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Can. J. Chem. Vol. 87, 2009
Fig. 3. Unreactive chelate complex of Ru with esterified double
bond.
17.6 Hz, J = 5.0 Hz, =CH), 6.06 (dt, 1H, J = 17.6 Hz, J =
5.0 Hz, =CH), 6.98 (dd, 1H, J = 7.9 Hz, J = 1.7 Hz, ArH),
7.40 (d, 1H, J = 6.9 Hz, ArH), 7.44 (m, 2H, ArH), 7.49 (dt,
1H, J = 7.1 Hz, J = 3.0 Hz, ArH), 7.53 (d, 1H, J = 8.1 Hz,
ArH), 7.63 (dd, 1H, J = 6.7 Hz, J = 1.0 Hz, ArH), 7.72 (dt,
1H, J = 7.7 Hz, J = 3.0 Hz, ArH), 7.80 (t, 1H, J = 7.0 Hz,
ArH), 8.04 (dt, 1H, J = 7.4 Hz, J = 2.3 Hz, ArH). MS m/z:
316 (M+). Anal. calcd. for C21H16O3: C, 79.73; H, 5.10.
Found: C, 79.61; H, 5.23.
J = 7.7 Hz, J = 1.3 Hz, ArH), 8.27 (d, 2H, J = 8.8 Hz, ArH).
MS m/z: 344 (M+). Anal. calcd. for C23H20O3: C, 80.21; H,
5.85. Found: C, 80.29; H, 6.11.
Compound 7c
Yield: 64%; colourless solid; mp 149–150 8C (dichloro-
methane–petroleum ether). IR (KBr, cm–1): 1649, 1701,
1
1739, 2849, 2920. H NMR (CDCl3, 400 MHz) dH: 3.37 (s,
Compound 6f
6H, -NCH3), 3.41 (d, 2H, J = 5.4 Hz, CH2), 5.09 (d, 2H, J =
5.4 Hz, OCH2), 5.77 (dt, 1H, J = 17.6 Hz, J = 5.0 Hz, =CH),
5.92 (dt, 1H, J = 17.6 Hz, J = 5.0 Hz, =CH), 6.90–7.04 (m,
2H, ArH), 7.47 (dd, 1H, J = 8.5 Hz, J = 1.7 Hz, ArH), 7.99
(dd, 1H, J = 7.5 Hz, J = 1.7 Hz, ArH). MS m/z: 328 (M+).
Anal. calcd. for C17H16N2O5: C, 62.19; H, 4.91; N, 8.53.
Found: C, 62.33; H, 5.09; N, 8.66.
Yield: 85%; colourless solid; mp 109–110 8C (dichloro-
methane–petroleum ether). IR (KBr, cm–1): 1663, 1704,
1
1741, 2851, 2918. H NMR (CDCl3, 400 MHz) dH: 3.39
(s, 3H, –NCH3), 3.40 (d, 2H, J = 6.3 Hz, –CH2), 3.43 (s, 3H,
–NCH3), 4.59 (d, 2H, J = 5.0 Hz, –OCH2), 5.08–5.16 (m, 2H,
=CH2), 5.19 (dd, 1H, J = 10.6 Hz, J = 1.3 Hz, =CHaHb),
5.39 (dd, 1H, J = 17.9 Hz, J = 1.3 Hz, =CHaHb), 5.77–
5.81 (m, 1H, =CH), 5.98–6.04 (m, 1H, =CH), 6.99 (d, 2H,
J = 8.1 Hz, ArH), 7.41 (dd, 1H, J = 7.7 Hz, J = 1.9 Hz,
ArH), 7.99 (dd, 1H, J = 8.2 Hz, J = 1.9 Hz, ArH). MS m/z:
356 (M+). Anal. calcd. for C19H20N2O5: C, 64.04; H, 5.66; N,
7.86. Found: C, 64.23; H, 5.83; N, 7.68.
Compound 7d
Yield: 63%; colourless solid; mp 120–121 8C (dichloro-
methane–petroleum ether. IR (KBr, cm–1): 1730, 2850,
1
2920. H NMR (CDCl3, 400 MHz) dH: 3.79 (d, 2H, J =
5.0 Hz, CH2), 4.61 (d, 2H, J = 5.0 Hz, OCH2), 5.88 (dt, 1H,
J = 17.6, J = 5.0 Hz, =CH), 6.03 (dt, 1H, J = 17.6 Hz, J =
5.0 Hz, =CH), 7.08 (d, 1H, J = 7.5 Hz, ArH), 7.29–7.33 (m,
2H, ArH), 7.49 (dt, 2H, J = 7.9 Hz, J = 3.0 Hz, ArH), 7.69
(dd, 1H, J = 6.9 Hz, J = 1.1 Hz, ArH), 7.79 (t, 1H, J =
8.0 Hz, ArH), 7.81 (dd, 1H, J = 6.8 Hz, J = 1.2 Hz, ArH),
8.01 (d, 1H, J = 8.8 Hz, ArH), 8.11 (d, 1H, J = 7.9 Hz,
ArH). MS m/z: 316 (M+). Anal. calcd. for C21H16O3: C,
79.73; H, 5.10. Found: C, 79.86; H, 4.89.
General methods for the synthesis of macrolides 7a–7f
To a solution of the substrate 6a (30 mg, 0.16 mmol) in dry
degassed dichloromethane (40 mL) under nitrogen atmos-
phere was added Grubbs second-generation catalyst (5 mol%,
17 mg) and the reaction was stirred at rt for 1 h. The mixture
was then refluxed for 2 days. The solvent was distilled off and
the residue was purified by flash column chromatography on
silica gel using 10% ethyl acetate-petroleum ether to afford
the compound 7a. Accordingly compounds 7b-7f were
synthesized. Compounds 7a-7f were recrystallized from
dichloromethane-petroleum ether (60–80 8C).
Compound 7e
Yield: 57%; colourless solid; mp 113–114 8C (dichloro-
methane–petroleum ether). IR (KBr, cm–1): 1731, 2851,
1
2921. H NMR (CDCl3, 400 MHz) dH: 3.47 (dd, 2H, J =
Compound 7a
5.7 Hz, J = 1.0 Hz, CH2), 4.62 (dd, 2H, J = 7.3 Hz, J =
1.0 Hz, OCH2), 6.00 (dt, 1H, J = 17.6 Hz, J = 5.0 Hz,
=CH), 6.09 (dt, 1H, J = 17.6 Hz, J = 5.0 Hz, =CH), 7.00
(d, 1H, J = 6.8 Hz, ArH) 7.08 (d, 1H, J = 7.3 Hz, ArH),
7.38–7.43 (m, 3H, ArH), 7.51 (dd, 2H, J = 8.8 Hz, J =
1.7 Hz, ArH), 7.85 (dt, 1H, J = 7.1 Hz, J = 3.0 Hz, ArH),
8.14 (d, 2H, J = 8.0 Hz, ArH). MS m/z: 316 (M+). Anal.
calcd. for C21H16O3: C, 79.73; H, 5.10. Found: C, 79.69; H,
5.33.
Yield: 62%; colourless solid; mp 104–105 8C (dichloro-
methane–petroleum ether). IR (KBr, cm–1): 1740, 2851,
1
2957. H NMR (CDCl3, 400 MHz) dH: 4.04 (d, 2H, J =
5.0 Hz, CH2), 4.59 (d, 2H, J = 5.0 Hz, OCH2), 5.96 (dt, 1H,
J = 17.6 Hz, J = 5.0 Hz, =CH), 6.09 (dt, 1H, J = 17.6 Hz,
J = 5.0 Hz, =CH), 6.94 (d, 1H, J = 6.8 Hz, ArH), 7.02 (dt,
1H, J = 6.0 Hz, J = 3.1 Hz, ArH), 7.30 (d, 1H, J = 7.1 Hz,
ArH), 7.45–7.55 (m, 3H, ArH), 7.76 (d, 1H, J = 7.1 Hz,
ArH), 7.84 (dd, 1H, J = 7.1 Hz, J = 1.4 Hz, ArH), 7.89 (d, 1H,
J = 6.6 Hz, ArH), 8.07 (d, 1H, J = 7.3 Hz, ArH). 13C NMR
(CDCl3, 100 MHz) dC: 29.1, 70.1, 112.9, 120.4, 120.7, 121.9,
124.2, 125.2, 125.3, 125.9, 126.4, 128.0, 128.7, 131.8, 132.1,
132.8, 133.6, 133.9, 146.5, 157.6, 166.9. HRMS: Calcd. for
C21H16O3: 339.0997 (M + Na). Found: 339.0990 (M + Na).
Compound 7f
Yield: 59%; colourless solid; mp 157–158 8C (dichloro-
methane–petroleum ether). IR (KBr, cm–1): 1650, 1705,
1
1734, 2851, 2921. H NMR (CDCl3, 400 MHz) dH: 3.36
(d, 2H, J = 5.6 Hz, CH2), 3.38 (s, 3H, –NCH3), 3.45 (s,
3H, –NCH3), 5.17 (d, 2H, J = 5.6 Hz, OCH2), 5.80 (dt,
1H, J = 17.6 Hz, J = 5.0 Hz, =CH), 6.03 (dt, 1H, J =
17.6 Hz, J = 5.0 Hz, =CH), 6.95 (d, 2H, J = 7.7 Hz, J =
1.7 Hz, ArH), 8.09 (dd, 2H, J = 8.9 Hz, J = 3.0 Hz, ArH).
MS m/z: 328 (M+). Anal. calcd. for C17H16N2O5: C, 62.19;
H, 4.91; N, 8.53. Found: C, 61.97; H, 5.11; N, 8.69.
Compound 7b
Yield: 59%; colourless solid; mp 96–97 8C (dichlorome-
thane–petroleum ether). IR (KBr, cm–1): 1742, 2850, 2921.
1H NMR (CDCl3, 400 MHz) dH: 3.49 (d, 2H, J = 5.0 Hz,
CH2), 4.63 (d, 2H, J = 5.0 Hz, OCH2), 5.85 (dt, 1H, J =
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