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N. Maezaki et al. / Tetrahedron 62 (2006) 10361–10378
5.38 (dd, J¼8.5, 8.5 Hz, 1H, CHOC(O)CF3), 5.86 (dt,
J¼14.6, 6.7 Hz, 1H, C]CHCH2), 6.78 (d, J¼8.5 Hz, 2H,
ArH), 7.15 (d, J¼8.5 Hz, 2H, ArH). 13C NMR (75 MHz,
CDCl3) d: 13.8, 15.9, 20.0, 22.1, 29.5, 30.7, 32.0, 55.2,
74.9, 82.2, 83.9, 113.7 (2C), 114.6 (q, JC–F¼286.5 Hz),
123.1, 129.4 (2C), 130.4, 139.5, 156.6 (q, JC–F¼41.7 Hz),
159.2. IR: 2960 (CH), 2877 (CH), 1782 (C]O). MS (FAB)
m/z 425 (MNa+). HRMS (FAB) calcd for C21H29F3NaO4
(MNa+): 425.1916; found: 425.1941.
Compound 11b (208 mg, 0.68 mmol) was converted into
allylic alcohol (208 mg, quant.) in a similar procedure
(reaction time 22 h) as described for (Z)-12a. [a]2D5 +25.1
1
(c 2.19, CHCl3). H NMR (500 MHz, CDCl3) d: 0.90 (t,
J¼6.7 Hz, 3H, CH2CH3), 0.96 (d, J¼6.7 Hz, 3H,
CH(CH3)2), 1.03 (d, J¼6.7 Hz, 3H, CH(CH3)2), 1.25–1.45
(m, 4H, CH2ꢂ2), 1.90 (septd, J¼6.7, 4.9 Hz, 1H,
CH(CH3)2), 2.01 (m, 2H, C]CHCH2), 2.45 (br, 1H, OH),
3.11 (dd, J¼6.7, 4.9 Hz, 1H, CHOPMB), 3.81 (s, 3H,
ArOCH3), 4.42 (dd, J¼8.5, 6.7 Hz, 1H, CHOH), 4.56 (d,
J¼11.0 Hz, 1H, CH2Ar), 4.64 (d, J¼11.0 Hz, 1H, CH2Ar),
5.42 (dd, J¼11.0, 8.5 Hz, 1H, CH(OH)CH]C), 5.55 (dt,
J¼11.0, 6.7 Hz, 1H, C]CHCH2), 6.89 (d, J¼8.5 Hz, 2H,
ArH), 7.29 (d, J¼8.5 Hz, 2H, ArH). 13C NMR (75 MHz,
CDCl3) d: 13.9, 17.4, 20.3, 22.3, 27.6, 29.8, 31.6, 55.2,
68.0, 75.0, 88.0, 113.8 (2C), 129.4 (2C), 129.7, 130.6,
133.6, 159.2. IR: 3473 (OH), 2958 (CH), 2871 (CH). MS
(FAB) m/z 329 (MNa+). HRMS (FAB) calcd for
C19H30NaO3 (MNa+): 329.2093; found: 329.2123. The
allylic alcohol (61 mg, 0.20 mmol) was converted into (Z)-
12b (73 mg, 90%) in a similar procedure as described for
(E)-12b. [a]2D6 ꢀ22.9 (c 0.32, CHCl3). 1H NMR (500 MHz,
CDCl3) d: 0.90 (t, J¼6.7 Hz, 3H, CH2CH3), 0.90 (d,
J¼6.7 Hz, 3H, CH(CH3)2), 0.98 (d, J¼6.7 Hz, 3H,
CH(CH3)2), 1.20–1.75 (m, 4H, CH2ꢂ2), 1.83 (qnd, J¼6.7,
3.1 Hz, 1H, CH(CH3)2), 2.10–2.35 (m, 2H, C]CHCH2),
3.41 (dd, J¼8.5, 3.1 Hz, 1H, CHOPMB), 3.80 (s, 3H,
ArOCH3), 4.49 (d, J¼11.0 Hz, 1H, CH2Ar), 4.65 (d,
J¼11.0 Hz, 1H, CH2Ar), 5.35 (dd, J¼11.0, 11.0 Hz, 1H,
CH(OC(O)CF3)CH]C), 5.74 (dt, J¼11.0, 6.7 Hz, 1H,
C]CHCH2), 5.80 (dd, J¼11.0, 8.5 Hz, 1H, CHOC(O)CF3),
6.86 (d, J¼8.5 Hz, 2H, ArH), 7.23 (d, J¼8.5 Hz, 2H, ArH).
13C NMR (75 MHz, CDCl3) d: 13.9, 16.1, 20.3, 22.4, 28.0,
29.6, 31.4, 55.3, 75.1, 84.1 (2C), 113.7 (2C), 114.6 (q,
JC–F¼285.8 Hz), 122.4, 129.4 (2C), 130.4, 138.1, 156.6 (q,
JC–F¼42.2 Hz), 159.2. IR: 2962 (CH), 2875 (CH), 1784
(C]O). MS (FAB) m/z 425 (MNa+). HRMS (FAB) calcd
for C21H29F3NaO4 (MNa+): 425.1916; found: 425.1937.
3.1.18. (Z,2S,3S)-2-(4-Methoxybenzyloxy)-4-nonen-3-yl
trifluoroacetate [(Z)-12a].
n-Bu
CF3C(O)O
Me
OPMB
A solution of 11a (55.3 mg, 0.200 mmol) in MeOH (2 mL)
was hydrogenated on Lindlar catalyst (2.8 mg, 5% w/w)
with stirring at rt for 21 h. Lindlar catalyst (2.8 mg, 5%
w/w) was added to the mixture and the stirring was continued
for 9 h, and then filtered off through Celite. The filtrate was
concentrated under reduced pressure and the residue was
chromatographed on silica gel with hexane–EtOAc (4:1) to
give the allylic alcohol (54.5 mg, 98%) as a colorless oil.
[a]2D4 +45.1 (c 1.33, CHCl3). 1H NMR d: 0.89 (t, J¼7.3 Hz,
3H, CH2CH3), 1.14 (d, J¼6.1 Hz, 3H, PMBOCHCH3), 1.28–
1.40 (m, 4H, CH2ꢂ2), 2.05–2.20 (m, 2H, CH]CHCH2),
2.77 (s, 1H, OH), 3.39 (dq, J¼8.5, 6.1 Hz, 1H, PMBOCH),
3.81 (s, 3H, OCH3), 4.25 (t, J¼8.5 Hz, 1H, CHOH), 4.40
(d, J¼11.0 Hz, 1H, CH2Ar), 4.62 (d, J¼11.0 Hz, 1H,
CH2Ar), 5.32 (dd, J¼11.0, 8.5 Hz, 1H, CH]CHCH2), 5.63
(dt, J¼11.0, 7.3 Hz, 1H, CH]CHCH2), 6.89 (d, J¼8.5 Hz,
2H, ArH), 7.27 (d, J¼8.5 Hz, 2H, ArH). 13C NMR d: 14.0,
15.5, 22.4, 27.8, 31.7, 55.2, 70.8, 71.2, 78.5, 113.7 (2C),
127.8, 129.3 (2C), 130.2, 135.0, 159.1. IR: 3458 (OH),
2958 (CH), 2931 (CH), 2871 (CH). MS (FAB) m/z 301
(MNa+). HRMS (FAB) calcd for C17H26NaO3 (MNa+):
301.1780; found: 301.1786. Compound (Z)-12a was ob-
tained as a colorless oil (160 mg, 85%) from 11a (139 mg,
0.500 mmol) as described for (E)-12a. [a]2D5 ꢀ18.4 (c 1.07,
CHCl3). 1H NMR d: 0.89 (t, J¼7.0 Hz, 3H, CH2CH3), 1.15
(d, J¼6.4 Hz, 3H, PMBOCHCH3), 1.26–1.39 (m, 4H,
CH2ꢂ2), 2.12–2.26 (m, 2H, CH]CHCH2), 3.67 (dq,
J¼7.6, 6.4 Hz, 1H, PMBOCH), 3.80 (s, 3H, OCH3), 4.47
(d, J¼11.6 Hz, 1H, CH2Ar), 4.55 (d, J¼11.6 Hz, 1H,
CH2Ar), 5.33 (ddt, J¼11.0, 9.8, 1.8 Hz, 1H, CH]CHCH2),
5.69 (dd, J¼9.8, 7.6 Hz, 1H, CHOC(O)CF3), 5.77 (dt,
J¼11.0, 7.9 Hz, 1H, CH]CHCH2), 6.87 (d, J¼8.5 Hz, 2H,
ArH), 7.23 (d, J¼8.5 Hz, 2H, ArH). 13C NMR d: 14.0,
15.9, 22.4, 27.9, 31.4, 55.3, 71.4, 75.0, 77.5, 113.7 (2C),
114.6 (q, JC–F¼285.6 Hz), 122.0, 129.2 (2C), 129.9, 138.9,
156.5 (q, JC–F¼41.9 Hz), 159.1. IR: 2958 (CH), 2935
(CH), 2870 (CH), 1782 (C]O). MS (FAB) m/z 397
(MNa+). HRMS (FAB) calcd for C19H25F3NaO4 (MNa+):
397.1603; found: 397.1603.
3.1.20. Dimethyl 2-[(E,2S,5S)-2-(4-methoxybenzyloxy)-3-
nonen-5-yl]malonate (syn-13a).
CH(CO2Me)2
Me
n-Bu
OPMB
The procedure was described in the communication.4 [a]D23
1
ꢀ46.9 (c 0.76, CHCl3). H NMR d: 0.87 (t, J¼6.7 Hz, 3H,
CH2CH3), 1.20–1.35 (m, 5H, CH2ꢂ3), 1.23 (d, J¼6.7 Hz,
3H, PMBOCHCH3), 1.42–1.49 (m, 1H, CH2CH2CH2CH3),
2.81 (qd, J¼8.9, 3.7 Hz, 1H, CHCH(CO2CH3)2), 3.42 (d,
J¼8.9 Hz, 1H, CH(CO2CH3)2), 3.69 (s, 3H, CO2CH3),
3.74 (s, 3H, CO2CH3), 3.80 (s, 3H, ArOCH3), 3.82–3.87
(m, 1H, PMBOCH), 4.22 (d, J¼11.3 Hz, 1H, CH2Ar), 4.44
(d, J¼11.3 Hz, 1H, CH2Ar), 5.43–5.50 (m, 2H, CH]CH),
6.87 (d, J¼8.5 Hz, 2H, ArH), 7.26 (d, J¼8.5 Hz, 2H,
ArH). 13C NMR d: 13.9, 21.9, 22.3, 29.1, 32.0, 42.7, 52.3,
52.4, 55.2, 57.0, 69.1, 74.7, 113.6 (2C), 129.3 (2C), 130.7,
131.9, 135.3, 158.9, 168.5, 168.7. IR: 2952 (CH), 2929
(CH), 2861 (CH), 1753 (C]O), 1738 (C]O). MS (FAB)
m/z 415 (MNa+). HRMS (FAB) calcd for C22H32NaO6
(MNa+): 415.2097; found: 415.2093.
3.1.19. (Z,3S,4S)-3-(4-Methoxybenzyloxy)-2-methyl-5-
decen-4-yl trifluoroacetate [(Z)-12b].
n-Bu
CF3C(O)O
i-Pr
OPMB