7830 J . Org. Chem., Vol. 61, No. 22, 1996
Yoshida et al.
7.1, 3H, Z isomer), 1.24 (t, J ) 7.1, 3H, E isomer), 1.62-1.82
(m, 1H), 1.91-2.17 (m, 3H), 3.14 (dt, J ) 7.4, 8.4, 1H, E
isomer), 3.51 (dt, J ) 7.3, 9.6, 1H, Z isomer), 3.55-3.74 (m,
2H), 4.12 (q, J ) 7.1, 2H, Z isomer), 4.13 (qq, J ) 7.1, 2H, E
isomer), 5.35 (ddt, J ) 9.6, 10.9, 1.7, 1H, Z isomer), 5.41 (ddt,
J ) 8.4, 15.4, 1.5, 1H, E isomer), 5.55 (dt, J ) 7.2, 10.9, 1H, Z
isomer), 5.57 (dt, J ) 6.6, 15.4, 1H, E isomer); 13C NMR δ
13.85, 13.91 (Z), 14.13 (Z and E), 22.09, 22.28 (Z), 27.25 (Z),
31.29, 31.62 (Z), 32.08, 35.14, 35.36 (Z), 40.94 (Z), 46.04, 60.50
(Z and E), 60.63 (Z and E), 126.62 (Z), 126.99, 133.38 (Z),
134.02, 174.53 (Z), 174.62; IR (neat) 3430, 2970, 2940, 2880,
1740, 1660, 1475, 1375, 1265, 1165, 1060, 975, 905, 865, 715;
Anal. Calcd for C12H22O3: C, 67.26; H, 10.35. Found: C,
67.42; H, 10.41.
Eth yl (E)- a n d (Z)-2-(2-h yd r oxyeth yl)-5-m eth yl-3-p en -
ten oa te (4b) (en tr y 2 in Ta ble 1): 1H NMR δ 0.97 (d, J )
6.6, 3H), 0.98 (d, J ) 6.6, 3H), 1.25 (t, J ) 7.1, 3H), 1.53-1.82
(m, 3H), 1.94-2.09 (m, 1H), 2.20-2.35 (m, 1H, E isomer),
2.56-2.76 (m, 1H, Z isomer), 3.14 (dt, J ) 7.7, 8.6, 1H, E
isomer), 3.53 (dt, J ) 7.3, 9.9, Z isomer), 3.50-3.78 (m, 2H),
4.14 (q, J ) 7.14, 2H Z isomer), 4.15 (q, J ) 7.0, 2H, E isomer),
5.23 (dd, J ) 9.9, 10.2, 1H, Z isomer), 5.38 (dd, J ) 10.2, 10.2,
1H, Z isomer), 5.56 (dd, J ) 6.4, 15.3, 1H, E isomer); 13C NMR
δ 14.0, 22.9, 26.8, 35.3, 41.0, 60.2, 60.5, 124.2, 140.6, 174.5;
IR (neat) 3423, 2960, 2870, 2362, 1734, 1466, 1369, 1259, 1174,
1055, 918, 735. Anal. Calcd for C11H20O3: C, 65.97; H, 10.06.
Found: C, 66.24; H, 10.09.
1H), 1.22 (t, J ) 7.1, 3H), 1.51-1.67 (m, 1H), 1.83-1.99 (m,
1H), 3.25 (dt, J ) 7.1, 10.4, 1H), 3.31-3.53 (m, 2H), 4.10 (q, J
) 7.1, 2H), 5.88 (d, J ) 13.8, 1H), 6.32 (dd, J ) 10.4, 13.8,
1H), 7.30-7.44 (m, 3H), 7.50-7.64 (m, 2H); 13C NMR δ -1.42,
-0.86, 14.07, 35.31, 46.61, 60.23, 60.67, 127.90, 129.14, 131.08,
133.78, 138.99, 146.38, 173.81; IR (neat) 3450, 3080, 3060,
2970, 1735, 1615, 1435, 1375, 1340, 1255, 1165, 1120, 1055,
825, 785, 735, 705, 675. Anal. Calcd for C16H24O3Si: C, 65.71;
H, 8.27. Found: C, 66.27; H, 8.69.
Eth yl (R)-(Z)-2-(2-h yd r oxyeth yl)-4-tr ibu tylsta n n yl-3-
bu ten oa te (4g) (en tr y 7 in Ta ble 1): [R]22 -71 (c 2.00,
D
1
CHCl3); H NMR δ 0.80-1.08 (m, 15H), 1.16-1.66 (m, 12H),
1.25 (t, J ) 7.0, 3H), 1.71-1.81 (m, 1H), 1.96-2.12 (m, 1H),
2.99 (ddd, J ) 6.5, 7.8, 9.8, 1H), 3.56-3.76 (m, 2H), 4.13 (qq,
J ) 7.1, 2H), 6.02 (d, J ) 12.5, J Sn-H 61.2Hz, 1H), 6.47 (dd, J
) 9.8, 12.5, J Sn-H 128.5, 1H); 13C NMR δ 10.32, 13.65, 14.14,
27.30, 29.12, 35.78, 50.50, 60.66, 60.70, 132.69, 145.56, 174.16;
IR (neat) 3440, 2960, 2930, 2880, 1740, 1600, 1470, 1425, 1380,
1340, 1260, 1155, 1050, 960, 865, 770, 685, 665. Anal. Calcd
for C20H40O3Sn: C, 53.71; H, 9.01. Found: C, 53.57; H, 9.23.
Eth yl (E)- a n d (Z)-2-(2-h yd r oxyp h en yl)-3-octen oa te
(4h ) (en tr y 8 in Ta ble 1): a 37:63 mixture of Z and E
1
isomers; H NMR δ 0.86 (t, J ) 6.7, 3H), 1.15-1.45 (m, 6H),
1.28 (t, J ) 7.1, 3H), 1.97-2.20 (m, 2H), 4.12-4.28 (m, 2H),
4.32 (d, J ) 7.6, E isomer), 4.65 (d, J ) 9.3, 1H, Z isomer),
5.54-5.70 (m, 1H), 5.87 (ddt, J ) 7.6, 15.3, 1.7, 1H, E isomer),
5.99 (ddt, J ) 9.3, 10.7, 1.5, 1H, Z isomer), 6.80-7.00 (m, 2H),
7.03-7.24 (m, 2H), 7.83 (br s, 1H, E isomer), 7.86 (br s, 1H, Z
isomer); 13C NMR δ 13.98 (4 peaks), 22.43, 22.47, 27.48, 28.63,
28.85, 31.32, 31.41, 32.35, 47.81, 53.08, 61.96, 62.02, 118.13
(2 peaks), 120.68, 120.77, 124.17, 120.40, 124.57 (2 peaks),
128.94, 129.09, 129.83, 130.13, 134.04, 134.74, 154.79, 154.89,
175.52; IR (neat) 3400, 2970, 2940, 2860, 1710, 1600, 1515,
1495, 1465, 1375, 1280, 1195, 1100, 1030, 975, 900, 855, 755.
Anal. Calcd for C17H24O3: C, 73.88; H, 8.75. Found: C, 73.73;
H, 8.95.
Eth yl (Z)-2-(2-h ydr oxyeth yl)-5,5-dim eth yl-3-pen ten oate
1
(4c) (en tr y 3 in Ta ble 1): H NMR δ 1.15 (s, 9H), 1.25 (t, J
) 7.2, 3H), 1.60-1.83 (m, 2H), 1.92-2.06 (m, 1H), 3.60-3.74
(m, 2H), 3.80 (dt, J ) 10.9, 7.1, 1H), 4.15 (q, J ) 7.1, 2H),
5.18, (dd, J ) 10.9, 11.5, 1H), 5.51 (d, J ) 11.5, 1H); 13C NMR
δ 14.1, 31.2, 33.5, 36.1, 41.6, 60.5, 60.6, 125.4, 142.7, 174.5;
IR (neat) 3448, 2956, 2871, 1734, 1477, 1410, 1365, 1336, 1205,
1161, 1053, 908, 858, 733. Anal. Calcd for C12H22O3: C, 67.26;
H, 10.35. Found: C, 66.81; H, 10.16.
Eth yl 2-(2-h yd r oxyeth yl)-4-p en tyl-3-octen oa te (4i) (en -
tr y 9 in Ta ble 1): 1H NMR δ 0.88 (t, J ) 7.0, 3H), 0.89 (t, J
) 6.8, 3H), 1.15-1.46 (m, 12H), 1.24 (t, J ) 7.1, 3H), 1.62 (br
s, 1H), 1.67-1.81 (m, 1H), 1.92-2.15 (m, 5H), 3.45 (dt, J )
7.2, 9.9, 1H), 3.56-3.74 (m, 2H), 4.12 (q, J ) 7.1, 2H), 5.10 (d,
J ) 9.9, 1H); 13C NMR δ 14.01, 14.04, 14.16, 22.52, 22.57,
27.72, 28.12, 30.35, 31.52, 31.96, 35.74, 36.68, 41.46, 60.47,
60.68, 121.73, 143.75, 174.99; IR (neat) 3430, 2970, 2940, 2860,
1740, 1660, 1475, 1375, 1260, 1165, 1105, 1060, 910, 865, 730.
Anal. Calcd for C18H34O3: C, 72.44; H, 11.48. Found: C,
72.38; H, 11.54.
Eth yl (E)- a n d (Z)-2-(2-h yd r oxyeth yl)-4-p h en yl-3-bu t-
en oa te (4d ) (en tr y 4 in Ta ble 1): a 65:35 mixture of Z and
E isomers; H NMR δ 1.27 (t, J ) 7.1, 3H, E isomer), 1.28 (t,
1
J ) 7.1, 3H, Z isomer), 1.60-1.96 (m, 2H), 1.98-2.19 (m, 1H),
3.39 (dt, J ) 7.6, 8.7, 1H, E isomer), 3.52-3.76 (m, 2H), 3.78
(dt, J ) 7.2, 10.6, 1H, Z isomer), 4.17 (q, J ) 7.1, 2H, E isomer),
4.18 (q, J ) 7.1, 2H, Z isomer), 5.67 (dd, J ) 10.6, 11.3, 1H, Z
isomer), 6.21 (dd, J ) 8.7, 15.9, 1H, E isomer), 6.52 (d, J )
15.9, 1H, E isomer), 6.63 (d, J ) 11.3, 1H, Z isomer), 7.18-
7.42 (m, 5 H); 13C NMR δ 14.15 (2 peaks), 35.18, 35.65, 41.56,
46.28, 60.27 (2 peaks), 60.86 (2 peaks), 126.32, 126.93, 127.22,
127.62, 128.37, 128.52, 128.60, 129.01, 131.77, 132.57, 136.43,
136.67, 174.07, 174.13; IR (neat) 3430, 3070, 3030, 2940, 2880,
1730, 1650, 1605, 1500, 1455, 1375, 1260, 1180, 1050, 970, 920,
860, 770, 735, 700. Anal. Calcd for C14H18O3: C, 71.77; H,
7.74. Found: C, 72.37; H, 7.67.
Resu lts of th e Rea ction of En tr y 11 in Ta ble 1. 1H
NMR analysis of the crude mixture showed that the reaction
provided several products but less than 5% of 4k . One of these
products was the allenyl-homocoupling product shown below
(32% yield).
Eth yl (Z)-2-(2-h yd r oxyeth yl)-4-(tr im eth ylsilyl)-3-bu t-
en oa te (4e) (en tr y 5 in Ta ble 1): 1H NMR δ 0.16 (s, 9H),
1.26 (t, J ) 7.1, 3H), 1.54 (br s, 1H), 1.70-1.88 (m, 1H), 1.95-
2.11 (m, 1H), 3.40 (dt, J ) 7.2, 10.3, 1H), 3.58-3.76 (m, 2H),
4.15 (q, J ) 7.1, 2H), 5.71 (d, J ) 13.8, 1H), 6.24 (dd, J ) 10.3,
13.8, 1H); 13C NMR δ 0.09, 14.10, 35.52, 46.77, 60.46, 60.72,
133.07, 144.72, 174.02; IR (neat) 3450, 2970, 1740, 1615, 1375,
1255, 1165, 1060, 850, 770, 695, 665. Anal. Calcd for
C11H22O3Si: C, 57.35; H, 9.62. Found: C, 56.85; H, 9.85.
Deuterolysis product: 1H NMR δ 3.40 (t, J ) 7.1, 1H), 5.71 (s,
1H); 13C NMR δ 0.09, 14.09, 35.53, 46.68, 60.44, 60.69, 132.85,
144.40 (t, J ) 24.7), 174.00.
Eth yl (E)-3-iod o-2-(2-h yd r oxyeth yl)-4-(tr im eth ylsilyl)-
3-bu ten oa te. The title compound is not stable enough to be
stored for elemental analysis: 1H NMR δ 0.18 (s, 9H), 1.27 (t,
J ) 7.1, 3H), 1.71 (br s, 1H), 1.70-1.87 (m, 1H), 2.10-2.25
(m, 1H), 3.35 (t, J ) 6.9, 1H), 3.56-3.80 (m, 2H), 4.17 (q, J )
7.1, 2H), 6.63 (s, 1H); 13C NMR δ -0.07, 14.08, 35.64, 52.98,
59.62, 61.36, 114.72, 148.65, 171.02; IR (neat) 3450, 2970,
2910, 1740, 1590, 1455, 1375, 1260, 1210, 1170, 1060, 1025,
915, 855, 770, 740, 700.
1H NMR δ 1.31 (t, J ) 7.1, 6H), 1.70-1.88 (m, 2H), 2.03-
2.16 (m, 4H), 2.73 (2d, J ) 5.6, 2H), 4.118 and 4.123 (2t, J )
6.8 and J ) 6.7, 4H), 4.19 (q, J ) 7.1, 4H), 4.78 (br s, 2H),
5.30-5.60 (m, 2H).
Deter m in a tion of Op tica l P u r ities of 4f a n d 4g. The
compound 4f was reduced by using LiAlH4 (THF, 0 °C to room
temperature), and the resulting diol [(Z)-5-(trimethylsilyl)-3-
(hydroxymethyl)-4-penten-1-ol] was converted to bis-MTPA
esters by treatment with (R)- or (S)-MTPA-Cl and pyridine in
CCl4. Optical purity of 4f was confirmed by 300 MHz 1H NMR
of these bis-MTPA esters; olefinic proton at the R-position of
the silyl group, δ 5.844 (d, J ) 14.1, 1H) vs 5.817 (d, J ) 14.1,
1H).
The diol [(Z)-5-(tributylstannyl)-3-(hydroxymethyl)-4-penten-
1-ol] derived from 4g by the reaction with LiAlH4 was
destannylated by treatment with aqueous diluted HCl-MeOH
to give 3-(hydroxymethyl)-4-penten-1-ol in essentially quan-
titative yield. The bis-MTPA esters of this compound were
Eth yl (R)-(Z)-2-(2-h yd r oxyeth yl)-4-(p h en yld im eth ylsi-
lyl)-3-bu ten oa te (4f) (en tr y 6 in Ta ble 1): [R]24 -135 (c
analyzed by 300 MHz H NMR to determine optical purity of
1
D
1
1.32, CHCl3); H NMR δ 0.41 (s, 3H), 0.47 (s, 3H), 1.10 (br s,
4g; olefinic protons of the terminal position, [δ 5.054 (d, J )