A R T I C L E S
Lo et al.
Isotope Labeling Experiments. The procedure described in the
stoichiometric reactions was followed, and PhC18O2H and Re218O7 were
used in separate reactions, respectively. According to the ESI-TOF mass
spectra of the isolated products, isopotomers with one 18O-incorporation
were observed along with peaks associated with their 16O-analogues.
Isotopomers with two or more 18O-incorporation were not observed.
The same result was obtained from 3b, 4b, and 5b. HRMS m/z 385.1237
(3b‚Na+ ) 385.1233), 387.1280 (3b‚Na+-18O1 ) 387.1276); 313.0677
(4b‚Na+ ) 313.0658), 315.0713 (4b‚Na+-18O1 ) 315.0701); 457.1816
(5b‚Na+ ) 457.1808), 459.1858 (5b‚Na+-18O1 ) 459.1851).
114.47 (q, J ) 285.8, CF3), 70.19, 69.76, 68.03, 64.58, 41.33 (CH2-
Ph), 26.02, 25.73, 25.38, 25.16.
Compound 3h: 1H NMR δ 7.66 (d, J ) 15.9, 1H), 7.52-7.49 (m,
2H), 7.37-7.35 (m, 3H), 6.42 (d, J ) 15.9, 1H), 4.37 (t, J ) 6.6, 2H),
4. 21 (t, J ) 6.3, 2H), 3.44 (t, J ) 6.2, 4H), 1.86-1.60 (m, 8H); 13C
NMR δ 167.03, 157.51 (q, J ) 42.1, COCF3), 144.67, 134.37, 130.24,
128.86, 128.03, 118.10, 114.50 (q, J ) 285.8, CF3), 70.36, 69.89, 68.08,
64.31, 26.23, 25.82, 25.59, 25.22.
1
Compound 3i: H NMR δ 4.36 (t, J ) 6.5, 2H), 4.06 (t, J ) 6.5,
2H), 3.42 (t, J ) 6.0, 2H), 3.40 (t, J ) 5.4, 2H), 2.03 (s, 3H), 1.85-
1.76 (m, 2H), 1.73-1.50 (m, 6H); 13C NMR δ 170.99, 157.32 (q, J )
41.2, COCF3), 114.41 (q, J ) 285.8, CF3), 70.17, 69.74, 67.96, 64.10,
26.03, 25.67, 25.34, 25.10, 20.72 (CH3); HRMS m/z 323.1074 (MNa+
) 323.1082).
Compound 1a: Homoallylic carboxylic acid 1a was obtained by
hydrolysis of its corresponding ethyl ester, which was prepared from
undecanal (Aldrich) according to conventional methods described for
the syntheses of homoallylic alcohols.5b 1H NMR δ 11.25 (br s, 1H),
5.50-5.30 (m, 2H), 2.42-2.36 (m, 2H), 2.32-2.27 (m, 2H), 1.96-
1.93 (m, 2H), 1.40-1.20 (m, 16H), 0.88-0.83 (m, 3H).
1
Compound 3j: H NMR δ 4.37 (t, J ) 6.5, 2H), 4.05 (t, J ) 6.2,
2H), 3.42 (t, J ) 6.3, 2H), 3.41 (t, J ) 5.4, 2H), 1.86-1.75 (m, 2H),
1.70-1.55 (M, 6H), 1.17 (s, 9H); 13C NMR δ 178.58, 157.48 (q, J )
42.1, COCF3), 114.49 (q, J ) 285.8, CF3), 70.37, 69.85, 68.06, 64.09,
38.69 (CMe3), 27.14 (CH3), 26.18, 25.79, 25.48, 25.22.
1
Compound 3a: H NMR (600 MHz) δ 5.45-5.35 (m, 2Η), 4.37
(t, J ) 6.6, 2Η, CH2OC(O)CF3), 4.07 (t, J ) 6.5, 2H, CH2OC(O)CH2-
CH2s), 3.43 (t, J ) 6.0, 2H), 3.41 (t, J ) 6.0, 2H), 2.35-2.32 (m,
2H, HCdCHsCH2CH2CO2s), 2.30-2.27 (m, 2H, HCdCHsCH2CH2-
CO2s), 1.95-1.93 (m, 2H, HCdCHsCH2C9H19), 1.84-1.82 (m, 2H,
CH2CH2OC(O)CF3), 1.69-1.59 (m, 6H), 1.32-1.23 (m, 16H), 0.86
(vt, J ) 5.9, 3H); 13C NMR (150.9 MHz) δ 173.32, 157.51 (q, J )
41.3, COCF3), 131.85 (HCdCHC10H21), 127.84 (HCdCHC10H21),
114.45 (q, J ) 285.8, CF3), 70.35, 69.88, 68.06 (CH2OC(O)CF3), 64.06
(CH2OC(O)CH2CH2s), 34.39, 32.49, 31.89, 29.62 (for 2 C), 29.49,
29.43, 29.33, 29.13, 27.93, 26.19, 25.81, 25.50, 25.22, 22.66, 14.09
(CH3). The assignment is based on COSY, HMBC, and APT spectra.
1
Compound 3k: H NMR δ 4.36 (t, J ) 6.6, 4H), 3.43 (t, J ) 6.0,
4H), 1.86-1.78 (m, 4H), 1.69-1.60 (m, 4H); 19F NMR δ -74.85.
HRMS m/z 377.0803 (MNa+ ) 377.0794).
1
Compound 3l: H NMR δ 4.06 (t, J ) 6.3, 4H), 3.41 (t, J ) 6.2,
4H), 2.03 (s, 6H), 1.72-1.58 (m, 8H). HRMS m/z 269.1357 (MNa+
)
269.1359).
Compound 3m: 1H NMR δ 8.02 (app d, J ) 7.8, 4H), 7.53 (app t,
J ) 7.2, 2H), 7.41 (app t, J ) 7.6, 4H), 4.33 (t, J ) 6.6, 4H, CH2-
OC(O)Ph), 3.47 (t, J ) 6.0, 4H), 1.90-1.68 (m, 8H); 13C NMR δ
166.62, 132.84, 130.37, 129.53, 128.31, 70.33, 64.79, 26.35, 25.63.
HRMS m/z 393.1677 (MNa+ ) 393.1672).
1
Compound 3b: H NMR δ 8.02 (app d, J ) 7.8, 2H), 7.53 (app t,
J ) 7.2, 1H), 7.41 (app t, J ) 7.6, 2H), 4.35 (t, J ) 6.3, 2H, CH2-
OCOCF3), 4.32 (t, J ) 6.6, 2H, CH2OCOPh), 3.45 (t, J ) 6.0, 2H),
3.43 (t, J ) 6.0, 2H), 1.85-1.60 (m, 8H); 13C NMR δ 166.56, 157.46
(q, J ) 42.1, COCF3), 132.82, 130.34, 129.49, 128.28, 114.49 (q, J )
285.8, CF3), 70.34, 69.87, 68.06, 64.70 (CH2OCOPh), 26.28, 25.79,
25.59, 25.20; 19F NMR δ -74.83. HRMS m/z 385.1219 385.1236
(MNa+ ) 385.1233).
Compound 3c: 1H NMR δ 7.90 (d, J ) 8.0, 2H), 7.21 (d, J ) 8.0,
2H), 4.36 (t, J ) 6.6, 2H), 4.30 (t, J ) 6.6, 2H), 3.45 (t, J ) 5.4, 2H),
3.43 (t, J ) 6.0, 2H), 2.38, (s, 3H), 1.85-1.60 (m, 8H); 13C NMR δ
166.69, 157.49 (q, J ) 41.2, COCF3), 143.49, 129.52, 129.00, 127.58,
114.49 (q, J ) 258.8, CF3), 70.37, 69.88, 68.07, 64.53, 26.28, 25.79,
25.59, 25.20, 21.60 (CH3).
Compound 3d: 1H NMR δ 7.96 (d, J ) 8.7, 2H), 6.88 (d, J ) 8.7,
2H), 4.35 (t, J ) 6.5, 2H), 4.28 (t, J ) 6.3, 2H), 3.44 (t, J ) 6.0, 2H),
3.42 (t, J ) 6.0, 2H), 1.85-1.60 (m, 8H); 13C NMR δ 166.33, 163.24,
157.45 (q, J ) 42.1, COCF3), 131.49, 122.74, 114.47 (q, J ) 285.8,
CF3), 113.50, 70.35, 69.85, 68.06, 64.38, 55.34 (OCH3), 26.28, 25.77,
25.61, 25.19.
1
Compound 4b: H NMR δ 8.02 (app d, J ) 7.8, 2H), 7.56 (app t,
J ) 7.2, 1H), 7.43 (app t, J ) 7.7, 2H), 4.42 (t, J ) 6.0, 2H), 4.36 (t,
J ) 6.0, 2H), 1.92-1.87 (m, 4H); 19F NMR δ -74.77.
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Compound 5b: H NMR δ 8.02 (app d, J ) 8.1, 2H), 7.54 (app t,
J ) 7.2, 1H), 7.42 (app t, J ) 7.7, 2H), 4.36 (t, J ) 6.6, 2H), 4.33 (t,
J ) 6.6, 2H), 3.48-3.38 (m, 8H), 1.90-1.58 (m, 12H); 13C NMR,
partial spectrum (carbon signals for COCF3 are not provided) δ 166.63,
132.84, 130.38, 129.52, 128.31, 70.75, 70.68, 70.22, 69.80, 68.11, 64.80,
26.47 (with high intensity, two 13C signals overlapping), 26.35, 25.83,
25.62, 25.42; 19F NMR δ -74.85. HRMS m/z 457.1806 (MNa+
)
457.1808).
Partial Hydrolysis of 3b. Compound 3b was further characterized
by partial hydrolysis to remove the trifluoroacetyl group. Compound
3b (20 mg) was dissolved in CH2Cl2 (5 mL), and a small amount of
silica gel was added. The resulting mixture was allowed to stir overnight
at room temperature. The solvent of the reaction mixture was
evaporated, and the residue was purified by column chromatography
(hexanes/EtOAc ) 2.5 :1) to afford the partially hydrolyzed product,
1
1
Compound 3e: H NMR δ 8.26 (AB pattern d, J ) 8.7, 2H), 8.19
PhCO2(CH2)4O(CH2)4OH, in quantitative yield. H NMR δ 8.00 (app
(AB pattern d, J ) 8.7, 2H), 4.38 (t, J ) 6.3, 2H), 4.37 (t, J ) 6.6,
2H), 3.46 (t, J ) 6.3, 2H), 3.44 (t, J ) 6.0, 2H), 1.90-1.60 (m, 8H);
13C NMR δ 164.71, 157.52 (q, J ) 42.1, COCF3), 150.48, 135.72,
130.66, 123.52, 114.50 (q, J ) 285.8, CF3), 70.27, 70.02, 68.06, 65.77,
26.24, 25.79, 25.58, 25.25.
d, J ) 8.0, 2H), 7.51 (app t, J ) 7.5, 1H), 7.39 (app t, J ) 7.6, 2H),
4.31 (t, J ) 6.5, 2H), 3.60 (t, J ) 6.2, 2H), 3.46 (t, J ) 6.3, 2H), 3.43
(t, J ) 5.7, 2H), 2.70 (br s, 1H, OH), 1.88-1.58 (m, 8H); 13C NMR δ
166.59, 132.80, 130.23, 129.45, 128.25, 70.85, 70.32, 64.67, 62.58
(CH2OH), 30.10, 26.69, 26.16, 25.51.
Compound 3f: 1H NMR δ 7.97 (d, J ) 8.4, 2H), 7.43 (d, J ) 8.4,
2H), 6.72 (dd, J ) 17.7, 10.8, 1H, CHdCH2), 5.84 (d, J ) 17.7, 1H),
5.35 (d, J ) 10.8, 1H), 4.36 (t, J ) 6.6, 2H), 4.32 (t, J ) 6.3, 2H),
3.45 (t, J ) 6.0, 2H), 3.43 (t, J ) 5.7, 2H), 1.87-1.59 (m, 8H); 13C
NMR δ 166.37, 157.47 (q, J ) 42.1, COCF3), 141.84, 135.95 (CHd
CH2), 129.81, 129.42, 126.03, 116.41 (CHdCH2), 114.49 (q, J ) 285.6,
CF3), 70.35, 69.89, 68.06, 64.70, 26.26, 25.77, 25.58, 25.19.
Partial Hydrolysis of 5b. Compound 5b (5 mg) was partially
hydrolyzed, as described in the case of 3b, to afford PhCO2(CH2)4O-
(CH2)4O(CH2)4OH in quantitative yield. H NMR δ 8.02 (app d, J )
8.0, 2H), 7.54 (app t, J ) 7.5, 1H), 7.42 (app t, J ) 7.8, 2H), 4.32 (t,
J ) 6.3, 2H), 3.64-3.60 (m, 2H), 3.47-3.39 (m, 8H), 2.50 (br s, 1H,
OH), 1.90-1.58 (m, 12H); 13C NMR δ 166.65, 132.84, 130.39, 129.53,
128.31, 70.88, 70.83, 70.63, 70.22, 64.83, 62.78 (CH2OH), 30.44, 26.99,
26.43, 26.40, 26.36, 25.63.
1
1
Compound 3g: H NMR δ 7.40-7.20 (m, 5H), 4.35 (t, J ) 6.6,
2H), 4.09 (t, J ) 6.3, 2H), 3.60 (s, 2H), 3.39 (t, J ) 6.3, 2H), 3.37 (t,
J ) 6.3, 2H), 1.86-1.76 (m, 2H), 1.73-1.52 (m, 6H); 13C NMR δ
171.54, 157.42 (q, J ) 42.1, COCF3), 134.06, 129.16, 128.45, 126.95,
Reactivity of Other Cyclic Ethers and Substituted THF. The
procedure described in the catalytic reactions of THF was followed.
See Tables 2 and 3 for yields.
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1252 J. AM. CHEM. SOC. VOL. 129, NO. 5, 2007