A COPPER-CATALYZED METHOD AND APPLICATION FOR PREPARING ALDEHYDES OR KETONES BY OXIDIZING ALCOHOLS WITH OXYGEN AS AN OXIDANT

Abstract

The present invention discloses a method for preparing aldehydes or ketones via aerobic oxidation of alcohols with the copper salts and nitroxide radicals as catalysts. Both oxygen and air could be used as oxidants, after 4 to 48 hours of reaction in an organic solvent at room temperature, the alcohols are efficiently oxidized to the corresponding aldehydes or ketones. The present invention has the following advantages: easy to operate, refraining from using chlorides which are corrosive to equipment, readily available raw materials and reagents, mils reaction conditions, the broad substrate scope, good functional group tolerance, convenient purification, environmentally friendly and no pollution. Thus, the method is suitable for industrial production.

Claims

1. A copper-catalyzed method for preparing aldehydes or ketones by oxidizing alcohols with oxygen as an oxidant, wherein, at 0-100° C., in an organic solvent, using the alcohol shown in formula (a) as raw material, oxygen or oxygen in the air is used as oxidant, copper salts and nitroxide radicals are used as catalysts, reacting 4-48 hours to oxidize the alcohol to produce aldehyde or ketone compounds shown in formula (b), the reaction process has the following reaction equation (1): ##STR00075## wherein, R.sup.1 and R.sup.2 is a hydrogen, an alkyl, an alkyl with functional groups, a cycloalkyl, a phenyl, an aryl, a heterocyclic group, an ethynyl, an alkynyl with functional groups, a vinyl, an alkenyl with functional groups, an allenyl, an allenyl with functional groups; the said aryl is phenyl, naphthyl, thiophene, furan, pyrrole with electron-donating or electron-withdrawing substituents at the ortho, meta, and para positions; the said heterocyclic group is thienyl, furyl or pyridyl, or thiophene, furan or pyridine with electron-donating or electron-withdrawing substituents.

2. The method of claim 1, wherein, R.sup.1 and R.sup.2 is a C1-C20 alkyl, a C1-C20 alkyl with functional groups, a C3-C8 cycloalkyl, a phenyl, an aryl, a heterocyclic group, an ethynyl, an alkynyl with functional groups, a vinyl, an alkenyl with functional groups, an allenyl, an allenyl with functional groups; the said heterocyclic group is thienyl, furyl or pyridyl, or thiophene, furan or pyridine with electron-donating or electron-withdrawing substituents; wherein, the C1-C20 alkyl with functional groups, said the functional group is selected from carbon-carbon double bond, carbon-carbon triple bond, ester group, acyl group, acyloxy group, amide group, halogen, carboxyl group, cyano group, phenyl, aryl, thienyl, furyl; the alkynyl with functional groups, the alkenyl with functional groups, and the allenyl with functional groups, said the functional group is selected from C1-C20 alkyl, C3-C6 cycloalkyl, carbon-carbon double bond, carbon-carbon triple bond, ester group, acyl group, acyloxy group, amide group, halogen, carboxyl group, cyano group, phenyl, aryl, thienyl, furyl, silicon group; wherein, the said aryl is phenyl, thiophene, furan, pyrrole with substituents at the ortho, meta, and para positions; the said substituent is selected from C1-C5 alkyl, ester group, hydroxyl group, acyl group, acyloxy group, nitro group, halogen, carboxyl group, cyano group, methoxyl group.

3. The method of claim 2, wherein, R1 and R2 is a C1-C20 alkyl, a C1-C20 alkyl with functional groups, a C3-C8 cycloalkyl, a phenyl, an aryl, a heterocyclic group, an ethynyl, an alkynyl with functional groups, a vinyl, an alkenyl with functional groups, an allenyl, an allenyl with functional groups; the said heterocyclic group is thienyl, furyl or pyridyl, or thiophene, furan or pyridine with electron-donating or electron-withdrawing substituents; wherein, the C1-C20 alkyl with functional groups, the said functional group is selected from carbon-carbon double bond, carbon-carbon triple bond, methoxycarbonyl, ethoxycarbonyl, formyl, acetyl, benzoyl, formyloxy, acetoxy, benzoyloxy, acetamide, benzamide, halogen, carboxyl group, cyano group, phenyl, aryl, thienyl, furyl; the alkynyl with functional groups, the alkenyl with functional groups, and the allenyl with functional groups, said the functional group is selected from C1-C20 alkyl, C3-C6 cycloalkyl, carbon-carbon double bond, carbon-carbon triple bond, methoxycarbonyl, ethoxycarbonyl, formyl, acetyl, benzoyl, formyloxy, acetoxy, benzoyloxy, acetamide, benzamide, halogen, carboxyl group, cyano group, phenyl, aryl, thienyl, furyl, silicon group; wherein, the said aryl is phenyl with substituents at the ortho, meta, and para positions; the said substituent is selected from C1-05 alkyl, methoxycarbonyl, ethoxycarbonyl, hydroxyl group, formyl, acetyl, benzoyl, formyloxy, acetoxy, benzoyloxy, nitro group, halogen, carboxyl group, cyano group, methoxyl group.

4. The method of claim 1, wherein, said the method comprises the following steps: 1) inserting an oxygen balloon into the dry reaction tube, pumping air three times, and adding a copper catalyst, a nitroxide radical, an alcohol organic solvent solution in sequence, or using air to supplement oxygen, or airflow, putting the reaction tube in the 25° C. oil bath and stirring for 4-48 hours; wherein, the organic solvent is based on the amount of alcohol shown in formula (a), and the dosage of the organic solvent is 1.0-10.0 mL/mmol; 2) after the completion of the reaction in step (1), raising the reaction tube from the oil bath, filtering the mixture with silica gel short column, washing with a certain amount of diethyl ether, concentrating, and subjecting to the flash column chromatography, so as to obtain the aldehyde or ketone compounds; said the diethyl ether is based on the amount of alcohol shown in formula (a), and the dosage of the diethyl ether is 3.75-75 mL/mmol.

5. The method of claim 1, wherein the organic solvent is any one or more of benzene, toluene, dichloromethane, 1,2-dichloroethane, 1,1-dichloroethane, 1,2-dichloropropane, 1,3-dichloropropane, nitromethane, diethyl ether, ethylene glycol dimethyl ether, tetrahydrofuran or acetonitrile.

6. The method of claim 1, wherein the organic solvent is based on the amount of alcohol shown in formula (a), and the dosage of the organic solvent is 1.0-10.0 mL/mmol.

7. The method of claim 1, wherein the copper salts are any one or more of tetrakiscopper hexa-fluorophosph, cuprous chloride, copper bromide, cuprous iodide, copper acetate or copper nitrate trihydrate.

8. The method of claim 1, wherein the copper salt is based on the amount of alcohol shown in formula (a), and the dosage of the copper salt is 0.025-0.1 mmol/mmol.

9. The method of claim 1, wherein the nitroxide radicals are any one or more of 2,2,6,6-tetramethylpiperidine oxide, 4-hydroxy-2,2,6,6-tetramethylpiperidine oxide, 4-methoxy-2,2,6,6-tetramethylpiperidine oxide, 4-acetylamino-2,2,6,6-tetramethylpiperidine oxide, 4-oxy-2,2,6,6-tetramethylpiperidine oxide, 4-amino-2,2,6,6-tetramethylpiperidine oxide, N-hydroxymaleimide, 9-azabicyclo [3.3.1] nonane nitroxide radical, 2-azaadamantane nitroxide radical.

10. The method of claim 1, wherein the nitroxide radical is based on the amount of alcohol shown in formula (a), and the dosage of the nitroxide radical is 0.025-0.1 mmol/mmol.

Description

EXAMPLE 1

[0026] ##STR00003##

[0027] An oxygen balloon was inserted into the dry reaction tube, pumped 02 for three times, Cu(NO.sub.3).sub.2.3H.sub.2O (24.6 mg, 0.1 mmol), TEMPO (16.2 mg, 0.1 mmol), and 1b (146.4 mg, 1.0 mmol) of MeCN solution (4 mL) were added sequentially. The reaction tube was stirred at 25° C. for 6 h. The mixture solution was filtered through a short column of silica gel (2 cm), and washed with ethyl ether, rotary evaporation to remove the solvent. The mixture solution was separated and purified by column chromatography on silica gel (eluent: petroleum ether/ethyl ether=60/1), to afford 2b (130.7 mg, 91%): white solid. Melting point: 44.2-44.7° C. (petroleum ether/ethyl acetate recrystallization); .sup.1H NMR (400 MHz, CDCl.sub.3): δ=8.06 (d, J=8.4 Hz, 2H, ArH), 7.29 (d, J=8.0 Hz, 2H, ArH), 3.40 (s, 3H, CH.sub.3), 2.44 (s, 1H, CH); .sup.13C NMR (100 MHz, CDCl.sub.3): δ=177.0, 145.7, 133.8, 129.8, 129.4, 80.34, 80.28, 21.8; MS (70 eV, EI) m/z (%): 144 (M.sup.+, 74.75), 115 (100); IR (neat): ν=3257, 2090, 1632, 1594, 1459, 1404, 1310, 1246, 1167, 1117 cm.sup.−1.

EXAMPLE 2

[0028] ##STR00004##

[0029] Operations were conducted by referring to Example 1. Cu(NO.sub.3).sub.2.3H.sub.2O (24.0 mg, 0.1 mmol), TEMPO (16.1 mg, 0.1 mmol), 1c (161.8 mg, 1.0 mmol), MeCN (4 mL), reacted 12.5 hours to afford 2c (134.0 mg, 84%) (eluent: petroleum ether/ethyl acetate=30/1): oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): δ=8.06 (dd, J.sub.1=7.8 Hz, J.sub.2=1.8 Hz, 1H, ArH), 7.55 (td, J.sub.1=8.0 Hz, J.sub.2=1.8 Hz, 1H, ArH), 7.07-6.97 (m, 2H, ArH), 3.94 (s, 3H, CH.sub.3), 3.37 (s, 1H, CH); .sup.13C NMR (100 MHz, CDCl.sub.3): δ=175.8, 159.8, 135.4, 132.9, 125.5, 120.1, 112.0, 81.9, 79.5, 55.6; MS (70 eV, EI) m/z (%): 161 (M.sup.++1, 7.26), 160 (M.sup.+, 64.37), 131 (100); IR (neat): ν=3234, 2089, 1647, 1595, 1573, 1484, 1462, 1434, 1286, 1253, 1224, 1164, 1116, 1019 cm.sup.−1.

EXAMPLE 3

[0030] ##STR00005##

[0031] Operations were conducted by referring to Example 1. Cu(NO.sub.3).sub.2.3H.sub.2O (24.1 mg, 0.1 mmol), TEMPO (16.3 mg, 0.1 mmol), 1d (162.2 mg, 1.0 mmol), MeCN (4 mL), reacted 13 hours to afford 2d (142.6 mg, 89%) (eluent: petroleum ether/ethyl acetate=30/1): oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): δ=7.80 (d, J=7.6 Hz, 1H, ArH), 7.64 (s, 1H, ArH), 7.42 (t, J=8.0 Hz, 1H, ArH), 7.19 (dd, J.sub.1=8.4 Hz, J.sub.2=2.0 Hz, 1H, ArH), 3.87 (s, 3H, CH.sub.3), 3.43 (s, 1H, CH); .sup.13C NMR (100 MHz, CDCl.sub.3): δ=177.1, 159.8, 137.4, 129.7, 122.9, 121.4, 112.8, 80.6, 80.3, 55.4; MS (70 eV, EI) m/z (%): 161 (M.sup.++1, 11.54), 160 (M.sup.+, 100); IR (neat): ν=3250, 2094, 1644, 1595, 1581, 1485, 1429, 1323, 1264, 1207, 1177, 1021, 1012 cm.sup.−1.

EXAMPLE 4

[0032] ##STR00006##

[0033] Operations were conducted by referring to Example 1. Cu(NO.sub.3).sub.2.3H.sub.2O (24.6 mg, 0.1 mmol), TEMPO (16.0 mg, 0.1 mmol), 1e (161.8 mg, 1.0 mmol), MeCN (4 mL), reacted 6 hours to afford 2e (143.6 mg, 90%) (eluent: petroleum ether/ethyl acetate=25/1): white solid. Melting point: 85.5-86.5° C. (petroleum ether/ethyl acetate recrystallization); .sup.1H NMR (400 MHz, CDCl.sub.3): δ=8.13 (d, J=9.2 Hz, 2H, ArH), 6.97 (d, J=8.8 Hz, 2H, ArH), 3.90 (s, 3H, CH.sub.3), 3.38 (s, 1H, CH); .sup.13C NMR (100 MHz, CDCl.sub.3): δ=175.8, 164.7, 132.0, 129.4, 113.8, 80.3, 80.1, 55.5; MS (70 eV, EI) m/z (%): 161 (M.sup.++1, 11.17), 160 (M.sup.+, 100); IR (neat): ν=3248, 2091, 1638, 1596, 1570, 1507, 1421, 1254, 1168, 1116, 1022, 1008 cm.sup.−1.

EXAMPLE 5

[0034] ##STR00007##

[0035] Operations were conducted by referring to Example 1. Cu(NO.sub.3).sub.2.3H.sub.2O (24.0 mg, 0.1 mmol), TEMPO (15.8 mg, 0.1 mmol), 1f (190.2 mg, 1.0 mmol), MeCN (4 mL), reacted 12.5 hours to afford 2f (170.3 mg, 90%) (eluent: petroleum ether/ethyl acetate=30/1): white solid. Melting point: 117.0-118.3° C. (petroleum ether/ethyl acetate recrystallization); .sup.1H NMR (400 MHz, CDCl.sub.3): δ=8.22 (d, J=8.4 Hz, 2H, ArH), 8.16 (d, J=8.4 Hz, 2H, ArH), 3.97 (s, 3H, CH.sub.3), 3.53 (s, 1H, CH); .sup.13C NMR (100 MHz, CDCl.sub.3): δ=176.6, 165.9, 139.0, 135.0, 129.8, 129.4, 81.8, 80.0, 52.5; MS (70 eV, EI) m/z (%): 189 (M.sup.++1, 5.41), 188 (M.sup.+, 41.74), 157 (100); IR (neat): ν=3217, 2096, 1717, 1636, 1606, 1437, 1275, 1233, 1195, 1119, 1006 cm.sup.−1.

EXAMPLE 6

[0036] ##STR00008##

[0037] Operations were conducted by referring to Example 1. Cu(NO.sub.3).sub.2.3H.sub.2O (24.4 mg, 0.1 mmol), TEMPO (15.8 mg, 0.1 mmol), 1g (137.8 mg, 1.0 mmol), MeCN (4 mL), reacted 6 hours to afford 2g (118.4 mg, 87%) (eluent: petroleum ether/ethyl acetate=30/1): white solid. Melting point: 32.4-34.0° C. (petroleum ether/ethyl acetate recrystallization); .sup.1H NMR (400 MHz, CDCl.sub.3): δ=7.97 (dd, J.sub.1=3.8 Hz, J.sub.2=0.6 Hz, 1H, ArH), 7.75 (dd, J.sub.1=4.8 Hz, J.sub.2=0.8 Hz, 1H, ArH), 7.18 (t, J=4.2 Hz, 1H, ArH), 3.37 (s, 1H, CH); .sup.13C NMR (100 MHz, CDCl.sub.3): δ=169.0, 144.0, 136.1, 135.9, 128.4, 79.8, 79.3; MS (70 eV, EI) m/z (%): 136 (M.sup.+, 100), 108 (95.16); IR (neat): ν=3244, 3103, 2095, 1616, 1512, 1406, 1354, 1266, 1231, 1201, 1082, 1051 cm.sup.−1.

EXAMPLE 7

[0038] ##STR00009##

[0039] Operations were conducted by referring to Example 1. Cu(NO.sub.3).sub.2.3H.sub.2O (24.0 mg, 0.1 mmol), TEMPO (16.0 mg, 0.1 mmol), 1h (182.1 mg, 1.0 mmol), DCE (4 mL), reacted 8 hours to afford 2h (160.4 mg, 89%) (eluent: petroleum ether/ethyl ether=40/1): oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): δ=3.20 (s, 1H, CH), 2.58 (t, J=7.4 Hz, 2H, CH.sub.2), 1.73-1.60 (m, 2H, CH.sub.2), 1.40-1.16 (m, 12H, 6×CH.sub.2), 0.88 (t, J=6.8 Hz, 3H, CH.sub.3); .sup.13C NMR (100 MHz, CDCl.sub.3): δ=187.5, 81.4, 78.2, 45.4, 31.8, 29.3, 29.22, 29.17, 28.8, 23.7, 22.6, 14.0.

EXAMPLE 8

[0040] ##STR00010##

[0041] Operations were conducted by referring to Example 1. Cu(NO.sub.3).sub.2.3H.sub.2O (23.9 mg, 0.1 mmol), TEMPO (16.1 mg, 0.1 mmol), 1a (187.2 mg, 1.0 mmol), MeCN (4 mL), reacted 4 hours to afford 2a (177.4 mg, 96%) (eluent: petroleum ether/ethyl ether=30/1): oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): δ=8.14 (d, J=7.2 Hz, 2H, ArH), 7.60 (t, J=7.2 Hz, 1H, ArH), 7.48 (t, J=7.8 Hz, 2H, ArH), 2.51 (t, J=7.0 Hz, 2H, CH.sub.2), 1.74-1.58 (m, 2H, CH.sub.2), 1.58-1.42 (m, 2H, CH.sub.2), 0.97 (t, J=7.4 Hz, 3H, CH.sub.3); .sup.13C NMR (100 MHz, CDCl.sub.3): δ=178.2, 136.9, 133.8, 129.5, 128.4, 96.8, 79.6, 29.8, 22.0, 18.8, 13.4; MS (70 eV, EI) m/z (%): 186 (M.sup.+, 12.46), 144 (100); IR (neat): ν=2957, 2933, 2868, 2232, 2200, 1641, 1588, 1452, 1314, 1257, 1172 cm.sup.−1.

EXAMPLE 9

[0042] ##STR00011##

[0043] Operations were conducted by referring to Example 1. Cu(NO.sub.3).sub.2.3H.sub.2O (24.0 mg, 0.1 mmol), TEMPO (16.0 mg, 0.1 mmol), 1a (188.0 mg, 1.0 mmol), DCE (4 mL), reacted 7 hours to afford 2a (185.2 mg, 100%) (eluent: petroleum ether/ethyl ether=40/1): oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): δ=8.18-8.10 (m, 2H, ArH), 7.63-7.57 (m, 1H, ArH), 7.48 (t, J=7.8 Hz, 2H, ArH), 2.51 (t, J=7.0 Hz, 2H, CH.sub.2), 1.74-1.58 (m, 2H, CH.sub.2), 1.58-1.42 (m, 2H, CH.sub.2), 0.97 (t, J=7.6 Hz, 3H, CH.sub.3); .sup.13C NMR (100 MHz, CDCl.sub.3): δ=178.1, 136.8, 133.8, 129.4, 128.4, 96.7, 79.6, 29.7, 22.0, 18.8, 13.4.

EXAMPLE 10

[0044] ##STR00012##

[0045] Operations were conducted by referring to Example 1. Cu(NO.sub.3).sub.2.3H.sub.2O (24.2 mg, 0.1 mmol), TEMPO (15.8 mg, 0.1 mmol), 1i (172.2 mg, 1.0 mmol), MeCN (4 mL), reacted 7 hours to afford 2i (166.6 mg, 98%) (eluent: petroleum ether/ethyl ether=30/1): oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): δ=8.16-8.05 (m, 2H, ArH), 7.59 (t, J=7.4 Hz, 1H, ArH), 7.47 (t, J=7.6 Hz, 2H, ArH), 1.64-1.48 (m, 1H, CH), 1.12-0.96 (m, 4H, CH.sub.2CH.sub.2); .sup.13C NMR (100 MHz, CDCl.sub.3): δ=177.7, 136.8, 133.6, 129.2, 128.3, 101.0, 75.4, 9.7, −0.2; MS (70 eV, EI) m/z (%): 170 (M.sup.++1, 10.75), 170 (M.sup.+, 70.44), 141 (100); IR (neat): ν=2207, 1635, 1596, 1579, 1449, 1356, 1311, 1264, 1172, 1046, 1023 cm.sup.−1.

EXAMPLE 11

[0046] ##STR00013##

[0047] Operations were conducted by referring to Example 1. Cu(NO.sub.3).sub.2.3H.sub.2O (24.2 mg, 0.1 mmol), TEMPO (16.0 mg, 0.1 mmol), 1i (172.3 mg, 1.0 mmol), DCE (4 mL), reacted 6 hours to afford 2i (163.5 mg, 96%) (eluent: petroleum ether/ethyl ether=30/1): oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): δ=8.20-8.05 (m, 2H, ArH), 7.65-7.54 (m, 1H, ArH), 7.47 (t, J=7.6 Hz, 2H, ArH), 1.66-1.48 (m, 1H, CH), 1.13-0.94 (m, 4H, CH.sub.2CH.sub.2); .sup.13C NMR (100 MHz, CDCl.sub.3): δ=177.8, 136.8, 133.6, 129.3, 128.3, 101.0, 75.4, 9.8, −0.1.

EXAMPLE 12

[0048] ##STR00014##

[0049] Operations were conducted by referring to Example 1. Cu(NO.sub.3).sub.2.3H.sub.2O (24.4 mg, 0.1 mmol), TEMPO (16.1 mg, 0.1 mmol), 1j (209.8 mg, 1.0 mmol), MeCN (4 mL), reacted 7 hours to afford 2j (203.4 mg, 98%) (eluent: petroleum ether/ethyl ether=30/1): white solid. Melting point: 45.3-46.6° C. (petroleum ether/ethyl acetate recrystallization); .sup.1H NMR (400 MHz, CDCl.sub.3): δ=8.23 (d, J=7.6 Hz, 2H, ArH), 7.70 (d, J=6.8 Hz, 2H, ArH), 7.64 (t, J=7.4 Hz, 1H, ArH), 7.57-7.48 (m, 3H, CH.sub.3), 7.43 (t, J=7.2 Hz, 2H, ArH); .sup.13C NMR (100 MHz, CDCl.sub.3): δ=177.8, 136.7, 134.0, 132.9, 130.7, 129.4, 128.54, 128.48, 119.9, 93.0, 86.8; MS (70 eV, EI) m/z (%): 206 (M.sup.+, 65.85), 178 (100); IR (neat): ν=2195, 1637, 1597, 1579, 1488, 1447, 1313, 1282, 1207, 1171, 1031, 1010 cm.sup.−1.

EXAMPLE 13

[0050] ##STR00015##

[0051] Operations were conducted by referring to Example 1. Cu(NO.sub.3).sub.2.3H.sub.2O (24.2 mg, 0.1 mmol), TEMPO (15.9 mg, 0.1 mmol), 1k (204.8 mg, 1.0 mmol), MeCN (4 mL), reacting 6 hours to afford 2k (197.2 mg, 97%) (eluent: petroleum ether/ethyl ether=60/1): oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): δ=8.15 (d, J=7.2 Hz, 2H, ArH), 7.62 (t, J=7.4 Hz, 1H, ArH), 7.50 (t, J=7.6 Hz, 2H, ArH), 0.33 (s, 9H, 3×CH.sub.3); .sup.13C NMR (100 MHz, CDCl.sub.3): δ=177.6, 136.4, 134.1, 129.6, 128.5, 100.8, 100.5, −0.8.

EXAMPLE 14

[0052] ##STR00016##

[0053] Operations were conducted by referring to Example 1. Cu(NO.sub.3).sub.2.3H.sub.2O (24.4 mg, 0.1 mmol), TEMPO (15.9 mg, 0.1 mmol), 1k (204.1 mg, 1.0 mmol), DCE (4 mL), reacted 10.5 hours to afford 2k (191.5 mg, 95%) (eluent: petroleum ether/ethyl ether=60/1): oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): δ=8.20-8.10 (m, 2H, ArH), 7.62 (t, J=7.6 Hz, 1H, ArH), 7.49 (t, J=7.6 Hz, 2H, ArH), 0.33 (s, 9H, 3×CH.sub.3); .sup.13C NMR (100 MHz, CDCl.sub.3): δ=177.6, 136.4, 134.1, 129.6, 128.5, 100.8, 100.5, −0.7.

EXAMPLE 15

[0054] ##STR00017##

[0055] Operations were conducted by referring to Example 1. Cu(NO.sub.3).sub.2.3H.sub.2O (24.4 mg, 0.1 mmol), TEMPO (16.0 mg, 0.1 mmol), 1l (222.8 mg, 1.0 mmol), MeCN (4 mL), reacted 4 hours to afford 21 (213.9 mg, 97%) (eluent: petroleum ether/ethyl ether=30/1): oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): δ=8.10 (t, J=1.8 Hz, 1H, ArH), 8.02 (d, J=7.6 Hz, 1H, ArH), 7.57 (dt, J.sub.1=7.6 Hz, J.sub.1=1.2 Hz, 1H, ArH), 7.43 (t, J=7.8 Hz, 1H, ArH), 2.52 (t, J=7.0 Hz, 2H, CH.sub.2), 1.74-1.60 (m, 2H, CH.sub.2), 1.58-1.44 (m, 2H, CH.sub.2), 0.97 (t, J=7.4 Hz, 3H, CH.sub.3); .sup.13C NMR (100 MHz, CDCl.sub.3): δ=176.6, 138.3, 134.7, 133.6, 129.8, 129.3, 127.5, 97.7, 79.2, 29.6, 22.0, 18.8, 13.4; MS (70 eV, EI) m/z (%): 222 (M.sup.+ (.sup.37C1), 10.02), 220 (M.sup.+ (.sup.35C1), 29.95), 139 (100); IR (neat): ν=2959, 2933, 2871, 2204, 1645, 1571, 1424, 1286, 1245 cm.sup.−1; HRMS calcd for C.sub.13H.sub.13O.sup.35Cl [M.sup.+]: 220.0655, found: 220.0657.

EXAMPLE 16

[0056] ##STR00018##

[0057] Operations were conducted by referring to Example 1. Cu(NO.sub.3).sub.2.3H.sub.2O (24.0 mg, 0.1 mmol), TEMPO (15.9 mg, 0.1 mmol), 1l (222.5 mg, 1.0 mmol), DCE (4 mL), reacted 23 hours to afford 21 (216.2 mg, 98%) (eluent: petroleum ether/ethyl ether=30/1): oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): δ=8.10 (t, J=1.8 Hz, 1H, ArH), 8.02 (d, J=7.6 Hz, 1H, ArH), 7.60-7.53 (m, 1H, ArH), 7.42 (t, J=7.8 Hz, 1H, ArH), 2.52 (t, J=7.0 Hz, 2H, CH.sub.2), 1.74-1.60 (m, 2H, CH.sub.2), 1.58-1.44 (m, 2H, CH.sub.2), 0.98 (t, J=7.4 Hz, 3H, CH.sub.3); .sup.13C NMR (100 MHz, CDCl.sub.3): δ=176.6, 138.4, 134.7, 133.6, 129.8, 129.3, 127.5, 97.7, 79.2, 29.7, 22.0, 18.8, 13.4.

EXAMPLE 17

[0058] ##STR00019##

[0059] Operations were conducted by referring to Example 1. Cu(NO.sub.3).sub.2.3H.sub.2O (24.4 mg, 0.1 mmol), TEMPO (16.0 mg, 0.1 mmol), 1m (266.2 mg, 1.0 mmol), MeCN (4 mL), reacted 6 hours to afford 2m (257.4 mg, 97%) (eluent: petroleum ether/ethyl ether=30/1): oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): δ=8.00 (d, J=7.6 Hz, 1H, ArH), 7.67 (d, J=8.0 Hz, 1H, ArH), 7.47-7.31 (m, 2H, ArH), 2.48 (t, J=7.0 Hz, 2H, CH.sub.2), 1.70-1.56 (m, 2H, CH.sub.2), 1.55-1.41 (m, 2H, CH.sub.2), 0.95 (t, J=7.4 Hz, 3H, CH.sub.3); .sup.13C NMR (100 MHz, CDCl.sub.3): δ=177.5, 137.4, 134.8, 133.0, 132.7, 127.2, 120.9, 98.0, 80.6, 29.5, 22.0, 18.9, 13.4; MS (70 eV, EI) m/z (%): 266 (M.sup.+ (.sup.81Br), 9.56), 264 (M.sup.+ (.sup.79Br), 9.29), 185 (100); IR (neat): ν=2187, 1648, 1580, 1474, 1386, 1262, 1063, 1008 cm.sup.−1.

EXAMPLE 18

[0060] ##STR00020##

[0061] Operations were conducted by referring to Example 1. Cu(NO.sub.3).sub.2.3H.sub.2O (24.4 mg, 0.1 mmol), TEMPO (16.0 mg, 0.1 mmol), 1m (267.2 mg, 1.0 mmol), DCE (4 mL), reacted 4.5 hours to afford 2m (260.6 mg, 98%) (eluent: petroleum ether/ethyl ether=30/1): oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): δ=8.00 (dd, J.sub.1=8.0 Hz, J.sub.2=1.6 Hz, 1H, ArH), 7.67 (d, J=8.0 Hz, 1H, ArH), 7.42 (td, J.sub.1=7.2 Hz, J.sub.2=1.2 Hz, 1H, ArH), 7.35 (td, J.sub.1=7.6 Hz, J.sub.2=1.6 Hz, 1H, ArH), 2.48 (t, J=7.0 Hz, 2H, CH.sub.2), 1.70-1.56 (m, 2H, CH.sub.2), 1.55-1.41 (m, 2H, CH.sub.2), 0.95 (t, J=7.2 Hz, 3H, CH.sub.3); .sup.13C NMR (100 MHz, CDCl.sub.3): δ=177.5, 137.3, 134.7, 133.0, 132.7, 127.1, 120.8, 97.9, 80.6, 29.5, 21.9, 18.9, 13.4.

EXAMPLE 19

[0062] ##STR00021##

[0063] Operations were conducted by referring to Example 1. Cu(NO.sub.3).sub.2.3H.sub.2O (24.4 mg, 0.1 mmol), TEMPO (16.0 mg, 0.1 mmol), 1n (222.8 mg, 1.0 mmol), MeCN (4 mL), reacted 4 hours to afford 2n (214.3 mg, 100%) (eluent: petroleum ether/ethyl ether=20/1): oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): δ=8.11 (d, J=8.4 Hz, 2H, ArH), 6.95 (d, J=8.4 Hz, 2H, ArH), 3.89 (s, 3H, CH.sub.3), 2.49 (t, J=7.2 Hz, 2H, CH.sub.2), 1.72-1.56 (m, 2H, CH.sub.2), 1.54-1.46 (m, 2H, CH.sub.2), 0.97 (t, J=7.2 Hz, 3H, CH.sub.3); .sup.13C NMR (100 MHz, CDCl.sub.3): δ=176.8, 164.2, 131.8, 130.2, 113.6, 95.8, 79.5, 55.4, 29.8, 22.0, 18.7, 13.4.

EXAMPLE 20

[0064] ##STR00022##

[0065] Operations were conducted by referring to Example 1. Cu(NO.sub.3).sub.2.3H.sub.2O (24.4 mg, 0.1 mmol), TEMPO (16.0 mg, 0.1 mmol), 1n (218.5 mg, 1.0 mmol), DCE (4 mL), reacted 4 hours to afford 2n (209.6 mg, 97%) (eluent: petroleum ether/ethyl ether=30/1 (300 mL), petroleum ether/ethyl ether=15/1): oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): δ=8.11 (d, J=8.8 Hz, 2H, ArH), 6.95 (d, J=8.8 Hz, 2H, ArH), 3.89 (s, 3H, CH.sub.3), 2.49 (t, J=7.6 Hz, 2H, CH.sub.2), 1.72-1.58 (m, 2H, CH.sub.2), 1.56-1.44 (m, 2H, CH.sub.2), 0.96 (t, J=7.4 Hz, 3H, CH.sub.3); .sup.13C NMR (100 MHz, CDCl.sub.3): δ=176.9, 164.2, 131.8, 130.2, 113.6, 95.8, 79.5, 55.4, 29.8, 22.0, 18.7, 13.4.

EXAMPLE 21

[0066] ##STR00023##

[0067] Operations were conducted by referring to Example 1. Cu(NO.sub.3).sub.2.3H.sub.2O (24.2 mg, 0.1 mmol), TEMPO (15.9 mg, 0.1 mmol), 1o (246.3 mg, 1.0 mmol), MeCN (4 mL), reacted 5 hours to afford 2o (243.0 mg, 99%) (eluent: petroleum ether/ethyl ether=20/1): oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): δ=8.19 (d, J=8.8 Hz, 2H, ArH), 8.13 (d, J=8.8 Hz, 2H, ArH), 3.96 (s, 3H, CH.sub.3), 2.53 (t, J=7.2 Hz, 2H, CH.sub.2), 1.73-1.62 (m, 2H, CH.sub.2), 1.58-1.45 (m, 2H, CH.sub.2), 0.98 (t, J=7.4 Hz, 3H, CH.sub.3); .sup.13C NMR (100 MHz, CDCl.sub.3): δ=177.1, 165.9, 139.8, 134.3, 129.5, 129.2, 97.9, 79.4, 52.3, 29.6, 21.9, 18.8, 13.3; MS (70 eV, EI) m/z (%): 244 (M.sup.+, 14.91), 202 (100); IR (neat): ν=2956, 2933, 2872, 2237, 2198, 1724, 1646, 1435, 1407, 1276, 1259, 1244, 1116, 1102, 1017 cm.sup.−1; HRMS calcd. for C.sub.15H.sub.16O.sub.3 (M.sup.+): 244.1099; Found: 244.1099.

EXAMPLE 22

[0068] ##STR00024##

[0069] Operations were conducted by referring to Example 1. Cu(NO.sub.3).sub.2.3H.sub.2O (24.2 mg, 0.1 mmol), TEMPO (16.0 mg, 0.1 mmol), 1p (224.2 mg, 1.0 mmol), DCE (4 mL), reacted 8 hours to afford 2p (180.1 mg, 81%) (eluent: petroleum ether/ethyl ether=60/1): yellow solid. Melting point: 64.0-65.6° C. (petroleum ether/ethyl acetate recrystallization); .sup.1H NMR (400 MHz, CDCl.sub.3): δ=11.75 (s, 1H, OH), 8.13 (d, J=8.4 Hz, 1H, ArH), 7.76-7.64 (m, 2H, ArH), 7.58-7.38 (m, 4H, ArH), 7.00 (t, J=8.0 Hz, 2H, ArH); .sup.13C NMR (100 MHz, CDCl.sub.3): δ=182.2, 162.7, 137.1, 133.1, 133.0, 131.1, 128.7, 120.7, 119.6, 119.4, 118.1, 96.0, 85.6.

EXAMPLE 23

[0070] ##STR00025##

[0071] Operations were conducted by referring to Example 1. Cu(NO.sub.3).sub.2.3H.sub.2O (24.1 mg, 0.1 mmol), TEMPO (16.0 mg, 0.1 mmol), 1q (213.0 mg, 1.0 mmol), MeCN (4 mL), reacted 6 hours to afford 2q (194.8 mg, 92%) (eluent: petroleum ether/ethyl ether=20/1): oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): δ=8.42 (s, 1H, ArH), 8.34 (dd, J.sub.1=8.0 Hz, J.sub.2=1.2 Hz, 1H, ArH), 7.87 (d, J=7.6 Hz, 1H, ArH), 7.63 (t, J=7.8 Hz, 1H, ArH), 2.55 (t, J=7.0 Hz, 2H, CH.sub.2), 1.75-1.63 (m, 2H, CH.sub.2), 1.62-1.45 (m, 2H, CH.sub.2), 0.98 (t, J=7.2 Hz, 3H, CH.sub.3); .sup.13C NMR (100 MHz, CDCl.sub.3): δ=175.6, 137.4, 136.5, 133.1, 132.9, 129.5, 117.7, 112.9, 98.9, 78.8, 29.5, 21.9, 18.8, 13.3; MS (70 eV, EI) m/z (%): 211 (M.sup.+, 7.31), 169 (100); IR (neat): ν=2959, 2933, 2872, 2219, 2200, 1647, 1598, 1579, 1465, 1427, 1292, 1265, 1180 cm.sup.−1; HRMS calcd. for C.sub.14H.sub.13NO (M.sup.+): 211.0997; Found: 211.0993.

EXAMPLE 24

[0072] ##STR00026##

[0073] Operations were conducted by referring to Example 1. Cu(NO.sub.3).sub.2.3H.sub.2O (24.4 mg, 0.1 mmol), TEMPO (15.7 mg, 0.1 mmol), 1r (233.3 mg, 1.0 mmol), MeCN (4 mL), reacted 7 hours to afford 2r (223.7 mg, 97%) (eluent: petroleum ether/ethyl ether=40/1): oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): δ=8.33 (d, J=9.2 Hz, 2H, ArH), 8.29 (d, J=9.2 Hz, 2H, ArH), 2.55 (t, J=7.0 Hz, 2H, CH.sub.2), 1.73-1.64 (m, 2H, CH.sub.2), 1.56-1.46 (m, 2H, CH.sub.2), 0.98 (t, J=7.2 Hz, 3H, CH.sub.3); .sup.13C NMR (100 MHz, CDCl.sub.3): δ=175.8, 150.6, 140.9, 130.2, 123.5, 99.3, 79.2, 29.5, 21.9, 18.8, 13.3; MS (70 eV, EI) m/z (%): 231 (M.sup.+, 4.21), 189 (100); IR (neat): ν=2959, 2934, 2871, 2237, 2199, 1650, 1602, 1524, 1343, 1320, 1257, 1104 cm.sup.−1.

EXAMPLE 25

[0074] ##STR00027##

[0075] Operations were conducted by referring to Example 1. Cu(NO.sub.3).sub.2.3H.sub.2O (24.2 mg, 0.1 mmol), TEMPO (16.0 mg, 0.1 mmol), is (177.8 mg, 1.0 mmol), MeCN (4 mL), reacted 10 hours to afford 2s (162.5 mg, 92%) (eluent: petroleum ether/ethyl ether=10/1): oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): δ=7.65 (s, 1H, H from furyl), 7.32 (d, J=3.2 Hz, 1H, H from furyl), 6.56 (dd, J.sub.1=3.6 Hz, J.sub.2=1.6 Hz, 1H, H from furyl), 2.47 (t, J=7.0 Hz, 2H, CH.sub.2), 1.74-1.58 (m, 2H, CH.sub.2), 1.56-1.42 (m, 2H, CH.sub.2), 0.96 (t, J=7.2 Hz, 3H, CH.sub.3); .sup.13C NMR (100 MHz, CDCl.sub.3): δ=164.9, 153.1, 147.6, 120.6, 112.4, 95.4, 78.8, 29.5, 21.8, 18.6, 13.3; MS (70 eV, EI) m/z (%): 176 (M.sup.+, 27.69), 95 (100); IR (neat): ν=2957, 2933, 2868, 2251, 2207, 1631, 1562, 1460, 1390, 1294, 1168, 1123, 1014 cm.sup.−1.

EXAMPLE 26

[0076] ##STR00028##

[0077] Operations were conducted by referring to Example 1. Cu(NO.sub.3).sub.2.3H.sub.2O (24.0 mg, 0.1 mmol), TEMPO (16.0 mg, 0.1 mmol), is (178.5 mg, 1.0 mmol), DCE (4 mL), reacted 10 hours to afford 2s (168.0 mg, 95%) (eluent: petroleum ether/ethyl ether=15/1): oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): δ=7.64 (s, 1H, H from furyl), 7.31 (d, J=3.2 Hz, 1H, H from furyl), 6.56 (t, J=1.6 Hz, 1H, H from furyl), 2.47 (t, J=7.0 Hz, 2H, CH.sub.2), 1.70-1.56 (m, 2H, CH.sub.2), 1.56-1.43 (m, 2H, CH.sub.2), 0.96 (t, J=7.2 Hz, 3H, CH.sub.3); .sup.13C NMR (100 MHz, CDCl.sub.3): δ=164.4, 152.7, 147.2, 120.1, 111.9, 94.9, 78.4, 29.1, 21.4, 18.2, 12.9.

EXAMPLE 27

[0078] ##STR00029##

[0079] Operations were conducted by referring to Example 1. Cu(NO.sub.3).sub.2.3H.sub.2O (23.8 mg, 0.1 mmol), TEMPO (15.9 mg, 0.1 mmol), 1t (169.1 mg, 1.0 mmol), MeCN (4 mL), reacted 9.5 hours to afford 2t (160.1 mg, 96%) (eluent: petroleum ether/ethyl ether=60/1): oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): δ=2.53 (t, J=7.4 Hz, 2H, CH.sub.2), 2.37 (t, J=7.0 Hz, 2H, CH.sub.2), 1.70-1.50 (m, 4H, CH.sub.2CH.sub.2), 1.50-1.25 (m, 4H, CH.sub.2CH.sub.2), 1.00-0.86 (m, 6H, 2×CH.sub.3); .sup.13C NMR (100 MHz, CDCl.sub.3): δ=188.3, 94.0, 80.7, 45.1, 29.6, 26.1, 22.0, 21.8, 18.4, 13.6, 13.3.

EXAMPLE 28

[0080] ##STR00030##

[0081] Operations were conducted by referring to Example 1. Cu(NO.sub.3).sub.2.3H.sub.2O (24.0 mg, 0.1 mmol), TEMPO (16.0 mg, 0.1 mmol), 1t (168.6 mg, 1.0 mmol), DCE (4 mL), reacted 9 hours to afford 2t (158.8 mg, 95%) (eluent: petroleum ether/ethyl ether=40/1): oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): δ=2.53 (t, J=7.4 Hz, 2H, CH.sub.2), 2.37 (t, J=7.0 Hz, 2H, CH.sub.2), 1.70-1.50 (m, 4H, CH.sub.2—CH.sub.2), 1.50-1.17 (m, 4H, CH.sub.2—CH.sub.2), 0.98-0.88 (m, 6H, 2×CH.sub.3); .sup.13C NMR (100 MHz, CDCl.sub.3): δ=188.4, 94.1, 80.8, 45.2, 29.7, 26.1, 22.0, 21.9, 18.5, 13.7, 13.4.

EXAMPLE 29

[0082] ##STR00031##

[0083] Operations were conducted by referring to Example 1. Cu(NO.sub.3).sub.2.3H.sub.2O (24.0 mg, 0.1 mmol), TEMPO (15.9 mg, 0.1 mmol), 1u (188.4 mg, 1.0 mmol), MeCN (4 mL), reacted 12 hours to afford 2u (173.2 mg, 93%) (eluent: petroleum ether/ethyl ether=30/1): oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): δ=7.58 (d, J=7.2 Hz, 2H, ArH), 7.50-7.34 (m, 3H, ArH), 2.67 (t, J=7.2 Hz, 2H, CH.sub.2), 1.80-1.66 (m, 2H, CH.sub.2), 1.48-1.32 (m, 2H, CH.sub.2), 0.95 (t, J=7.4 Hz, 3H, CH.sub.3); .sup.13C NMR (100 MHz, CDCl.sub.3): δ=188.2, 132.9, 130.5, 128.5, 120.0, 90.4, 87.8, 45.1, 26.1, 22.1, 13.7; MS (70 eV, EI) m/z (%): 186 (M.sup.+, 1.30), 129 (100); IR (neat): ν=2958, 2932, 2872, 2200, 1666, 1489, 1272, 1125, 1067 cm.sup.−1.

EXAMPLE 30

[0084] ##STR00032##

[0085] Operations were conducted by referring to Example 1. Cu(NO.sub.3).sub.2.3H.sub.2O (24.2 mg, 0.1 mmol), TEMPO (16.2 mg, 0.1 mmol), 1u (188.4 mg, 1.0 mmol), DCE (4 mL), reacted 11.5 hours to afford 2u (179.8 mg, 96%) (eluent: petroleum ether/ethyl ether=30/1): oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): δ=7.61-7.54 (m, 2H, ArH), 7.49-7.35 (m, 3H, ArH), 2.67 (t, J=7.4 Hz, 2H, CH.sub.2), 1.80-1.66 (m, 2H, CH.sub.2), 1.47-1.34 (m, 2H, CH.sub.2), 0.95 (t, J=7.2 Hz, 3H, CH.sub.3); .sup.13C NMR (100 MHz, CDCl.sub.3): 6=187.9, 132.8, 130.4, 128.4, 119.9, 90.3, 87.7, 45.0, 26.0, 21.9, 13.6.

EXAMPLE 31

[0086] ##STR00033##

[0087] Operations were conducted by referring to Example 1. Cu(NO.sub.3).sub.2.3H.sub.2O (24.1 mg, 0.1 mmol), TEMPO (16.0 mg, 0.1 mmol), 1v (214.1 mg, 1.0 mmol), MeCN (4 mL), reacted 17 hours to afford 2v (200.7 mg, 95%) (eluent: petroleum ether/ethyl ether=30/1): oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): δ=7.59 (d, J=7.2 Hz, 2H, ArH), 7.50-7.34 (m, 3H, ArH), 2.57-2.44 (m, 1H, CH), 2.06 (d, J=11.2 Hz, 2H, CH.sub.2), 1.82 (dd, J.sub.1=9.2 Hz, J.sub.2=3.6 Hz, 2H, CH.sub.2), 1.69 (d, J=12.0 Hz, 1H, one proton of CH.sub.2), 1.50 (dd, J.sub.1=23.2 Hz, J.sub.2=11.4 Hz, 2H, CH.sub.2), 1.42-1.16 (m, 3H, 3H from Cy); .sup.13C NMR (100 MHz, CDCl.sub.3): δ=191.3, 132.9, 130.5, 128.5, 120.1, 91.2, 87.1, 52.2, 28.2, 25.7, 25.3; MS (70 eV, EI) m/z (%): 212 (M.sup.+, 4.97), 129 (100); IR (neat): ν=2929, 2853, 2196, 1660, 1488, 1445, 1262, 1142, 1089, 1069 cm.sup.−1.

EXAMPLE 32

[0088] ##STR00034##

[0089] Operations were conducted by referring to Example 1. Cu(NO.sub.3).sub.2.3H.sub.2O (24.0 mg, 0.1 mmol), TEMPO (16.0 mg, 0.1 mmol), 1v (214.2 mg, 1.0 mmol), DCE (4 mL), reacted 8 hours to afford 2v (211.4 mg, 100%) (eluent: petroleum ether/ethyl ether=30/1): oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): δ=7.58 (d, J=7.2 Hz, 2H, ArH), 7.50-7.34 (m, 3H, ArH), 2.57-2.44 (m, 1H, CH), 2.06 (d, J=10.8 Hz, 2H, CH.sub.2), 1.89-1.76 (m, 2H, CH.sub.2), 1.74-1.16 (m, 6H, CH.sub.2CH.sub.2CH.sub.2); .sup.13C NMR (100 MHz, CDCl.sub.3): δ=191.3, 132.9, 130.4, 128.5, 120.1, 91.2, 87.1, 52.2, 28.2, 25.7, 25.3.

EXAMPLE 33

[0090] ##STR00035##

[0091] Operations were conducted by referring to Example 1. Cu(NO.sub.3).sub.2.3H.sub.2O (24.0 mg, 0.1 mmol), TEMPO (16.0 mg, 0.1 mmol), 1w (258.3 mg, 1.0 mmol), MeCN (4 mL), reacted 8 hours to afford 2w (244.7 mg, 95%) (eluent: petroleum ether/ethyl ether=60/1): white solid. Melting point: 93.0-94.7° C. (petroleum ether/ethyl acetate recrystallization); .sup.1H NMR (400 MHz, CDCl.sub.3): δ=9.24 (d, J=8.8 Hz, 1H, ArH), 8.65 (d, J=6.8 Hz, 1H, ArH), 8.10 (d, J=8.0 Hz, 1H, ArH), 7.92 (d, J=8.0 Hz, 1H, ArH), 7.80-7.38 (m, 8H, ArH); .sup.13C NMR (100 MHz, CDCl.sub.3): δ=179.6, 135.0, 134.5, 133.8, 132.9, 130.6, 130.5, 128.9, 128.6, 128.5, 126.7, 125.9, 124.4, 120.2, 91.6, 88.4; MS (70 eV, EI) m/z (%): 257 (M.sup.++1, 16.50), 256 (M.sup.+, 86.95), 255 (100); IR (neat): ν=2192, 1629, 1589, 1570, 1508, 1285, 1176, 1100, 1072 cm.sup.−1.

EXAMPLE 34

[0092] ##STR00036##

[0093] Operations were conducted by referring to Example 1. Cu(NO.sub.3).sub.2.3H.sub.2O (24.3 mg, 0.1 mmol), TEMPO (15.9 mg, 0.1 mmol), 1w (258.8 mg, 1.0 mmol), DCE (4 mL), reacted 5 hours to afford 2w (243.2 mg, 95%) (eluent: petroleum ether/ethyl ether=40/1): white solid. .sup.1H NMR (400 MHz, CDCl.sub.3): δ=9.24 (d, J=8.8 Hz, 1H, ArH), 8.65 (d, J=7.2 Hz, 1H, ArH), 8.09 (d, J=8.4 Hz, 1H, ArH), 7.91 (d, J=8.0 Hz, 1 H, ArH), 7.76-7.38 (m, 8H, ArH); .sup.13C NMR (100 MHz, CDCl.sub.3): δ=179.6, 135.0, 134.5, 133.8, 132.85, 132.82, 130.6, 130.5, 128.9, 128.6, 128.5, 126.7, 125.9, 124.4, 120.2, 91.6, 88.4.

EXAMPLE 35

[0094] ##STR00037##

[0095] Operations were conducted by referring to Example 1. Cu(NO.sub.3).sub.2.3H.sub.2O (23.7 mg, 0.1 mmol), TEMPO (16.0 mg, 0.1 mmol), 1x (211.0 mg, 1.0 mmol), MeCN (4 mL), reacted 8 hours to afford 2x (159.0 mg, 76%) (eluent: petroleum ether/ethyl ether=60/1): red solid. Melting point: 92.0-93.4° C. (petroleum ether/ethyl acetate recrystallization); .sup.1H NMR (400 MHz, CDCl.sub.3): δ=9.42 (s, 1H, CHO), 7.56 (d, J=8.8 Hz, 2H, ArH), 7.47 (d, J=8.0 Hz, 2H, ArH); .sup.13C NMR (100 MHz, CDCl.sub.3): δ=176.5, 134.4, 132.1, 126.2, 118.3, 93.5, 89.0; MS (70 eV, EI) m/z (%): 210 (M.sup.+ (.sup.81Br), 86.41), 208 (M.sup.+ (.sup.79Br), 86.47), 101 (100); IR (neat): ν=2949, 2866, 2203, 1649, 1578, 1460, 1427, 1284, 1238, 1030 cm.sup.−1.

EXAMPLE 36

[0096] ##STR00038##

[0097] Operations were conducted by referring to Example 1. Cu(NO.sub.3).sub.2.3H.sub.2O (24.2 mg, 0.1 mmol), TEMPO (16.0 mg, 0.1 mmol), 1x (211.2 mg, 1.0 mmol), DCE (4 mL), reacted 19 hours to afford 2x (135.8 mg, 65%) (eluent: petroleum ether/ethyl ether=60/1): red solid. .sup.1H NMR (400 MHz, CDCl.sub.3): δ=9.42 (s, 1H, CHO), 7.56 (d, J=8.0 Hz, 2H, ArH), 7.46 (d, J=8.0 Hz, 2H, ArH); .sup.13C NMR (100 MHz, CDCl.sub.3): δ=176.5, 134.5, 132.1, 126.2, 118.3, 93.5, 89.0.

EXAMPLE 37

[0098] ##STR00039##

[0099] Operations were conducted by referring to Example 1. Cu(NO.sub.3).sub.2.3H.sub.2O (24.2 mg, 0.1 mmol), TEMPO (16.0 mg, 0.1 mmol), 3a (187.6 mg, 1.0 mmol), DCE (4 mL), reacted 10 hours to afford 4a (164.4 mg, 93%, Z:E>99:1) (eluent: petroleum ether/ethyl ether=20/1) (before separation afforded a crude mixture Z:E=95:5, as determined by .sup.1H NMR analysis): oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): 10.05 (d, J=6.8 Hz, 1H, CHO), 7.42-7.28 (m, 5H, ArH), 6.64 (dt, J.sub.1=11.2 Hz, J.sub.2=5.6 Hz, 1H, CH═), 6.07 (ddt, J.sub.1=11.2 Hz, J.sub.2=6.4 Hz, J.sub.3=2.0 Hz, 1H, CH═), 4.59 (s, 2H, ArCH.sub.2), 4.53 (dd, J.sub.1=5.6 Hz, J.sub.2=2.0 Hz, 2H, OCH.sub.2); .sup.13C NMR (100 MHz, CDCl.sub.3): δ=191.4, 147.5, 137.2, 129.6, 128.5, 127.9, 127.7, 73.0, 66.9.

EXAMPLE 38

[0100] ##STR00040##

[0101] Operations were conducted by referring to Example 1. Cu(NO.sub.3).sub.2.3H.sub.2O (24.4 mg, 0.1 mmol), TEMPO (16.0 mg, 0.1 mmol), 3b (155.4 mg, 1.0 mmol), DCE (10 mL), reacted 14 hours to afford 4b (126.3 mg, 83%, E:Z=97:3) (eluent: petroleum ether/ethyl ether=50/1 (400 mL), petroleum ether/ethyl ether=20/1 (300 mL)) (before separation afforded a crude mixture E:Z=96:4, as determined by .sup.1H NMR analysis): oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): δ=10.00 (d, J=8.0 Hz, 1H, CHO), 5.88 (d, J=8.0 Hz, 1H, CH═), 5.08 (d, J=6.4 Hz, 1H, CH═), 2.30-2.16 (m, 4H, 2×CH.sub.2), 2.17 (s, 3H, CH.sub.3), 1.69 (s, 3H, CH.sub.3), 1.61 (s, 3H, CH.sub.3); .sup.13C NMR (100 MHz, CDCl.sub.3): δ=191.1, 163.6, 132.7, 127.2, 122.3, 40.4, 25.5, 25.4, 17.5, 17.3.

EXAMPLE 39

[0102] ##STR00041##

[0103] Operations were conducted by referring to Example 1. Cu(NO.sub.3).sub.2.3H.sub.2O (24.6 mg, 0.1 mmol), TEMPO (16.1 mg, 0.1 mmol), 3c (153.6 mg, 1.0 mmol), DCE (10 mL), reacted 30 hours to afford 4c (118.1 mg, 80%, Z:E=94:6) (eluent: petroleum ether/ethyl ether=15/1) (before separation afforded a crude mixture Z:E=93:7, as determined by .sup.1H NMR analysis): oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): δ=9.90 (d, J=8.4 Hz, 1H, CHO), 5.88 (d, J=8.4 Hz, 1H, CH═), 5.10 (t, J=7.0 Hz, 1H, CH═), 2.59 (t, J=7.6 Hz, 2H, CH.sub.2), 2.24 (dd, J.sub.1=14.6 Hz, J.sub.2=7.4 Hz, 2H, CH.sub.2), 1.99 (s, 3H, CH.sub.3), 1.69 (s, 3H, CH.sub.3), 1.61 (s, 3H, CH.sub.3); .sup.13C NMR (100 MHz, CDCl.sub.3): δ=190.2, 163.3, 133.1, 128.1, 121.8, 32.1, 26.5, 25.1, 24.5, 17.2; the following signals are discernible for E-4c: δ=190.8, 132.4, 126.9, 122.1, 40.1, 25.2, 17.1.

EXAMPLE 40

[0104] ##STR00042##

[0105] Operations were conducted by referring to Example 1. Cu(NO.sub.3).sub.2.3H.sub.2O (24.2 mg, 0.1 mmol), TEMPO (16.0 mg, 0.1 mmol), 3d (177.3 mg, 1.0 mmol), DCE (4 mL), reacted 10 hours to afford 4d (161.3 mg, 96%, E:Z>99:1) (eluent: petroleum ether/ethyl ether=50/1) (before separation afforded a crude mixture E:Z>99:1, as determined by .sup.1H NMR analysis): oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): δ=9.51 (d, J=8.0 Hz, 1H, CHO), 6.86 (dt, J.sub.1=15.8 Hz, J.sub.2=7.0 Hz, 1H, CH═), 6.18-6.07 (m, 1H, CH═), 2.38-2.27 (m, 2H, CH.sub.2), 1.56-1.44 (m, 2H, CH.sub.2), 1.40-1.20 (m, 10H, 5×CH.sub.2), 0.89 (t, J=6.8 Hz, 3H, CH.sub.3); .sup.13C NMR (100 MHz, CDCl.sub.3): δ=194.0, 158.9, 132.9, 32.6, 31.7, 29.2, 29.06, 29.04, 27.7, 22.5, 14.0.

EXAMPLE 41

[0106] ##STR00043##

[0107] Operations were conducted by referring to Example 1. Cu(NO.sub.3).sub.2.3H.sub.2O (24.2 mg, 0.1 mmol), TEMPO (16.0 mg, 0.1 mmol), 3e (199.4 mg, 1.0 mmol), DCE (4 mL), reacted 18 hours to afford 4e (178.9 mg, 91%) (eluent: petroleum ether/ethyl ether=100/1) (before separation afforded a crude mixture E:Z>99:1, as determined by .sup.1H NMR analysis): oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): δ=6.83 (dt, J.sub.1=16.0 Hz, J.sub.2=7.0 Hz, 1H, ═CH), 6.09 (d, J=16.0 Hz, 1H, ═CH), 2.56 (q, J=7.4 Hz, 2H, CH.sub.2), 2.20 (q, J=7.2 Hz, 2H, CH.sub.2), 1.56-1.18 (m, 12H, 6×CH.sub.2), 1.10 (t, J=7.4 Hz, 3H, CH.sub.3), 0.88 (t, J=6.6 Hz, 3H, CH.sub.3); .sup.13C NMR (100 MHz, CDCl.sub.3): δ=201.0, 147.0, 129.9, 33.0, 32.3, 31.7, 29.2, 29.0, 28.0, 22.5, 13.9, 8.0; MS (70 eV, EI) m/z (%): 196 (M.sup.+, 2.27), 167 (100); IR (neat): ν=2925, 2855, 1699, 1675, 1630, 1460, 1355, 1200, 1116 cm.sup.−1; HRMS calcd. for C.sub.13H.sub.24O (M.sup.+): 196.1827; Found: 196.1830.

EXAMPLE 42

[0108] ##STR00044##

[0109] Operations were conducted by referring to Example 1. Cu(NO.sub.3).sub.2.3H.sub.2O (24.1 mg, 0.1 mmol), TEMPO (16.0 mg, 0.1 mmol), 5a (241.5 mg, 1.0 mmol), DCE (4 mL), reacted 12.2 hours to afford 6a (194.5 mg, 84%) (eluent: petroleum ether/ethyl ether=30/1): white solid. .sup.1H NMR (400 MHz, CDCl.sub.3): δ=9.96 (s, 1H, CHO), 7.92 (d, J=8.0 Hz, 2H, ArH), 7.60 (d, J=8.0 Hz, 2H, ArH); .sup.13C NMR (100 MHz, CDCl.sub.3): δ=191.4, 138.4, 135.5, 130.8, 102.8.

EXAMPLE 43

[0110] ##STR00045##

[0111] Operations were conducted by referring to Example 1. Cu(NO.sub.3).sub.2.3H.sub.2O (24.0 mg, 0.1 mmol), TEMPO (16.0 mg, 0.1 mmol), 5b (165.8 mg, 1.0 mmol), DCE (4 mL), reacted 18 hours to afford 6b (159.8 mg, 98%) (eluent: petroleum ether/ethyl ether=20/1): oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): δ=7.54 (d, J=7.6 Hz, 1H, ArH), 7.50 (s, 1H, ArH), 7.36 (t, J=7.8 Hz, 1H, ArH), 7.10 (dd, =8.4 Hz, J.sub.2=2.4 Hz, 1H, ArH), 3.86 (s, 3H, CH.sub.3), 2.99 (q, J=7.4 Hz, 2H, CH.sub.2), 1.22 (t, J=7.2 Hz, 3H, CH.sub.3); .sup.13C NMR (100 MHz, CDCl.sub.3): δ=200.1, 159.3, 137.8, 129.0, 120.1, 118.7, 111.8, 54.9, 31.4, 7.7; MS (70 eV, EI) m/z (%): 165 (M.sup.++1, 3.73), 164 (M.sup.+, 35.35), 135 (100); IR (neat): ν=2976, 2938, 1686, 1582, 1485, 1461, 1429, 1286, 1254, 1197, 1171, 1044, 1020 cm.sup.−1.

EXAMPLE 44

[0112] ##STR00046##

[0113] Operations were conducted by referring to Example 1. Cu(NO.sub.3).sub.2.3H.sub.2O (24.1 mg, 0.1 mmol), TEMPO (16.0 mg, 0.1 mmol), 7a (247.4 mg, 1.0 mmol), DCE (4 mL), reacted 21 hours to afford 8a (187.8 mg, 78%) (eluent: petroleum ether/ethyl ether=60/1): white solid. .sup.1H NMR (400 MHz, CDCl.sub.3): δ=9.77 (t, J=1.6 Hz, 1H, CHO), 2.42 (td, J.sub.1=7.0 Hz, J.sub.2=1.9 Hz, 2H, CH.sub.2), 1.68-1.56 (m, 2H, CH.sub.2), 1.37-1.20 (m, 24H, 12×CH.sub.2), 0.88 (t, J=7.0 Hz, 3H, CH.sub.3); .sup.13C NMR (100 MHz, CDCl.sub.3): δ=202.9, 43.9, 31.9, 29.7, 29.64, 29.62, 29.61, 29.5, 29.4, 29.3, 29.1, 22.7, 22.0, 14.1.

EXAMPLE 45

[0114] ##STR00047##

[0115] Operations were conducted by referring to Example 1. Cu(NO.sub.3).sub.2.3H.sub.2O (24.1 mg, 0.1 mmol), TEMPO (16.0 mg, 0.1 mmol), 7b (213.3 mg, 1.0 mmol), DCE (4 mL), reacted 48 hours to afford 8b (188.3 mg, 89%) (eluent: petroleum ether/ethyl ether=60/1): white solid. Melting point: 32.6-33.5° C. (petroleum ether/ethyl acetate recrystallization); .sup.1H NMR (400 MHz, CDCl.sub.3): δ=2.46-2.34 (m, 4H, 2×CH.sub.2), 1.62-1.52 (m, 2H, CH.sub.2), 1.34-1.18 (m, 16H, 8×CH.sub.2), 1.05 (t, J=7.2 Hz, 3H, CH.sub.3), 0.88 (t, J=6.8 Hz, 3H, CH.sub.3); .sup.13C NMR (100 MHz, CDCl.sub.3): δ=211.8, 42.3, 35.7, 31.8, 29.5, 29.4, 29.35, 29.25, 29.2, 23.9, 22.6, 14.0, 7.7; MS (70 eV, EI) m/z (%): 213 (M.sup.++1, 1.00), 212 (M.sup.+, 2.03), 72 (100); IR (neat): ν=2960, 2916, 2872, 2849, 1709, 1702, 1471, 1463, 1455, 1374, 1231, 1131, 1114 cm.sup.−1.

EXAMPLE 46

[0116] ##STR00048##

[0117] Operations were conducted by referring to Example 1. Cu(NO.sub.3).sub.2.3H.sub.2O (24.4 mg, 0.1 mmol), TEMPO (16.0 mg, 0.1 mmol), 9a (152.0 mg, 1.0 mmol), DCE (4 mL), reacted 22 hours to afford 10a (128.2 mg, 85%) (eluent: petroleum ether/ethyl ether=60/1): oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): δ=9.47 (d, J=7.2 Hz, 1H), 5.89-5.81 (m, 1H), 5.75 (t, J=6.0 Hz, 1H), 2.28-2.13 (m, 1H), 1.92-1.56 (m, 5H), 1.40-1.08 (m, 5H); .sup.13C NMR (100 MHz, CDCl.sub.3): δ=218.5, 192.3, 102.0, 99.4, 36.6, 32.8, 32.7, 25.7.

EXAMPLE 47

[0118] ##STR00049##

[0119] Operations were conducted by referring to Example 1. Cu(NO.sub.3).sub.2.3H.sub.2O (24.0 mg, 0.1 mmol), TEMPO (16.0 mg, 0.1 mmol), 9b (198.1 mg, 1.0 mmol), DCE (4 mL), reacted 24 hours to afford 10b (141.8 mg, 72%) (eluent: petroleum ether/ethyl ether=60/1): oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): δ=9.49 (d, J=7.2 Hz, 1H), 5.85-5.71 (m, 2H), 2.24-2.14 (m, 2H), 1.54-1.42 (m, 2H), 1.42-1.20 (m, 12H, 6×CH.sub.2), 0.88 (t, J=6.6 Hz, 3H); .sup.13C NMR (100 MHz, CDCl.sub.3): δ=219.1, 192.3, 98.6, 96.3, 31.8, 29.5, 29.25, 29.21, 28.9, 28.8, 27.4, 22.6, 14.0.

EXAMPLE 48

[0120] ##STR00050##

[0121] An oxygen balloon was inserted into the dry 250 mL flask, pumped 02 for three times, Cu(NO.sub.3).sub.2.3H.sub.2O (182.3 mg, 0.75 mmol), TEMPO (120.3 mg, 0.75 mmol), 1a (5.6549 g, 30 mmol) of MeCN solution (30 mL) were added sequentially. The flask was stirred at 25° C. for 15 h. The mixture solution was filtered through a short column of silica gel, and washed with ethyl ether, rotary evaporation to remove the solvent. The mixture solution was separated and purified by column chromatography on silica gel (eluent: petroleum ether/ethyl ether=30/1), to afford 2a (5.4919 g, 98%): oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): δ=8.14 (d, J=7.2 Hz, 2H, ArH), 7.60 (t, J=7.4 Hz, 1H, ArH), 7.48 (t, J=7.6 Hz, 2H, ArH), 2.51 (t, J=7.0 Hz, 2H, CH.sub.2), 1.73-1.60 (m, 2H, CH.sub.2), 1.57-1.45 (m, 2H, CH.sub.2), 0.97 (t, J=7.4 Hz, 3H, CH.sub.3); .sup.13C NMR (100 MHz, CDCl.sub.3): δ=178.1, 136.8, 133.8, 129.4, 128.4, 96.8, 79.6, 29.7, 22.0, 18.8, 13.4.

EXAMPLE 49

[0122] ##STR00051##

[0123] Cu(NO.sub.3).sub.2.3H.sub.2O (968.2 mg, 4.0 mmol), TEMPO (636.7 mg, 4.0 mmol), 1a (7.5332 g, 40.0 mmol) of MeCN solution (80 mL) were added sequentially into a dry 250 mL three-necked flask. A 42 L airbag was connected to the three-necked flask, and the three-necked flask was stirred at 25° C., after 1.5 hours, a 2 L 02 bag was connected to the three-necked flask to supplement oxygen. The three-necked flask was stirred at 25° C. for 4.5 h. The mixture solution was filtered through a short column of silica gel, and then washed with ethyl ether, rotary evaporation to remove solvent. The mixture solution was separated and purified by column chromatography on silica gel (eluent: petroleum ether/ethyl ether=30/1), to afford 2a (7.4587 g, 100%): oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): δ=8.14 (d, J=8.0 Hz, 2H, ArH), 7.60 (t, J=7.4 Hz, 1H, ArH), 7.48 (t, J=7.6 Hz, 2H, ArH), 2.51 (t, J=7.2 Hz, 2H, CH.sub.2), 1.74-1.62 (m, 2H, CH.sub.2), 1.58-1.46 (m, 2H, CH.sub.2), 0.97 (t, J=7.4 Hz, 3H, CH.sub.3); .sup.13C NMR (100 MHz, CDCl.sub.3): δ=178.1, 136.8, 133.8, 129.4, 128.4, 96.7, 79.6, 29.7, 21.9, 18.8, 13.4.

EXAMPLE 50

[0124] ##STR00052##

[0125] Cu(NO.sub.3).sub.2.3H.sub.2O (967.8 mg, 4.0 mmol), TEMPO (639.4 mg, 4.0 mmol), 1g (5.5340 g, 40.0 mmol) of MeCN solution (120 mL) were added sequentially into a dry 250 mL three-necked flask. The three-necked flask was connected with the air cylinder and the air flow released slowly (high purity air, 30 mL/min), The three-necked flask was stirred at 25° C. for 46 h. The mixture solution was filtered through a short column of silica gel, and then washed with ethyl ether, rotary evaporation to remove solvent. The mixture solution was separated and purified by column chromatography on silica gel (eluent: petroleum ether/ethyl ether=30/1), to afford 2g (4.3224 g, 79%): white solid; .sup.1H NMR (400 MHz, CDCl.sub.3): δ=7.98 (d, J.sub.1=3.6 Hz, 1H, ArH), 7.75 (d, J=4.8 Hz, 1H, ArH), 7.18 (t, J=4.2 Hz, 1H, ArH), 3.36 (s, 1H, CH); .sup.13C NMR (100 MHz, CDCl.sub.3): δ=169.0, 144.0, 136.1, 135.9, 128.4, 79.8, 79.4.

EXAMPLE 51

[0126] ##STR00053##

[0127] Operations were conducted by referring to Example 1. Cu(NO.sub.3).sub.2.3H.sub.2O (24.4 mg, 0.1 mmol), 4-OH-TEMPO (18.0 mg, 0.1 mmol), 1f (190.4 mg, 1.0 mmol), MeCN (4 mL), reacted 18 hours to afford 2f (166.3 mg, 88%) (eluent: petroleum ether/ethyl ether=30/1): white solid. .sup.1H NMR (400 MHz, CDCl.sub.3) δ=8.22 (d, J=7.6 Hz, 2H, ArH), 8.16 (d, J=7.6 Hz, 2H, ArH), 3.97 (s, 3H, CH.sub.3), 3.52 (s, 1H, CH); .sup.13C NMR (100 MHz, CDCl.sub.3): δ=176.6, 166.0, 139.0, 135.0, 129.8, 129.5, 81.7, 80.0, 52.5.

EXAMPLE 52

[0128] ##STR00054##

[0129] Operations were conducted by referring to Example 1. Cu(NO.sub.3).sub.2.3H.sub.2O (24.4 mg, 0.1 mmol), 4-OH-TEMPO (17.4 mg, 0.1 mmol), 3d (177.6 mg, 1.0 mmol), DCE (4 mL), reacted 22 hours to afford 4d (166.2 mg, 99%, E:Z>99:1) (eluent: petroleum ether/ethyl ether=60/1) (before separation afforded a crude mixture E:Z>99:1, as determined by .sup.1H NMR analysis): oily liquid; .sup.1H NMR (400 MHz, CDCl.sub.3): δ=9.51 (d, J=7.6 Hz, 1H, CHO), 6.85 (dt, J.sub.1=15.6 Hz, J=7.0 Hz, 1H, CH═), 6.18-6.07 (dd, J.sub.1=15.6 Hz, J=8.0 Hz, 1H, CH═), 2.34 (dd, J.sub.1=14.4 Hz, J=7.2 Hz, 2H, CH.sub.2), 1.56-1.44 (m, 2H, CH.sub.2), 1.40-1.20 (m, 10H, 5×CH.sub.2), 0.89 (t, J=6.6 Hz, 3H, CH.sub.3); .sup.13C NMR (100 MHz, CDCl.sub.3): δ=194.0, 158.9, 132.9, 32.6, 31.7, 29.2, 29.05, 29.03, 27.7, 22.5, 14.0.

EXAMPLE 53

[0130] ##STR00055##

[0131] Operations were conducted by referring to Example 1. Cu(NO.sub.3).sub.2.3H.sub.2O (24.4 mg, 0.1 mmol), 4-OH-TEMPO (17.9 mg, 0.1 mmol), 5a (241.0 mg, 1.0 mmol), DCE (4 mL), reacted 7 hours to afford 6a (215.6 mg, 93%) (eluent: petroleum ether/ethyl ether=30/1): white solid. .sup.1H NMR (400 MHz, CDCl.sub.3): δ=9.96 (s, 1H, CHO), 7.92 (d, J=8.0 Hz, 2H, ArH), 7.59 (d, J=8.0 Hz, 2H, ArH); .sup.13C NMR (100 MHz, CDCl.sub.3): δ=191.4, 138.4, 135.5, 130.8, 102.8.

EXAMPLE 54

[0132] ##STR00056##

[0133] Operations were conducted by referring to Example 1. Cu(NO.sub.3).sub.2.3H.sub.2O (24.3 mg, 0.1 mmol), 4-OH-TEMPO (17.6 mg, 0.1 mmol), 7a (247.1 mg, 1.0 mmol), DCE (4 mL), reacted 36 hours to afford 8a (192.7 mg, 80%) (eluent: petroleum ether/ethyl ether=60/1): white solid. .sup.1H NMR (400 MHz, CDCl.sub.3): δ=9.76 (s, 1H, CHO), 2.42 (t, J=7.2 Hz, 2H, CH.sub.2), 1.63 (t, J=6.8 Hz, 2H, CH.sub.2), 1.37-1.18 (m, 24H, 12×CH.sub.2), 0.88 (t, J=6.6 Hz, 3H, CH.sub.3); .sup.13C NMR (100 MHz, CDCl.sub.3): δ=202.8, 43.9, 31.9, 29.6, 29.65, 29.63, 29.55, 29.4, 29.3, 29.1, 22.7, 22.0, 14.1.

EXAMPLE 55

[0134] ##STR00057##

[0135] Operations were conducted by referring to Example 1. Cu(NO.sub.3).sub.2.3H.sub.2O (24.4 mg, 0.1 mmol), TEMPO (16.0 mg, 0.1 mmol), 3c (158.5 mg, 1.0 mmol), DCE (10 mL), reacted 41 hours to afford a crude mixture of 4c, (78% NMR yield, Z:E=92:8, as determined by .sup.1H NMR analysis).

EXAMPLE 56

[0136] ##STR00058##

[0137] Operations were conducted by referring to Example 1. Cu(NO.sub.3).sub.2.3H.sub.2O (24.4 mg, 0.1 mmol), 4-OH-TEMPO (17.4 mg, 0.1 mmol), 3c (159.1 mg, 1.0 mmol), DCE (10 mL), reacted 41 hours to afford a crude mixture of 4c, (58% NMR yield, Z:E=93:7, raw material remaining 27%, as determined by .sup.1H NMR analysis).

EXAMPLE 57

[0138] ##STR00059##

[0139] Operations were conducted by referring to Example 1. Cu(NO.sub.3).sub.2.3H.sub.2O (9.9 mg, 0.04 mmol), TEMPO (6.6 mg, 0.04 mmol), 1a (75.4 mg, 0.4 mmol), NMP (1.6 mL), reacted 8 hours to afford 2a, (11% NMR yield, raw material remaining 84%, as determined by .sup.1H NMR analysis).

EXAMPLE 58

[0140] ##STR00060##

[0141] Operations were conducted by referring to Example 1. Cu(NO.sub.3).sub.2.3H.sub.2O (9.8 mg, 0.04 mmol), TEMPO (6.5 mg, 0.04 mmol), 1a (75.2 mg, 0.4 mmol), cyclohexane (1.6 mL), reacted 8 hours to afford 2a, (12% NMR yield, raw material remaining 76%, as determined by .sup.1H NMR analysis).

EXAMPLE 59

[0142] ##STR00061##

[0143] Operations were conducted by referring to Example 1. Cu(NO.sub.3).sub.2.3H.sub.2O (9.8 mg, 0.04 mmol), TEMPO (6.6 mg, 0.04 mmol), 1a (74.9 mg, 0.4 mmol), MeNO.sub.2 (1.6 mL), reacted 8 hours to afford 2a, (37% NMR yield, raw material remaining 56%, as determined by .sup.1H NMR analysis).

EXAMPLE 60

[0144] ##STR00062##

[0145] Operations were conducted by referring to Example 1. Cu(NO.sub.3).sub.2.3H.sub.2O (9.9 mg, 0.04 mmol), TEMPO (6.4 mg, 0.04 mmol), 1a (75.2 mg, 0.4 mmol), dioxane (1.6 mL), reacted 8 hours to afford 2a, (42% NMR yield, raw material remaining 50%, as determined by .sup.1H NMR analysis).

EXAMPLE 61

[0146] ##STR00063##

[0147] Operations were conducted by referring to Example 1. Cu(NO.sub.3).sub.2.3H.sub.2O (9.7 mg, 0.04 mmol), TEMPO (6.4 mg, 0.04 mmol), 1a (75.7 mg, 0.4 mmol), THF (1.6 mL), reacted 8 hours to afford 2a, (49% NMR yield, raw material remaining 46%, as determined by .sup.1H NMR analysis).

EXAMPLE 62

[0148] ##STR00064##

[0149] Operations were conducted by referring to Example 1. Cu(NO.sub.3).sub.2.3H.sub.2O (9.8 mg, 0.04 mmol), TEMPO (6.4 mg, 0.04 mmol), 1a (75.2 mg, 0.4 mmol), Et.sub.2O (1.6 mL), reacted 8 hours to afford 2a, (85% NMR yield, raw material remaining 12%, as determined by .sup.1H NMR analysis).

EXAMPLE 63

[0150] ##STR00065##

[0151] Operations were conducted by referring to Example 1. Cu(NO.sub.3).sub.2.3H.sub.2O (9.8 mg, 0.04 mmol), TEMPO (6.4 mg, 0.04 mmol), 1a (75.0 mg, 0.4 mmol), DCM (1.6 mL), reacted 8 hours to afford 2a, (91% NMR yield, raw material remaining 5%, as determined by .sup.1H NMR analysis).

EXAMPLE 64

[0152] ##STR00066##

[0153] Operations were conducted by referring to Example 1. Cu(NO.sub.3).sub.2.3H.sub.2O (9.9 mg, 0.04 mmol), TEMPO (6.4 mg, 0.04 mmol), 1a (75.0 mg, 0.4 mmol), toluene (1.6 mL), reacted 8 hours to afford 2a, (92% NMR yield, raw material remaining 8%, as determined by .sup.1H NMR analysis).

EXAMPLE 65

[0154] ##STR00067##

[0155] Operations were conducted by referring to Example 1. Cu(MeCN).sub.4PF.sub.6 (14.9 mg, 0.04 mmol), TEMPO (6.4 mg, 0.04 mmol), 1a (75.3 mg, 0.4 mmol), MeCN (1.6 mL), reacted 4 hours to afford 2a, (6% NMR yield, raw material remaining 90%, as determined by .sup.1H NMR analysis).

EXAMPLE 66

[0156] ##STR00068##

[0157] Operations were conducted by referring to Example 1. CuCl (4.0 mg, 0.04 mmol), TEMPO (6.4 mg, 0.04 mmol), 1a (75.3 mg, 0.4 mmol), MeCN (1.6 mL), reacted 4 hours to afford 2a, (9% NMR yield, raw material remaining 91%, as determined by .sup.1H NMR analysis).

EXAMPLE 67

[0158] ##STR00069##

[0159] Operations were conducted by referring to Example 1. CuBr.sub.2 (8.9 mg, 0.04 mmol), TEMPO (6.4 mg, 0.04 mmol), 1a (75.4 mg, 0.4 mmol), MeCN (1.6 mL), reacted 4 hours to afford 2a, (12% NMR yield, raw material remaining 84%, as determined by .sup.1H NMR analysis).

EXAMPLE 68

[0160] ##STR00070##

[0161] Operations were conducted by referring to Example 1. CuI (7.7 mg, 0.04 mmol), TEMPO (6.6 mg, 0.04 mmol), 1a (75.3 mg, 0.4 mmol), MeCN (1.6 mL), reacted 4 hours to afford 2a, (19% NMR yield, raw material remaining 78%, as determined by .sup.1H NMR analysis).

EXAMPLE 69

[0162] ##STR00071##

[0163] Operations were conducted by referring to Example 1. Cu(OAc).sub.2 (7.4 mg, 0.04 mmol), TEMPO (6.4 mg, 0.04 mmol), 1a (75.3 mg, 0.4 mmol), MeCN (1.6 mL), reacted 4 hours to afford 2a, (43% NMR yield, raw material remaining 57%, as determined by .sup.1H NMR analysis).

EXAMPLE 70

[0164] ##STR00072##

[0165] Operations were conducted by referring to Example 1. Cu(NO.sub.3).sub.2.3H.sub.2O (9.8 mg, 0.04 mmol), TEMPO (6.4 mg, 0.04 mmol), 1a (75.4 mg, 0.4 mmol), MeCN (1.6 mL), reacted 4 hours to afford 2a, (96% NMR yield as determined by .sup.1H NMR analysis).

EXAMPLE 71

[0166] ##STR00073##

[0167] Operations were conducted by referring to Example 1. TEMPO (6.3 mg, 0.04 mmol), 1a (75.4 mg, 0.4 mmol), MeCN (1.6 mL), reacted 4 hours to afford 2a, (1% NMR yield, raw material remaining 94%, as determined by .sup.1H NMR analysis).

EXAMPLE 72

[0168] ##STR00074##

[0169] Operations were conducted by referring to Example 1. Cu(NO.sub.3).sub.2.3H.sub.2O (9.8 mg, 0.04 mmol), 1a (75.4 mg, 0.4 mmol), MeCN (1.6 mL), reacted 4 hours to afford 2a, (3% NMR yield, raw material remaining 94%, as determined by .sup.1H NMR analysis).

[0170] The present invention is not limited to the specific embodiments disclosed and described above. Without departing from the spirit and scope of the inventive concept, some modifications and changes to the present invention should also fall within the protection scope of the claims of the present invention, and the appended claims shall be the protection scope. In addition, although some specific terms are used in this specification, these terms are only for the convenience of description and do not constitute any limitation to the present invention.