PROCESS FOR PREPARING BIPHENYLAMINES FROM ANILIDES BY RUTHENIUM CATALYSIS

Abstract

The present invention relates to a novel process for preparing substituted biphenylamides of the general formula (V)

##STR00001##

characterized in that
anilides of the formula (II)

##STR00002##

in a solvent other than tetrahydrofuran,
are reacted with an organoboron compound of the formula (III)

##STR00003##

in the presence of a catalyst system consisting of a ruthenium catalyst, an activator, an oxidizing agent and a metal triflate.

Claims

1. A process for the preparation of one or more biphenylamides of formula (V) ##STR00040## wherein R.sup.1 is hydrogen, hydroxyl, fluorine, chlorine, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy, C.sub.1-C.sub.4-alkylthio or C.sub.1-C.sub.4-haloalkyl, R.sup.2 is C.sub.1-C.sub.4-alkyl, C.sub.6-C.sub.10-aryl or C.sub.6-C.sub.10-aryl-CH.sub.2, and X.sup.1 is hydrogen, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy, fluorine or chlorine, X.sup.2 is hydrogen, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy, fluorine or chlorine, X.sup.3 is hydrogen, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy, fluorine or chlorine, comprising reacting one or more anilides of formula (II) ##STR00041## wherein R.sup.1 and R.sup.2 are each as defined above, in a solvent other than tetrahydrofuran, with an organoboron compound of formula (III) ##STR00042## wherein X.sup.1, X.sup.2 and X.sup.3 are each as defined above, and which is selected from one of the following groups consisting of: (I) boronic acids of formula (III) in which Q is a hydroxyl group, m is 2, p is 1, or the anhydrides, dimers or trimers of these boronic acids; (II) boronic acid derivatives of formula (III) in which Q is F, Cl, Br, I, C.sub.1-C.sub.4-alkyl, C.sub.6-C.sub.10-aryl, C.sub.1-C.sub.4-alkoxy or C.sub.6-C.sub.10-aryloxy, m is 2, p is 1; (III) borinic acids of formula (III) in which Q is OH, F, Cl, Br, I, C.sub.1-C.sub.4-alkyl, C.sub.6-C.sub.10-aryl, C.sub.1-C.sub.4-alkoxy or C.sub.6-C.sub.10-aryloxy, m is 1, p is 2; (IV) cyclic boronic esters of formula (III) in which Q is a C.sub.2-C.sub.3-alkyldioxy radical which, together with the boron atom to which it is bonded, forms a 5- or 6-membered ring optionally substituted by one or more C.sub.1-C.sub.4-alkyl radicals, m is 2, p is 1; (V) boronates of formula (III) in which Q is OH, F, Cl, Br, I, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy or C.sub.6-C.sub.10-aryloxy, m is 3, p is 1 and the negative charge of the boronate anion is compensated for by a cation, (VI) triarylboranes of formula (III) in which m is 0, p is 3; (VII) tetraarylborates of formula (IV) in which m is 0, p is 4 and the negative charge of the tetraarylborate anion is compensated for by a cation, in the presence of a catalyst system consisting of a ruthenium catalyst, an activator, an oxidizing agent and a metal triflate.

2. A process according to claim 1, wherein an amide of formula (Ia) is deprotected in a second stage to give a free amine of formula (I).

3. A process according to claim 1, wherein the solvent is selected from the group comprising N,N-dialkylalkanamides, dimethoxyethane (DME), methanol, ethyl acetate and water, and mixtures of these solvents.

4. A process according to claim 1, wherein the solvent is selected from the group comprising N,N-dialkylalkanamides and mixtures of these solvents.

5. A process according to claim 1, wherein the catalyst is [{RuCl.sub.2(p-cymene)}.sub.2].

6. A process according to claim 1, wherein the oxidizing agent is Ag.sub.2O.

7. A process according to claim 1, wherein the metal of the metal triflate is selected from the group comprising Li, Na, K, Mg, Ca, Mn, Fe, Co, Ni, Cu and Zn.

8. A process according to claim 1, wherein the metal of the metal triflate is selected from the group comprising sodium, potassium, manganese, zinc and iron and nickel.

9. A process according to claim 1, wherein the activator is selected from the group comprising AgSbF.sub.6, KPF.sub.6, NaPF.sub.6, AgF and AgBF.sub.4.

10. A process according to claim 1, wherein the boronic acid is a boronic acid of formula (III) with Q=OH, m=2 and p=1.

11. A process according to claim 1, wherein the boronic acid is a boronic acid of formula (III) with Q=OH, m=2 and p=1, the solvent is DMF, the catalyst is [{RuCl.sub.2(p-cymene)}.sub.2], the metal triflate is iron(III) triflate, the oxidizing agent is Ag.sub.2O and the activator is AgSbF.sub.6.

12. A process for preparing one or more biphenylamides of formula (Ia) ##STR00043## in which R.sup.1 is hydrogen, hydroxyl, fluorine, chlorine, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy, C.sub.1-C.sub.4-alkylthio or C.sub.1-C.sub.4-haloalkyl, R.sup.2 is C.sub.1-C.sub.4-alkyl, C.sub.6-C.sub.10-aryl or C.sub.6-C.sub.10-aryl-CH.sub.2, and X.sup.1 is hydrogen, C.sub.1-C.sub.3-alkyl, C.sub.1-C.sub.4-alkoxy, fluorine or chlorine, X.sup.2 is hydrogen, C.sub.1-C.sub.3-alkyl, C.sub.1-C.sub.4-alkoxy, fluorine or chlorine, X.sup.3 is hydrogen, C.sub.1-C.sub.3-alkyl, C.sub.1-C.sub.4-alkoxy, fluorine or chlorine, comprising reacting one or more anilides of formula (II) ##STR00044## in which R.sup.1 and R.sup.2 are each as defined above, with an organoboron compound of formula (III) ##STR00045## in which X.sup.1, X.sup.2 and X.sup.3 are each as defined above, and which is selected from one of the following groups consisting of: (i) boronic acids of formula (III) in which Q is a hydroxyl group, m is 2, p is 1, or the anhydrides, dimers or trimers of these boronic acids; (II) boronic acid derivatives of formula (III) in which Q is F, Cl, Br, I, C.sub.1-C.sub.4-alkyl, C.sub.6-C.sub.10-aryl, C.sub.1-C.sub.4-alkoxy or C.sub.6-C.sub.10-aryloxy, m is 2, p is 1; (III) borinic acids of formula (III) in which Q is OH, F, Cl, Br, I, C.sub.1-C.sub.4-alkyl, C.sub.6-C.sub.10-aryl, C.sub.1-C.sub.4-alkoxy or C.sub.6-C.sub.10-aryloxy, m is 1, p is 2; (IV) cyclic boronic esters of formula (III) in which Q is a C.sub.2-C.sub.3-alkyldioxy radical which, together with the boron atom to which it is bonded, forms a 5- or 6-membered ring optionally substituted by one or more C.sub.1-C.sub.4-alkyl radicals, m is 2, p is 1; (V) boronates of formula (III) in which Q is OH, F, Cl, Br, I, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy or C.sub.6-C.sub.10-aryloxy, m is 3, p is 1 and the negative charge of the boronate anion is compensated for by a cation, (VI) triarylboranes of formula (III) in which m is 0, p is 3; (VII) tetraarylborates of formula (IV) in which m is 0, p is 4 and the negative charge of the tetraarylborate anion is compensated for by a cation, in the presence of a catalyst system consisting of a ruthenium catalyst, an activator, an oxidizing agent and a metal sulphate.

13. A process for preparing one or more biphenylamides of formula (Ia) ##STR00046## in which R.sup.1 is hydrogen, hydroxyl, fluorine, chlorine, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy, C.sub.1-C.sub.4-alkylthio or C.sub.1-C.sub.4-haloalkyl, R.sup.2 is C.sub.1-C.sub.4-alkyl, C.sub.6-C.sub.10-aryl or C.sub.6-C.sub.10-aryl-CH.sub.2, X.sup.1 is hydrogen, C.sub.1-C.sub.3-alkyl, C.sub.1-C.sub.4-alkoxy, fluorine or chlorine, X.sup.2 is hydrogen, C.sub.1-C.sub.3-alkyl, C.sub.1-C.sub.4-alkoxy, fluorine or chlorine, X.sup.3 is hydrogen, C.sub.1-C.sub.3-alkyl, C.sub.1-C.sub.4-alkoxy, fluorine or chlorine, comprising reacting one or more anilides of formula (II) ##STR00047## in which R.sup.1 and R.sup.2 are each as defined above, are reacted with an organoboron compound of formula (III) ##STR00048## in which X.sup.1, X.sup.2 and X.sup.3 are each as defined above, and which is selected from one of the following groups consisting of: (i) boronic acids of formula (III) in which Q is a hydroxyl group, m is 2, p is 1, or the anhydrides, dimers or trimers of these boronic acids; (II) boronic acid derivatives of formula (III) in which Q is F, Cl, Br, I, C.sub.1-C.sub.4-alkyl, C.sub.6-C.sub.10-aryl, C.sub.1-C.sub.4-alkoxy or C.sub.6-C.sub.10-aryloxy, m is 2, p is 1; (III) borinic acids of formula (III) in which Q is OH, F, Cl, Br, I, C.sub.1-C.sub.4-alkyl, C.sub.6-C.sub.10-aryl, C.sub.1-C.sub.4-alkoxy or C.sub.6-C.sub.10-aryloxy, m is 1, p is 2; (IV) cyclic boronic esters of formula (III) in which Q is a C.sub.2-C.sub.3-alkyldioxy radical which, together with the boron atom to which it is bonded, forms a 5- or 6-membered ring optionally substituted by one or more C.sub.1-C.sub.4-alkyl radicals, m is 2, p is 1; (V) boronates of formula (III) in which Q is OH, F, Cl, Br, I, C.sub.1-C.sub.4-alkyl, C.sub.6-C.sub.10-aryl, C.sub.1-C.sub.4-alkoxy or C.sub.6-C.sub.10-aryloxy, m is 3, p is 1 and the negative charge of the boronate anion is compensated for by a cation, (VI) triarylboranes of formula (III) in which m is 0, p is 3; (VII) tetraarylborates of formula (IV) in which m is 0, p is 4 and the negative charge of the tetraarylborate anion is compensated for by a cation, in the presence of a catalyst system consisting of a ruthenium catalyst, an activator, an oxidizing agent and a metal oxide.

Description

PREPARATION EXAMPLES

Example 1

N-([1,1-Biphenyl]-2-yl)acetamide

[0109] ##STR00010##

[0110] In a baked-out closable reaction vessel, a suspension consisting of acetanilide (135 mg, 1.0 mmol), [{RuCl.sub.2(p-cymene)}.sub.2] (30.6 mg, 5.0 mol %), AgSbF.sub.6 (68.7 mg, 0.2 mmol), Ag.sub.2O (232 mg, 1.0 mmol), Cu(OTf).sub.2 (72.3 mg, 0.2 mmol) and phenylboronic acid (183 mg, 1.5 mmol) in dry DMF (3.0 ml) was stirred in a nitrogen atmosphere at 110 C. for 20 h. The reaction mixture was then diluted at room temperature with EtOAc (75 ml) and filtered through Celite and silica gel, and the filtrate was concentrated. The crude product thus obtained was purified by chromatography on silica gel (n-hexane/EtOAc: 7/3). 162 mg of N-([1,1-biphenyl]-2-yl)acetamide were obtained as a colourless solid (77% of theory). M.p.=113-115 C. .sup.1H NMR (CDCl.sub.3, 300 MHz): =8.21 (d, J=8.2 Hz, 1H), 7.51-7.30 (m, 6H), 7.24-7.13 (m, 3H), 1.98 (s, 3H). .sup.13C NMR (CDCl.sub.3, 75 MHz): =168.2 (C.sub.q), 138.1 (C.sub.q), 134.6 (C.sub.q), 132.2 (C.sub.q), 130.0 (CH), 129.1 (CH), 129.0 (CH), 128.2 (CH), 127.9 (CH), 124.3 (CH), 121.7 (CH), 24.4 (CH.sub.3). IR (neat): 3284, 3230, 3054, 3027, 1658, 1531, 1433, 1301, 755, 741, 703, 662, 520 cm.sup.1. MS (EI) m/z (relative intensity): 211 ([M.sup.+]34), 169 (100), 139 (7), 115 (5), 43 (15). HR-MS (ESI) m/z calculated for C.sub.14H.sub.13NO [M.sup.+] 211.0997. found 211.0996.

Example 2: (Comp.)

N-([1,1-Biphenyl]-2-yl)acetamide

[0111] ##STR00011##

[0112] The procedure was as described in Example 1, except that the reaction was conducted in THF rather than in DMF. 116 mg of N-([1,1-biphenyl]-2-yl)acetamide were obtained as a colourless solid (55% of theory).

Example 2a

N-([1,1-Biphenyl]-2-yl)acetamide

[0113] ##STR00012##

[0114] The procedure was as described in Example 1, except that the reaction was conducted in ethyl acetate rather than in DMF. N-([1,1-Biphenyl]-2-yl)acetamide was obtained as a colourless solid (55% of theory).

Example 2b

N-([1,1-Biphenyl]-2-yl)acetamide

[0115] ##STR00013##

[0116] The procedure was as described in Example 1, except that the reaction was conducted in methanol rather than in DMF. N-([1,1-Biphenyl]-2-yl)acetamide was obtained as a colourless solid (70% of theory).

Example 2c

N-([1,1-Biphenyl]-2-yl)acetamide

[0117] ##STR00014##

[0118] The procedure was as described in Example 1, except that the reaction was conducted in dichloroethane rather than in DMF. N-([1,1-Biphenyl]-2-yl)acetamide was obtained as a colourless solid (57% of theory).

Example 2d

N-([1,1-Biphenyl]-2-yl)acetamide

[0119] ##STR00015##

[0120] The procedure was as described in Example 1, except that the reaction was conducted in water rather than in DMF. N-([1,1-Biphenyl]-2-yl)acetamide was obtained as a colourless solid (43% of theory).

Example 2e

N-([1,1-Biphenyl]-2-yl)acetamide

[0121] ##STR00016##

[0122] The procedure was as described in Example 1, except that the reaction was conducted in DMA rather than in DMF. N-([1,1-Biphenyl]-2-yl)acetamide was obtained as a colourless solid (46% of theory).

Example 2f

N-([1,1-Biphenyl]-2-yl)acetamide

[0123] ##STR00017##

[0124] The procedure was as described in Example 1, except that the reaction was conducted in DME rather than in DMF. N-([1,1-Biphenyl]-2-yl)acetamide was obtained as a colourless solid (50% of theory).

Example 22

N-([1,1-Biphenyl]-2-yl)acetamide

[0125] ##STR00018##

[0126] The procedure was as described in Example 1, except that the reaction was conducted in a 1:1 mixture of DMF and THF rather than in DMF. N-([1,1-Biphenyl]-2-yl)acetamide was obtained as a colourless solid (65% of theory).

Example 3a

N-([1,1-Biphenyl]-2-yl)acetamide

[0127] ##STR00019##

[0128] In a baked-out closable reaction vessel, a suspension consisting of

[0129] acetanilide (135 mg, 1.0 mmol), [{RuCl.sub.2(p-cymene)}2] (30.6 mg, 5.0 mol %), AgSbF.sub.6 (68.7 mg, 0.2 mmol), Ag.sub.2O (232 mg, 1.0 mmol), Fe(OTf).sub.3 (101 mg, 0.2 mmol) and phenylboronic acid (183 mg, 1.5 mmol) in dry DMF (3.0 ml) was stirred in a nitrogen atmosphere at 110 C. for 20 h. The reaction mixture was then diluted at room temperature with EtOAc (75 ml) and filtered through Celite and silica gel, and the filtrate was concentrated. The crude product thus obtained was purified by chromatography on silica gel (n-hexane/EtOAc: 7/3). 171 mg of N-([1,1-biphenyl]-2-yl)acetamide were obtained as a colourless solid (81% of theory).

Example 3b

N-([1,1-Biphenyl]-2-yl)acetamide

[0130] ##STR00020##

[0131] The procedure was as described in Example 3a, except that the reaction was conducted in THF rather than in DMF. N-([1,1-Biphenyl]-2-yl)acetamide was obtained in a yield of 56% of theory.

Example 4

N-([1,1-Biphenyl]-2-yl)acetamide

[0132] ##STR00021##

[0133] In a baked-out closable reaction vessel, a suspension consisting of

[0134] acetanilide (135 mg, 1.0 mmol), [{RuCl.sub.2(p-cymene)}.sub.2] (30.6 mg, 5.0 mol %), AgSbF.sub.6 (68.7 mg, 0.2 mmol), Ag.sub.2O (232 mg, 1.0 mmol), Cu(OTf).sub.2 (72.3 mg, 0.2 mmol) and diphenylborinic acid (137 mg, 0.75 mmol) in dry DMF (3.0 ml) was stirred in a nitrogen atmosphere at 110 C. for 20 h. The reaction mixture was then diluted at room temperature with EtOAc (75 ml) and filtered through Celite and silica gel, and the filtrate was concentrated. The crude product thus obtained was purified by chromatography on silica gel (n-hexane/EtOAc: 7/3). 84.4 mg of N-([1,1-biphenyl]-2-yl)acetamide were obtained as a colourless solid (40% of theory).

Example 5

N-(4-Methyl-[1,1-biphenyl]-2-yl)acetamide

[0135] ##STR00022##

[0136] In a baked-out closable reaction vessel, a suspension consisting of N-(m-tolyl)acetamide (149 mg, 1.0 mmol), [{RuCl.sub.2(p-cymene)}.sub.2] (30.6 mg, 5.0 mol %), AgSbF.sub.6 (68.7 mg, 0.2 mmol), Ag.sub.2O (232 mg, 1.0 mmol), Cu(OTf).sub.2 (72.3 mg, 0.2 mmol) and phenylboronic acid (183 mg, 1.5 mmol) in dry DMF (3.0 ml) was stirred in a nitrogen atmosphere at 110 C. for 20 h. The reaction mixture was then diluted at room temperature with EtOAc (75 ml) and filtered through Celite and silica gel, and the filtrate was concentrated. The crude product thus obtained was purified by chromatography on silica gel (n-hexane/EtOAc: 7/3). 175 mg of N-(4-methyl-[1,1-biphenyl]-2-yl)acetamide were obtained as a colourless solid (78% of theory). M.p.=139-141 C. .sup.1H NMR (CDCl.sub.3, 300 MHz): =8.04 (s, 1H), 7.50-7.28 (m, 5H), 7.21-7.08 (m, 2H), 6.98 (d, J=7.6 Hz, 1H), 2.38 (s, 3H), 1.98 (s, 3H). .sup.13C NMR (CDCl.sub.3, 125 MHz): =168.0 (C.sub.q), 138.3 (C.sub.q), 138.1 (C.sub.q), 134.3 (C.sub.q), 129.7 (CH), 129.4 (C.sub.q), 129.2 (CH), 128.9 (CH), 127.6 (CH), 125.1 (CH), 122.2 (CH), 24.6 (CH.sub.3), 21.5 (CH.sub.3). IR (neat): 3224, 3029, 2916, 1652, 1539, 1476, 1412, 1297, 820, 763, 724, 700, 611, 524 cm.sup.1. MS (EI) m/z (relative intensity): 225 ([M.sup.+] 54), 183 (100), 167 (30), 43 (20). HR-MS (ESI) m/z calculated for C.sub.15H.sub.15NO [M.sup.+] 225.1154. found 225.1159.

Example 6

N-(5-Methyl-[1,1-biphenyl]-2-yl)acetamide

[0137] ##STR00023##

[0138] In a baked-out closable reaction vessel, a suspension consisting of

[0139] N-(p-tolyl)acetamide (149 mg, 1.0 mmol), [{RuCl.sub.2(p-cymene)}.sub.2] (30.6 mg, 5.0 mol %), AgSbF.sub.6 (68.7 mg, 0.2 mmol), Ag.sub.2O (232 mg, 1.0 mmol), Cu(OTf).sub.2 (72.3 mg, 0.2 mmol) and phenylboronic acid (183 mg, 1.5 mmol) in dry DMF (3.0 ml) was stirred in a nitrogen atmosphere at 110 C. for 20 h. The reaction mixture was then diluted at room temperature with EtOAc (75 ml) and filtered through Celite and silica gel, and the filtrate was concentrated. The crude product thus obtained was purified by chromatography on silica gel (n-hexane/EtOAc: 7/3). 178 mg of N-(5-methyl-[1,1-biphenyl]-2-yl)acetamide were obtained as a colourless solid (79% of theory). M.p.=107-109 C. .sup.1H NMR (CDCl.sub.3, 300 MHz): =8.06 (d, J=8.3 Hz, 1H), 7.50-7.31 (m, 5H), 7.16 (dd, J=8.3, 2.2 Hz, 1H), 7.04 (m, 2H), 2.33 (s, 3H), 1.99 (s, 3H). .sup.13C NMR (CDCl.sub.3, 126 MHz): =168.0 (C.sub.q), 138.3 (C.sub.q), 134.0 (C.sub.q), 132.3 (C.sub.q), 132.0 (C.sub.q), 131.0 (CH), 129.1 (CH), 128.9 (CH), 128.8 (CH), 127.7 (CH), 121.9 (CH), 24.5 (CH.sub.3), 20.9 (CH.sub.3). IR (neat): 3235, 3057, 3029, 2922, 1655, 1524, 1505, 1488, 1366, 761, 734, 691, 603, 580 cm.sup.1. MS (EI) m/z (relative intensity): 225 ([M.sup.+] 54), 183 (100), 167 (18), 43 (22). HR-MS (ESI) m/z calculated for C.sub.15H.sub.15NO [M+] 225.1154. found 225.1154.

Example 7

N-(3,4-Dichloro-5-fluoro-[1,1-biphenyl]-2-yl)acetamide

[0140] ##STR00024##

[0141] In a baked-out closable reaction vessel, a suspension consisting of

[0142] N-(4-fluorophenyl)acetamide (153 mg, 1.0 mmol), [{RuCl.sub.2(p-cymene)}.sub.2] (30.6 mg, 5.0 mol %), AgSbF.sub.6 (68.7 mg, 0.2 mmol), Ag.sub.2O (232 mg, 1.0 mmol), Cu(OTf).sub.2 (72.3 mg, 0.2 mmol) and 3,4-dichlorophenylboronic acid (286 mg, 1.5 mmol) in dry DMF (3.0 ml) was stirred in a nitrogen atmosphere at 110 C. for 20 h. The reaction mixture was then diluted at room temperature with EtOAc (75 ml) and filtered through Celite and silica gel, and the filtrate was concentrated. The crude product thus obtained was purified by chromatography on silica gel (n-hexane/EtOAc: 7/3). 188 mg of N-(3,4-dichloro-5-fluoro-[1,1-biphenyl]-2-yl)acetamide were obtained as a colourless solid (63% of theory). M.p.=146-148 C. .sup.1H NMR (CDCl.sub.3, 300 MHz): =8.02-7.94 (m, 1H), 7.53 (d, J=8.2 Hz, 1H), 7.44 (d, J=2.0 Hz, 1H), 7.18 (dd, J=8.2, 2.1 Hz, 1H), 7.12-7.01 (m, 1H), 6.96-6.93 (m, 2H), 2.02 (s, 3H). .sup.13C NMR (CDCl.sub.3, 75 MHz): =168.5 (C.sub.q), 159.5 (C.sub.q, J.sub.C-F=246.4 Hz), 137.2 (C.sub.q, J.sub.C-F=1.6 Hz), 133.3 (C.sub.q), 133.0 (C.sub.q, J.sub.C-F=7.6 Hz), 132.8 (C.sub.q), 131.0 (CH), 130.9 (CH), 130.4 (C.sub.q, J.sub.C-F=2.7 Hz), 128.2 (CH), 125.4 (CH, J.sub.C-F=8.0 Hz), 116.5 (CH, J.sub.C-F=23.2 Hz), 115.7 (CH, J.sub.C-F=21.9 Hz), 24.2 (CH.sub.3). .sup.19F NMR (282 MHz, CDCl.sub.3) =116.6 (s). IR (neat): 3242, 3190, 1652, 1529, 1472, 1371, 1183, 863, 823, 702, 685, 607, 501 cm.sup.1. MS (EI) m/z (relative intensity): 297 ([M.sup.+] 48), 255 (100), 219 (40), 185 (52), 157 (17), 43 (60). HR-MS (ESI) m/z calculated for C.sub.14H.sub.10Cl.sub.2FNO [M.sup.+] 297.0123. found 297.0128.

Example 8

N-([1,1-Biphenyl]-2-yl)acetamide

[0143] ##STR00025##

[0144] In a baked-out closable reaction vessel, a suspension consisting of

[0145] acetanilide (135 mg, 1.0 mmol), [{RuCl.sub.2(p-cymene)}.sub.2] (30.6 mg, 5.0 mol %), AgSbF.sub.6 (68.7 mg, 0.2 mmol), Ag.sub.2O (232 mg, 1.0 mmol), Na(OTf) (34.4 mg, 0.2 mmol) and phenylboronic acid (183 mg, 1.5 mmol) in dry DMF (3.0 ml) was stirred in a nitrogen atmosphere at 110 C. for 20 h. The reaction mixture was then diluted at room temperature with EtOAc (75 ml) and filtered through Celite and silica gel, and the filtrate was concentrated. According to NMR analysis, the crude product thus obtained contained 65% of theory of N-([1,1-biphenyl]-2-yl)acetamide.

Example 9

N-([1,1-Biphenyl]-2-yl)acetamide

[0146] ##STR00026##

[0147] The procedure was as described in Example 8, except that the reaction was conducted in the presence of 0.2 mmol of Zn(OTf).sub.2 rather than NaOTf. N-([1,1-Biphenyl]-2-yl)acetamide was obtained in a yield of 74% of theory.

Example 10

N-([1,1-Biphenyl]-2-yl)acetamide

[0148] ##STR00027##

[0149] The procedure was as described in Example 8, except that the reaction was conducted in the presence of 0.2 mmol of Mn(OTf).sub.2 rather than NaOTf. N-([1,1-Biphenyl]-2-yl)acetamide was obtained in a yield of 76% of theory.

Example 11

N-([1,1-Biphenyl]-2-yl)acetamide

[0150] ##STR00028##

[0151] The procedure was as described in Example 8, except that the reaction was conducted in the presence of 0.2 mmol of Ni(OTf).sub.2 rather than NaOTf. N-([1,1-Biphenyl]-2-yl)acetamide was obtained in a yield of 82% of theory.

Example 12

N-([1,1-Biphenyl]-2-yl)acetamide

[0152] ##STR00029##

[0153] In a baked-out closable reaction vessel, a suspension consisting of

[0154] acetanilide (135 mg, 1.0 mmol), [{RuCl.sub.2(p-cymene)}.sub.2] (30.6 mg, 5.0 mol %), AgSbF.sub.6 (68.7 mg, 0.2 mmol), Ag.sub.2O (232 mg, 1.0 mmol), CuSO.sub.4 (31.9 mg, 0.2 mmol) and phenylboronic acid (183 mg, 1.5 mmol) in dry DMF (3.0 ml) was stirred in a nitrogen atmosphere at 110 C. for 20 h. The reaction mixture was then diluted at room temperature with EtOAc (75 ml) and filtered through Celite and silica gel, and the filtrate was concentrated. The crude product thus obtained was purified by chromatography on silica gel (n-hexane/EtOAc: 7/3). 91 mg of N-([1,1-biphenyl]-2-yl)acetamide were obtained as a colourless solid (43% of theory).

Example 13

N-(3,4,5-Trifluoro-[1,1-biphenyl]-2-yl)acetamide

[0155] ##STR00030##

[0156] In a baked-out closable reaction vessel, a suspension consisting of

[0157] acetanilide (135 mg, 1.0 mmol), [{RuCl.sub.2(p-cymene)}.sub.2] (30.6 mg, 5.0 mol %), AgSbF.sub.6 (68.7 mg, 0.2 mmol), Ag.sub.2O (232 mg, 1.0 mmol), Cu(OTf).sub.2 (72.3 mg, 0.2 mmol) and 3,4,5-trifluorophenylboronic acid (264 mg, 1.5 mmol) in dry DMF (3.0 ml) was stirred in a nitrogen atmosphere at 110 C. for 20 h. The reaction mixture was then diluted at room temperature with EtOAc (75 ml) and filtered through Celite and silica gel, and the filtrate was concentrated. The crude product thus obtained was purified by chromatography on silica gel (n-hexane/EtOAc: 7/3). 180 mg of N-(3,4,5-trifluoro-[1,1-biphenyl]-2-yl)acetamide were obtained as a colourless solid (68% of theory). M.p.=140-141 C. .sup.1H NMR (CDCl.sub.3, 300 MHz): =8.08 (d, J=8.1 Hz, 1H), 7.40 (ddd, J=8.5, 5.9, 3.1 Hz, 1H), 7.24-7.17 (m, 2H), 7.06-6.97 (m, 2H), 6.93 (s, 1H), 2.07 (s, 3H). .sup.13C NMR (CDCl.sub.3, 126 MHz): =168.1 (C.sub.q), 151.39 (ddd, J.sub.C-F=251.6, 10.0, 4.2 Hz) (C.sub.q), 139.5 (dt, J.sub.C-F=253.1, 15.0 Hz) (C.sub.q), 134.5 (C.sub.q), 134.5 (C.sub.q), 130.5 (C.sub.q), 129.8 (CH), 129.5 (CH), 125.1 (CH), 123.3 (CH), 113.5 (dd, J.sub.C-F=16.1, 5.4 Hz) (CH), 24.3 (CH.sub.3). .sup.19F NMR (282 MHz, CDCl.sub.3) =132-8-133.0 (m), 161.0 (tt, J.sub.C-F=20.6, 6.5 Hz). IR (neat): 3263, 3040, 2934, 2864, 1660, 1526, 1483, 1417, 1359, 1278, 1241, 1036, 872, 857, 762, 695, 669, 634, 606, 547, 465 cm.sup.1. MS (EI) m/z (relative intensity): 265 ([M.sup.+] 29), 223 (100), 203 (16), 175 (5), 169 (5), 84 (6), 43 (41). HR-MS (ESI) m/z calculated for C.sub.14H.sub.10F.sub.3NO [M.sup.+] 265.0714. found 265.0718.

Example 14

N-(4-Chloro-[1,1-biphenyl]-2-yl)acetamide

[0158] ##STR00031##

[0159] In a baked-out closable reaction vessel, a suspension consisting of

[0160] acetanilide (135 mg, 1.0 mmol), [{RuCl.sub.2(p-cymene)}.sub.2] (30.6 mg, 5.0 mol %), AgSbF.sub.6 (68.7 mg, 0.2 mmol), Ag.sub.2O (232 mg, 1.0 mmol), Cu(OTf).sub.2 (72.3 mg, 0.2 mmol) and 4-chlorophenylboronic acid (234 mg, 1.5 mmol) in dry DMF (3.0 ml) was stirred in a nitrogen atmosphere at 110 C. for 20 h. The reaction mixture was then diluted at room temperature with EtOAc (75 ml) and filtered through Celite and silica gel, and the filtrate was concentrated. The crude product thus obtained was purified by chromatography on silica gel (n-hexane/EtOAc: 7/3). 172 mg of N-(4-chloro-[1,1-biphenyl]-2-yl)acetamide were obtained as a colourless solid (70% of theory).

[0161] M.p.=114-116 C. .sup.1H NMR (CDCl.sub.3, 300 MHz): =8.16 (d, J=8.2 Hz, 1H), 7.46-7.40 (m, 2H), 7.39-7.32 (m, 1H), 7.31-7.26 (m, 2H), 7.20-7.17 (m, 2H), 7.01 (s, 1H), 2.01 (s, 3H). .sup.13C NMR (CDCl.sub.3, 126 MHz): =168.1 (C.sub.q), 136.5 (C.sub.q), 134.4 (C.sub.q), 134.0 (C.sub.q), 131.3 (C.sub.q), 130.5 (CH), 129.9 (CH), 129.1 (CH), 128.6 (CH), 124.6 (CH), 122.2 (CH), 24.6 (CH.sub.3). IR (neat): 3247, 3031, 2924, 2854, 1635, 1527, 1369, 1283, 1086, 828, 756, 607, 530, 489 cm.sup.1. MS (EI) m/z (relative intensity): 245 ([M.sup.+] 35), 203 (100), 167 (43), 139 (12), 84 (17), 43 (36). HR-MS (ESI) m/z calculated for C.sub.14H.sub.12ClNO [M.sup.+] 245.0607. found 245.0599.

Example 15

N-(5-Methoxy-[1,1-biphenyl]-2-yl)acetamide

[0162] ##STR00032##

[0163] In a baked-out closable reaction vessel, a suspension consisting of

[0164] 4-methoxyacetanilide (165 mg, 1.0 mmol), [{RuCl.sub.2(p-cymene)}.sub.2] (30.6 mg, 5.0 mol %), AgSbF.sub.6 (68.7 mg, 0.2 mmol), Ag.sub.2O (232 mg, 1.0 mmol), Cu(OTf).sub.2 (72.3 mg, 0.2 mmol) and 4-chlorophenylboronic acid (234 mg, 1.5 mmol) in dry DMF (3.0 ml) was stirred in a nitrogen atmosphere at 110 C. for 20 h. The reaction mixture was then diluted at room temperature with EtOAc (75 ml) and filtered through Celite and silica gel, and the filtrate was concentrated. The crude product thus obtained was purified by chromatography on silica gel (n-hexane/EtOAc: 7/3). 183 mg of N-(5-methoxy-[1,1-biphenyl]-2-yl)acetamide were obtained as a colourless solid (76% of theory). M.p.=112-114 C. .sup.1H NMR (CDCl.sub.3, 300 MHz): =7.95 (d, J=8.9 Hz, 1H), 7.50-7.28 (m, 5H), 6.98 (s, 1H), 6.88 (dd, J=8.9, 3.0 Hz, 1H), 6.78 (d, J=3.0 Hz, 1H), 3.78 (s, 3H), 1.97 (s, 3H). .sup.13C NMR (CDCl.sub.3, 126 MHz): =168.2 (C.sub.q), 156.3 (C.sub.q), 138.1 (C.sub.q), 134.7 (C.sub.q), 128.9 (CH), 128.8 (CH), 127.8 (CH), 127.6 (C.sub.q), 124.3 (CH), 115.3 (CH), 113.3 (CH), 55.5 (CH.sub.3), 24.2 (CH.sub.3).

[0165] IR (neat): 3263, 3058, 2969, 2939, 2838, 1664, 1480, 1270, 1207, 1178, 1033, 701, 599, 512 cm.sup.1. MS (EI) m/z (relative intensity): 241 ([M.sup.+] 71), 199 (76), 184 (100), 154 (21), 128 (11), 43 (34). HR-MS (ESI) m/z calculated for C.sub.15H.sub.15NO.sub.2 [M.sup.+] 241.1103. found 241.1106.

Example 16

N-(4-Methoxy-[1,1-biphenyl]-2-yl)acetamide

[0166] ##STR00033##

[0167] In a baked-out closable reaction vessel, a suspension consisting of

[0168] 3-methoxyacetanilide (165 mg, 1.0 mmol), [{RuCl.sub.2(p-cymene)}.sub.2] (30.6 mg, 5.0 mol %), AgSbF.sub.6 (68.7 mg, 0.2 mmol), Ag.sub.2O (232 mg, 1.0 mmol), Cu(OTf).sub.2 (72.3 mg, 0.2 mmol) and 4-chlorophenylboronic acid (234 mg, 1.5 mmol) in dry DMF (3.0 ml) was stirred in a nitrogen atmosphere at 110 C. for 20 h. The reaction mixture was then diluted at room temperature with EtOAc (75 ml) and filtered through Celite and silica gel, and the filtrate was concentrated. The crude product thus obtained was purified by chromatography on silica gel (n-hexane/EtOAc: 7/3). 174 mg of N-(4-methoxy-[1,1-biphenyl]-2-yl)acetamide were obtained as a colourless solid (72% of theory). M.p.=91-93 C. .sup.1H NMR (CDCl.sub.3, 300 MHz): =7.98 (d, J=2.6 Hz, 1H), 7.49-7.42 (m, 2H), 7.40-7.36 (m, 1H), 7.35-7.32 (m, 1H), 7.32-7.29 (m, 1H), 7.17 (s, 1H), 7.12 (d, J=8.5 Hz, 1H), 6.72 (dd, J=8.5, 2.6 Hz, 1H), 3.84 (s, 3H), 2.00 (s, 3H). .sup.13C NMR (CDCl.sub.3, 126 MHz): =168.1 (C.sub.q), 159.4 (C.sub.q), 137.9 (C.sub.q), 135.6 (C.sub.q), 130.6 (CH), 129.3 (CH), 129.0 (CH), 127.6 (CH), 124.2 (C.sub.q), 110.5 (CH), 106.2 (CH), 55.5 (CH.sub.3), 24.8 (CH.sub.3). IR (neat): 3415, 3241, 3033, 2953, 2831, 1652, 1309, 1233, 762, 724, 698, 621, 525 cm.sup.1. MS (EI) m/z (relative intensity): 241 ([M.sup.+] 74), 199 (100), 170 (16), 156 (19), 84 (9), 43 (34). HR-MS (ESI) m/z calculated for C.sub.15H.sub.15NO.sub.2 [M.sup.+] 241.1103. found 241.1107.

Example 17

N-(5-Ethyl-[1,1-biphenyl]-2-yl)acetamide

[0169] ##STR00034##

[0170] In a baked-out closable reaction vessel, a suspension consisting of

[0171] 4-ethylacetanilide (163 mg, 1.0 mmol), [{RuCl.sub.2(p-cymene)}.sub.2] (30.6 mg, 5.0 mol %), AgSbF.sub.6 (68.7 mg, 0.2 mmol), Ag.sub.2O (232 mg, 1.0 mmol), Cu(OTf).sub.2 (72.3 mg, 0.2 mmol) and phenylboronic acid (183 mg, 1.5 mmol) in dry DMF (3.0 ml) was stirred in a nitrogen atmosphere at 110 C. for 20 h. The reaction mixture was then diluted at room temperature with EtOAc (75 ml) and filtered through Celite and silica gel, and the filtrate was concentrated. The crude product thus obtained was purified by chromatography on silica gel (n-hexane/EtOAc: 7/3). 151 mg of N-(5-ethyl-[1,1-biphenyl]-2-yl)acetamide were obtained as a colourless solid (63% of theory). M.p.=64-65 C. .sup.1H NMR (CDCl.sub.3, 300 MHz): =8.07 (d, J=8.3 Hz, 1H), 7.54-7.31 (m, 5H), 7.20 (dd, J=8.3, 2.3 Hz, 1H), 7.13 (s, 1H), 7.09 (d, J=2.3 Hz, 1H), 2.65 (q, J=7.6 Hz, 2H), 2.00 (s, 3H), 1.25 (t, J=7.6 Hz, 3H). .sup.13C NMR (CDCl.sub.3, 126 MHz): =168.0 (C.sub.q), 140.3 (C.sub.q), 138.3 (C.sub.q), 132.5 (C.sub.q), 132.1 (C.sub.q), 129.3 (CH), 129.0 (CH), 128.8 (CH), 127.6 (CH), 127.5 (CH), 122.2 (CH), 28.3 (CH.sub.2), 24.4 (CH.sub.3), 15.6 (CH.sub.3). IR (neat): 3424, 3267, 3027, 2964, 2930, 2871, 1659, 1513, 1487, 1410, 1368, 1297, 767, 699, 509 cm.sup.1. MS (EI) m/z (relative intensity): 239 ([M.sup.+] 58), 197 (58), 182 (100), 180 (19), 167 (16), 43 (37). HR-MS (ESI) m/z calculated for C.sub.16H.sub.17NO [M.sup.+] 239.1310. found 239.1306.

Example 18

N-(5-Hydroxy-[1,1-biphenyl]-2-yl)acetamide

[0172] ##STR00035##

[0173] In a baked-out closable reaction vessel, a suspension consisting of

[0174] 4-hydroxyacetanilide (151 mg, 1.0 mmol), [{RuCl.sub.2(p-cymene)}.sub.2] (30.6 mg, 5.0 mol %), AgSbF.sub.6 (68.7 mg, 0.2 mmol), Ag.sub.2O (232 mg, 1.0 mmol), Cu(OTf).sub.2 (72.3 mg, 0.2 mmol) and phenylboronic acid (183 mg, 1.5 mmol) in dry DMF (3.0 ml) was stirred in a nitrogen atmosphere at 110 C. for 20 h. The reaction mixture was then diluted at room temperature with EtOAc (75 ml) and filtered through Celite and silica gel, and the filtrate was concentrated. The crude product thus obtained was purified by chromatography on silica gel (n-hexane/EtOAc: 7/3). 157 mg of N-(5-hydroxy-[1,1-biphenyl]-2-yl)acetamide were obtained as a colourless solid (69% of theory). .sup.1H NMR (CDCl.sub.3, 300 MHz): =7.59 (d, J=9.5 Hz, 1H), 7.53 (s, 1H), 7.43-7.32 (m, 3H), 7.30-7.24 (m, 2H), 7.05 (s, 1H), 6.73-6.67 (m, 2H), 1.99 (s, 3H). .sup.13C NMR (CDCl.sub.3, 126 MHz): =169.7 (C.sub.q), 154.1 (C.sub.q), 138.1 (C.sub.q), 136.1 (C.sub.q), 128.8 (CH), 128.6 (CH), 127.6 (CH), 126.0 (C.sub.q), 125.7 (CH), 117.1 (CH), 115.3 (CH), 23.9 (CH.sub.3). IR (neat): 3268, 3057, 2959, 2926, 2795, 1524, 1488, 1433, 1299, 1199, 726, 699, 646, 506 cm.sup.1. MS (EI) m/z (relative intensity): 227 ([M.sup.+] 44), 185 (100), 154 (11), 43 (14). HR-MS (ESI) m/z calculated for C.sub.14H.sub.13NO.sub.2 [M.sup.+] 227.0946. found 227.0945.

Example 19

N-(4-Methyl-[1,1-biphenyl]-2-yl)acetamide

[0175] ##STR00036##

[0176] In a baked-out closable reaction vessel, a suspension consisting of

[0177] acetanilide (135 mg, 1.0 mmol), [{RuCl.sub.2(p-cymene)}.sub.2] (30.6 mg, 5.0 mol %), AgSbF.sub.6 (68.7 mg, 0.2 mmol), Ag.sub.2O (232 mg, 1.0 mmol), Cu(OTf).sub.2 (72.3 mg, 0.2 mmol) and 4-methylphenylboronic acid (204 mg, 1.5 mmol) in dry DMF (3.0 ml) was stirred in a nitrogen atmosphere at 110 C. for 20 h. The reaction mixture was then diluted at room temperature with EtOAc (75 ml) and filtered through Celite and silica gel, and the filtrate was concentrated. The crude product thus obtained was purified by chromatography on silica gel (n-hexane/EtOAc: 7/3). 185 mg of N-(4-methyl-[1,1-biphenyl]-2-yl)acetamide were obtained as a colourless solid (82% of theory). M.p.=106-108 C. .sup.1H NMR (CDCl.sub.3, 300 MHz): =8.24 (d, J=8.2 Hz, 1H), 7.44-7.06 (m, 8H), 2.41 (s, 3H), 2.01 (s, 3H). .sup.13C NMR (CDCl.sub.3, 126 MHz): =168.0 (C.sub.q), 137.6 (C.sub.q), 135.0 (C.sub.q), 134.6 (C.sub.q), 132.0 (C.sub.q), 130.0 (CH), 129.7 (CH), 128.9 (CH), 128.1 (CH), 124.1 (CH), 121.4 (CH), 24.6 (CH.sub.3), 21.2 (CH.sub.3). IR (neat): 3340, 2956, 2921, 2853, 1515, 1442, 1282, 817, 756, 680, 598, 522, 488 cm.sup.1. MS (EI) m/z (relative intensity): 225 ([M.sup.+] 55), 183 (100), 167 (37), 43 (26). HR-MS (ESI) m/z calculated for C.sub.15H.sub.15NO [M.sup.+] 225.1154. found 225.1149.

Example 20

N-(4-Methoxy-[1,1-biphenyl]-2-yl)acetamide

[0178] ##STR00037##

[0179] In a baked-out closable reaction vessel, a suspension consisting of

[0180] acetanilide (135 mg, 1.0 mmol), [{RuCl.sub.2(p-cymene)}.sub.2] (30.6 mg, 5.0 mol %), AgSbF.sub.6 (68.7 mg, 0.2 mmol), Ag.sub.2O (232 mg, 1.0 mmol), Cu(OTf).sub.2(72.3 mg, 0.2 mmol) and 4-methoxyphenylboronic acid (228 mg, 1.5 mmol) in dry DMF (3.0 ml) was stirred in a nitrogen atmosphere at 110 C. for 20 h. The reaction mixture was then diluted at room temperature with EtOAc (75 ml) and filtered through Celite and silica gel, and the filtrate was concentrated. The crude product thus obtained was purified by chromatography on silica gel (n-hexane/EtOAc: 7/3). 200 mg of N-(4-methyl-[1,1-biphenyl]-2-yl)acetamide were obtained as a colourless solid (83% of theory). M.p.=135-137 C. .sup.1H NMR (CDCl.sub.3, 300 MHz): =8.20 (d, J=8.2 Hz, 1H), 7.34-7.24 (m, 3H), 7.23-7.09 (m, 3H), 6.98 (d, J=8.6 Hz, 2H), 3.84 (s, 3H), 2.00 (s, 3H). .sup.13C NMR (CDCl.sub.3, 126 MHz): =168.3 (C.sub.q), 159.3 (C.sub.q), 134.8 (C.sub.q), 132.0 (C.sub.q), 130.3 (CH), 130.2 (C.sub.q), 130.1 (CH), 128.0 (CH), 124.3 (CH), 121.6 (CH), 114.4 (CH), 55.2 (CH.sub.3), 24.4 (CH.sub.3). IR (neat): 3351, 3012, 2921, 2842, 1690, 1602, 1512, 1439, 1362, 1294, 1239, 1175, 1031, 832, 800, 770, 663, 581, 560, 534 cm.sup.1. MS (EI) m/z (relative intensity): 241 ([M.sup.+] 54), 199 (100), 184 (37), 154 (24), 128 (12), 43 (30). HR-MS (ESI) m/z calculated for C.sub.15H.sub.15NO.sub.2 [M.sup.+] 241.1103. found 241.1110.

Example 21

N-(Biphenyl-2-yl)-2-methylpropanamide

[0181] ##STR00038##

[0182] In a baked-out closable reaction vessel, a suspension consisting of

[0183] 2-methyl-N-phenylpropanamide (163 mg, 1.0 mmol), [{RuCl.sub.2(p-cymene)}.sub.2] (30.6 mg, 5.0 mol %), AgSbF.sub.6 (68.7 mg, 0.2 mmol), Ag.sub.2O (232 mg, 1.0 mmol), Cu(OTf).sub.2 (72.3 mg, 0.2 mmol) and phenylboronic acid (183 mg, 1.5 mmol) in dry DMF (3.0 ml) was stirred in a nitrogen atmosphere at 110 C. for 20 h. The reaction mixture was then diluted at room temperature with EtOAc (75 ml) and filtered through Celite and silica gel, and the filtrate was concentrated. The crude product thus obtained was purified by chromatography on silica gel (n-hexane/EtOAc: 7/3). 131 mg of N-(biphenyl-2-yl)-2-methylpropanamide were obtained as a colourless solid (55% of theory). M.p.=126-128 C. .sup.1H NMR (CDCl.sub.3, 300 MHz): =8.33 (d, J=8.2 Hz, 1H), 7.54-7.33 (m, 6H), 7.28-7.13 (m, 3H), 2.4 (hept, J=6.8 Hz, 1H), 1.2 (d, J=6.8 Hz, 6H). .sup.13C NMR (CDCl.sub.3, 126 MHz): =174.8 (C.sub.q), 138.1 (C.sub.q), 134.9 (C.sub.q), 132.1 (C.sub.q), 129.9 (CH), 129.3 (CH), 129.0 (CH), 128.4 (CH), 128.0 (CH), 124.0 (CH), 121.3 (CH), 36.7 (CH), 19.3 (CH.sub.3). IR (neat): 3218, 2964, 1649, 1520, 1480, 1239, 1203, 1099, 776, 748, 726, 702, 542 cm.sup.1. MS (EI) m/z (relative intensity): 239 ([M.sup.+] 29), 169 (100), 71(6), 43 (30). HR-MS (ESI) m/z calculated for C.sub.16H.sub.17NO [M.sup.+] 239.1310. found 239.1314.

Example 22

N-(Biphenyl-2-yl)-2,2-dimethylpropanamide

[0184] ##STR00039##

[0185] In a baked-out closable reaction vessel, a suspension consisting of

[0186] 2,2-dimethyl-N-phenylpropanamide (177 mg, 1.0 mmol), [{RuCl.sub.2(p-cymene)}.sub.2] (30.6 mg, 5.0 mol %), AgSbF.sub.6 (68.7 mg, 0.2 mmol), Ag.sub.2O (232 mg, 1.0 mmol), Cu(OTf).sub.2 (72.3 mg, 0.2 mmol) and phenylboronic acid (183 mg, 1.5 mmol) in dry DMF (3.0 ml) was stirred in a nitrogen atmosphere at 110 C. for 20 h. The reaction mixture was then diluted at room temperature with EtOAc (75 ml) and filtered through Celite and silica gel, and the filtrate was concentrated. The crude product thus obtained was purified by chromatography on silica gel (n-hexane/EtOAc: 7/3). 114 mg of N-(biphenyl-2-yl)-2,2-dimethylpropanamide were obtained as a colourless solid (45% of theory). M.p.=68-69 C. .sup.1H NMR (CDCl.sub.3, 300 MHz): =8.37 (dd, J=8.2, 1.2 Hz, 1H), 7.54-7.33 (m, 7H), 7.24 (dd, J=7.4, 1.7 Hz, 1H), 7.17 (dd, J=7.4, 1.7 Hz, 1H), 1.09 (s, 9H). .sup.13C NMR (CDCl.sub.3, 126 MHz): =176.1 (C.sub.q), 138.0 (C.sub.q), 135.0 (C.sub.q), 132.0 (C.sub.q), 129.6 (CH), 129.2 (CH), 128.9 (CH), 128.4 (CH), 127.9 (CH), 123.8 (CH), 120.8 (CH), 39.8 (C.sub.q), 27.4 (CH.sub.3). IR (neat): 3259, 3056, 2970, 2904, 2868, 1646, 1503, 1477, 771, 743, 700, 647 cm.sup.1. MS (EI) m/z (relative intensity): 253 ([M.sup.+] 53), 169 (60), 57 (100), 41 (17). HR-MS (ESI) m/z calculated for C.sub.17H.sub.19NO [M.sup.+] 253.1467. found 253.1472.