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Helvetica Chimica Acta – Vol. 89 (2006)
the mixture, and the org. phase was extracted with Et
filtered, and concentrated in vacuo. The crude residue was purified by FC (SiO2 (100 g); Et CTHREUNG
O (230 ml). The org. layer was dried (Na2SO4),
2AO/hexane
5 :95; Rf ((E/Z)-6b) 0.10, Rf ((E)-6c) 0.43, Rf ((Z)-6c) 0.48) to give (E/Z)-6c. Colorless oil (2.92 g,
90%). Purity: 91.5% (GLC; dec.). GLC: tR ((Z)-6b) 7.69, tR ((E)-6b) 7.76, tR ((Z)-6c) 7.78, tR ((E)-6c)
7.87 ((E/Z) 65 :35). IR (nujol): 2954m, 2925m, 2866m, 1728s, 1670w, 1462m, 1377m, 1366m, 1273w,
1156s (br.). 1H-NMR (300 MHz): 0.85–0.88 (m, 4 Me); 1.00–1.60 (m, 19 H , CH , CH); 1.71 (s,
2
=CMe, (E)-isomer); 1.76 (d, J=1, =CMe, (Z)-isomer); 2.01 (t, J=7.6, =(Me)CH2, (E)-isomer); 2.10
(t, J=7.5, =(Me)CH2, (Z)-isomer); 4.66 (d, J=7.5, OCH2, (Z)-isomer); 4.69 (d, J=7.6, OCH2, (E)-iso-
mer); 5.36 (mc, =CH); 8.06 (s, OCHO). EI-MS: 324.4 (4, M+), 278.3 (27, [MÀHCOOH]+), 123.1 (100,
[C9H15]+). Anal. calc. for C21H40O2 (324.55): C 77.72, H12.42; found: C 77.72, H12.42.
(all-rac,E/Z)-Phytyl Acetate (all-rac,E/Z)-6d). A mixture of (all-rac,E/Z)-5b (6.23 g, 20.0 mmol;
(E/Z) 72 :28), pyridine (1.98 g, 25.0 mmol), Ac2O (2.04 g, 20.0 mmol), and hexane (5 ml) was stirred at
r.t. for 18 h. Then, H2O (30 ml) was added, and the resulting mixture was extracted with Et2CAHTREOUNG (350
ml). The org. phases were combined and washed with 10% aq. HCl (330 ml), neutralized with sat.
aq. NaHCO3 soln. (50 ml), washed with brine (50 ml) and H2O (50 ml), and dried (Na2SO4). After filtra-
tion, the solvent was removed in vacuo, and the crude residue was purified by FC (SiO2 (120 g); Et2CAHTREOUNG /
hexane 1:4; Rf ((E,Z)-6b) 0.15, Rf ((E,Z)-6d) 0.66) to give (E,Z)-(all-rac)-6d. Colorless oil (5.62 g,
16.6 mmol, 83%). Purity: 98.2% (GLC). GLC: tR ((Z)-5b) 7.69, tR ((E)-5b) 7.76, tR ((Z)-5d) 7.97 min,
tR ((E)-5d) 8.06 min ((E/Z) 71:29). IR (MIR): 2952m, 2926m, 2868m, 1742s, 1673w, 1462m (br.),
1378m, 1365m, 1228s, 1020m. 1H-NMR (400 MHz): 0.84–0.88 (m, 4 Me); 1.00–1.60 (m, 19 H , CH ,
CH2); 1.69 (s, =CMe, (E)-isomer); 1.75 (d, J=0.8, =CMe; (Z)-isomer); 2.00 (t, J=7.2, =C(Me)CH2,
(E)-isomer); 2.04 (s, Ac); 2.08 (t, J=7.0, =C(Me)CH2, (Z)-isomer); 4.56 (d, J=7.0, OCH2, (Z)-isomer);
4.58 (d, J=7.2, OCH2, (E)-isomer); 5.35 (mc, =CH). EI-MS: 278.3 (47, [MÀHÀAcO]+), 123.1 (100,
[C9H15]+). Anal. calc. for C22H42O2 (338.57): C 78.05, H12.50; found: C 78.20, H12.61.
(R,R,E)-Phytyl Acetate ((R,R,E)-6d). Obtained from (R,R,E)-6b ((E/Z) 99.7:0.3) by the same pro-
cedure as described above. Yield: 61%. Purity: 96.5% ((E/Z) 99.7:0.3 (GLC)). [a]2D0 =À0.57 (c=1.04,
CH2Cl2).
(all-rac,E/Z)-Phytyl Benzoate (6e). A mixture of (all-rac,E/Z)-6b (15.02 g, 48.6 mmol; (E/Z) 72 :28),
benzoic anhydride (11.56 g, 51.1 mmol), and DMAP (300 mg, 2.4 mmol) in hexane (30 ml) was stirred at
r.t. for 20 h. Then, H2O (50 ml) was added, and the org. phase was extracted with Et2ACHTREOUGN (350 ml). The
org. layer was washed with 10% aq. HCl (315 ml), neutralized with sat. aq. NaHCO3 soln. (50 ml),
washed with brine (50 ml) and H2O (50 ml), and dried (Na2SO4). After filtration, the solvent was
removed in vacuo, and the crude residue was purified by FC (SiO2 (140 g); AcOEt/hexane 5 :95; Rf
((E/Z)-6b) 0.17, Rf ((E/Z)-6e) 0.74) to give 6e (14.8 g, 76%). Purity: 99.5% (GLC). GLC: tR ((Z)-6b)
7.69, tR ((E)-6b) 7.76, tR ((Z)-6e) 9.89, tR ((E)-6e) 10.08 ((E/Z) 68 :32). IR (MIR): 2952m, 2926m,
2867m, 1720s, 1602w, 1586w, 1461m, 1451m, 1377m, 1314m, 1267s (br.), 1175m, 1106m, 1097m, 1069m,
1
1027m. H-NMR (400 MHz): 0.82–0.95 (m, 4 Me); 0.99–1.60 (m, 19 H , CH , CH); 1.75 (s, =CMe);
2
1.78 (d, J=0.8, =CMe); 2.03 (t, J=7.6, =CMeCH2, (E)-isomer); 2.13 (t, J=7.6, =CMeCH2, (Z)-isomer);
4.81 (d, J=7.6, OCH2, (Z)-isomer); 4.84 (d, J=6.8, OCH2, (E)-isomer); 5.46 (mc, =CH); 7.43 (dd, J=8.0,
8.4, 2 arom. H); 7.54 (t, J=8.4, 1.3, arom. H); 8.05 (dd, J=8.0, 1.3, 2 arom. H). EI-MS: 278.3 (3,
[MÀHÀC6H5COO]+), 123 (33, [C9H15]+), 105 (100, [C6H5CO]+). Anal. calc. for C27H44O2 (400.64): C
80.94, H11.07; found: C 80.97, H11.07.
General Procedure for Ru-Catalyzed Reactions. a) Reactions in Toluene at Ambient Pressure. A
Schlenk tube placed under Ar and equipped with a magnetic stirring bar was charged with 4a (8.4 mg,
0.01 mmol) (or 4b), tridecane (36.8 mg, 0.2 mmol), and anh. toluene (2 ml). Then, a soln. of substrate
5, 7, or 8 (0.2 mmol) and metathesis partner 6 (0.4 mmol) dissolved in toluene (4 ml) was added at r.t.
The resulting brown soln. was stirred at r.t. for 10 min, and then at 808 for 16–18 h. The progress of
the reaction was monitored by GLC: tR (tridecane) 4.77, tR (5a) 6.85, tR (5b) 7.16, tR (5c) 7.56, tR (5d)
7.77, tR (5e) 9.37, tR (5f) 8.29, tR (7a) 15 (br.), tR (7b) 14.65, tR (8a) 6.46, tR ((E)-8b) 6.86, tR ((Z)-8b)
6.89, tR (8c) 7.18, tR (6a) 6.49, tR ((Z)-6b) 7.69, tR ((E)-6b) 7.76, tR ((Z)-6c) 7.78, tR ((E)-6c) 7.87, tR
((Z)-6d) 7.97, tR ((E)-6d) 8.06, tR ((Z)-6e) 9.89, tR ((E)-6e) 10.08, tR ((Z)-2b) 12.96, tR ((E)-2b) 13.14,
tR ((E,Z)-2d) 13.49, tR ((Z)-2e) 19.59, tR ((E)-2e) 20.51, tR ((Z)-2f) 14.73, tR ((E)-2f) 15.07, tR ((Z,E)-
3b) 9.5 (br.)), tR ((E)-9) 12.44, tR ((Z)-9) 12.65; 8d decomposed under GLC conditions. After 16–18 h,