH2), 18.2 (CH3), 18.1 (CH2), 12.3 (CH), ‒1.3 (CH3); HRMS
(ESI), calcd for C35H66N2O6Si2Na+ (M+Na)+ 689.4357, found
689.4359. (E)-47: a colorless oil; [α]27D +11.1 (c 1.00, CHCl3);
IR (film) 3461, 2944, 2866, 1693, 1463, 1437, 1414, 1366,
1250, 1175, 1132, 1104, 838, 765, 681 cm-1; 1H NMR (500
MHz, CDCl3, 60 °C) δ 5.80‒5.40 (m, 1H), 4.80‒4.35 (m, 1H),
4.26‒4.13 (m, 3H), 4.09 (dd, J = 12.9, 5.7 Hz, 1H), 4.08‒3.96
(m, 1H), 3.84 (d, J = 11.8 Hz, 1H), 3.74‒3.57 (m, 3H),
3.13‒2.95 (m, 1H), 2.87 (d, J = 12.6 Hz, 1H), 2.70‒2.54 (m,
2H), 2.24 (dd, J = 15.5, 12.9 Hz, 1H), 2.13 (ddd, J = 13.5, 3.8,
3.8 Hz, 1H), 1.98‒1.86 (m, 1H), 1.72‒1.65 (m, 1H), 1.60‒1.38
(m, 14H), 1.12‒1.04 (m, 21H), 1.01 (t, J = 8.3 Hz, 2H), 0.06 (s,
9H); 13C NMR (125 MHz, CDCl3, 1:1 mixture of rotamers) δ
156.8 (C), 156.8 (C), 155.7 (C), 155.4 (C), 139.1 (C), 138.5 (C),
126.6 (CH), 125.5 (CH), 79.7 (C), 79.7 (C), 63.9 (CH2), 63.9
(CH2), 63.8 (CH2), 63.7 (CH2), 58.4 (CH2), 58.4 (CH2), 53.0
(CH), 51.8 (CH), 50.9 (CH2), 50.7 (CH2), 49.0 (CH2), 48.8
(CH2), 47.1 (CH2), 47.1 (CH2), 35.8 (CH), 35.8 (CH), 35.1 (C),
35.0 (CH), 34.8 (CH), 34.7 (C), 32.8 (CH2), 32.4 (CH2), 29.5
(CH2), 29.4 (CH2), 28.6 (CH2), 28.6 (CH3), 28.6 (CH3), 28.5
(CH2), 26.8 (CH2), 26.8 (CH2), 18.1 (CH3), 18.1 (CH3), 17.9
(CH2), 17.9 (CH2), 12.0 (CH), 12.0 (CH), ‒1.3 (CH3), ‒1.3
(CH3); HRMS (ESI), calcd for C35H66N2O6Si2Na+ (M+Na)+
689.4357, found 689.4354.
Skipped diene ((Z,Z)-10): A solution of allylic carbonate 50
(667 mg, 920 µmol), vinylstannane 9 (960 mg, 2.30 mmol) and
DMF (9.2 mL) was added to a mixture of LiCl (195 mg, 4.60
mmol) and Pd2(dba)3∙CHCl3 (47.6 mg, 46.0 µmol) at room
temperature. After stirring at room temperature for 1 h, the
mixture was quenched with KF aq (1 M, 5 mL) at 0 °C, stirred
for 1 h at room temperature, and extracted with hexane (3x 10
mL). The combined organic extracts were washed with brine (5
mL), dried over Na2SO4 and concentrated. The residue was
purified by silica gel column chromatography (EtOAc/hexane
1:19 to 1:14) to afford a mixture of skipped dienes (Z,Z)-10 and
(E,Z)-10. Two skipped dienes were then separated by MPLC
(Yamazen Ultra Pack Column B, 26×300 mm, Et2O/hexane 1:4
to 2:3, 20 mL/min, (Z,Z)-10: TR = 32.0 min, (E,Z)-10: TR
=
36.0 min) to afford skipped diene (Z,Z)-10 (611 mg, 85%) and
skipped diene (E,Z)-10 (42.6 mg, 6%). Skipped diene (Z,Z)-10:
a colorless oil; [α]26 +26.5 (c 1.00, CHCl3); IR (film) 2946,
D
2866, 1741, 1692, 1463, 1436, 1414, 1250, 1175, 1131, 859,
839, 765, 682 cm-1; 1H NMR (500 MHz, CDCl3, 60 °C) δ
5.40‒5.27 (m, 2H), 5.23‒4.90 (m, 2H), 4.25‒4.10 (m, 2H),
4.10‒3.91 (m, 1H), 3.91‒3.78 (m, 1H), 3.77‒3.55 (m, 6H), 3.12
(d, J = 14.0 Hz, 1H), 3.05‒2.90 (m, 2H), 2.84 (d, J = 13.2 Hz,
1H), 2.61 (d, J = 12.6 Hz, 1H), 2.55 (dd, J = 13.7, 13.7 Hz, 1H),
2.31 (t, J = 7.5 Hz, 2H), 2.26 (dd, J = 13.7, 6.9 Hz, 1H),
2.16‒2.07 (m, 3H), 1.98‒1.89 (m, 1H), 1.70 (tt, J = 7.5, 7.5 Hz,
2H), 1.78‒1.63 (m, 1H), 1.60‒1.40 (m, 13H), 1.35‒1.26 (m,
1H), 1.13‒1.04 (m, 21H), 1.00 (t, J = 8.3 Hz, 2H), 0.06 (s, 9H);
13C NMR (125 MHz, CDCl3, 1:1 mixture of rotamers) δ 174.3
(C), 174.1 (C), 156.8 (C), 156.8 (C), 155.4 (C), 155.2 (C),
136.8 (C), 136.1 (C), 129.4 (CH), 129.3 (CH), 129.0 (CH),
128.8 (CH), 124.9 (CH), 123.9 (CH), 79.8 (C), 79.4 (C), 63.9
(CH2), 63.9 (CH2), 63.8 (CH2), 63.8 (CH2), 51.6 (CH3), 51.5
(CH3), 50.9 (CH2), 50.7 (CH2), 49.0 (CH2), 48.7 (CH2), 47.2
(CH2), 47.2 (CH2), 45.2 (CH), 44.0 (CH), 35.9 (CH), 35.7 (CH),
35.6 (CH2), 35.6 (CH), 35.3 (CH2), 35.22 (C), 35.18 (CH), 34.9
(C), 33.60 (CH2), 33.56 (CH2), 32.8 (CH2), 32.5 (CH2), 30.2
(CH2), 29.7 (CH2), 28.63 (CH3), 28.57 (CH3), 26.9 (CH2), 26.9
(CH2), 26.7 (CH2), 26.6 (CH2), 26.1 (CH2), 26.0 (CH2), 25.0
(CH2), 24.9 (CH2), 18.2 (CH3), 18.2 (CH3), 17.9 (CH2), 17.9
(CH2), 12.1 (CH), 12.1 (CH), ‒1.3 (CH3), ‒1.3 (CH3); HRMS
(ESI), calcd for C42H76N2O7Si2Na+ (M+Na)+ 799.5089, found
Allylic carbonate (50): Methyl chloroformate (140 µL, 1.8
mmol) was added to a solution of allylic alcohol (Z)-47 (614
mg, 920 µmol), pyridine (150 µL, 1.8 mmol) and CH2Cl2 (9.0
mL) at 0 °C. This solution was maintained for 2 h at 0 °C, and
concentrated. The residue was purified by silica gel column
chromatography (EtOAc/hexane 1:4) to give allylic carbonate
799.5090. Skipped diene (E,Z)-10: a colorless oil; [α]24 +2.1
D
(c 1.00, CHCl3); IR (film) 2946, 2866, 1741, 1694, 1463, 1436,
1414, 1366, 1318, 1250, 1175, 1131, 882, 860, 839, 765, 687
50 (670 mg, 100%): a colorless oil; [α]28 +49.6 (c 1.00,
D