Tetrahedron
8
MHz, CDCl3): δ = 7.37 (td, 1H, J = 8.0, 7.0 Hz), 7.47 (s, 1H),
7.52 (td, 1H, J = 8.5, 7.0 Hz), 6.57 (d, 1H, J = 8.5 Hz), 7.69 (d,
1H, J = 8.0 Hz); 13C{1H}NMR (100 MHz, CDCl3): δ = 111.8,
112.1, 118.5, 122.6, 124.5, 125.5, 127.3, 128.4, 155.7; HRMS
(ESI) Calcd for C9H6NO [M+H]+ = 144.0444, Found = 144.0444.
reaction mixture, and the product was extracted with AcOEt (10.0
mL × 3). The organic layer was dried over Na2SO4. After
filtration and removal of the solvent, the residue was purified by
silica-gel column chromatography (chloroform: n-hexane = 1:1)
to give 2-methoxybenzonitrile 2A (315.6 mg, 79%).
4.3.9 2-Benzothiophenecarbonitrile (2I): Yield: 453.7 mg
4.3.1 2-Methoxybenzonitrile (2A): Yield: 315.6 mg (79%); Oil
(commercially available); IR (neat) 2228 cm-1; 1H-NMR (400
MHz, CDCl3): δ = 3.94 (s, 3H), 6.97-7.03 (m, 2H), 7.50-7.58 (m,
2H); 13C{1H}NMR (100 MHz, CDCl3): δ = 55.9, 101.7, 111.2,
116.5, 120.7, 133.7, 134.4, 161.2.
1
(95%); yellow liquid; IR (neat) 2216 cm-1; H-NMR (400 MHz,
CDCl3): δ = 7.48 (td, 1H, J = 8.0, 7.0 Hz), 7.54 (td, 1H, J = 8.0,
7.7 Hz), 7.86-7.91 (m, 3H); 13C{1H}NMR (100 MHz, CDCl3): δ =
109.6, 114.5, 122.3, 125.2, 125.7, 127.8, 135.0, 137.4, 141.2;
HRMS (ESI) Calcd for C9H6NS [M+H]+ = 160.0125, Found =
160.0125.
4.3.2 2,6-Dimethoxybenzonitrile (2B): Yield: 381.8 mg (78%);
yellow solid (commercially available); Mp: 113-114 °C; IR (neat)
2229 cm-1; 1H-NMR (400 MHz, CDCl3): δ = 3.91 (s, 6 H), 6.55 (d,
2H, J = 8.5 Hz), 7.44 (t, 1H, J = 8.5 Hz); 13C{1H}NMR (100 MHz,
CDCl3): δ = 56.2, 91.3, 103.8, 104.4, 134.6, 162.7.
4.3.10 2-Cyano-1-methylindole (2J): Yield: 459.2 mg (98%);
yellow solid; Mp: 70 °C; IR (neat) 2221 cm-1; 1H-NMR (400 MHz,
CDCl3): δ = 3.91 (s, 3H), 7.16 (s, 1H), 7.21 (dd, 1H, J = 8.0, 6.8
Hz), 7.36 (d, 1H, J = 8.0 Hz), 7.41 (dd, 1H, J = 8.3, 6.8 Hz), 7.67
(d, 1H, J = 8.3 Hz); 13C{1H}NMR (100 MHz, CDCl3): δ = 31.5,
110.06, 110.14, 112.6, 113.6, 121.3, 122.3, 125.8, 126.0, 137.9;
HRMS (ESI) Calcd for C10H9N2 [M+H]+ = 157.0760, Found =
157.0765.
4.3.3 2,5-Dimethoxybenzonitrile (2C): Yield: 460.2 mg (94%);
yellow solid (commercially available); Mp: 79-80 °C; IR (neat)
2224 cm-1; 1H-NMR (400 MHz, CDCl3): δ = 3.79 (s, 3 H), 3.89 (s,
3H), 6.90 (d, 1H, J = 9.1 Hz), 7.06 (d, 1H, J = 3.2 Hz), 7.10 (dd,
1H, J = 9.1, 3.2 Hz); 13C{1H}NMR (100 MHz, CDCl3): δ = 55.9,
56.4, 101.7, 112.5, 116.4, 117.5, 120.8, 153.1, 155.7.
4.3.11 2-Cyano-5-ethylfuran (2K): Yield: 290.7 mg (80%);
yellow liquid; IR (neat) 2228 cm-1; 1H-NMR (400 MHz,
CDCl3): δ = 1.27 (t, 3H, J = 7.6 Hz), 2.71 (q, 2H, J = 7.6 Hz),
6.13 (d, 1H, J = 3.5 Hz), 7.01 (d, 1H, J = 3.5 Hz); 13C{1H}NMR
(100 MHz, CDCl3): δ = 11.6, 21.6, 106.2, 112.0, 123.1, 124.2,
163.6; HRMS (ESI) Calcd for C7H8NO [M+H]+ = 122.0600,
Found = 122.0600.
4.3.4 2,3-Dimethoxybenzonitrile (2D): Yield: 445.5 mg (91%);
yellow solid (commercially available); Mp: 47 °C; IR (neat) 2230
cm-1; 1H-NMR (400 MHz, CDCl3): δ = 3.90 (s, 3H), 4.03 (s, 3H),
7.10-7.16 (m, 3H); 13C{1H}NMR (100 MHz, CDCl3): δ = 56.0,
61.6, 106.9, 116.2, 116.9, 124.4 (2C), 151.6, 152.6.
4.3.12 2-Cyano-5-ethylthiophene (2L): Yield: 366.3 mg (89%);
1
yellow liquid; IR (neat) 2217 cm-1; H-NMR (400 MHz, CDCl3):
4.3.5 2-(Methoxymethoxy)-5-methylbenzonitrile (2E): Yield:
δ = 1.34 (t, 3H, J = 7.5 Hz), 2.90 (q, 2H, J = 7.5 Hz), 6.81 (d, 1H,
J = 3.6 Hz), 7.46 (d, 1H, J = 3.6 Hz), 13C{1H}NMR (100 MHz,
CDCl3): δ = 15.6, 23.6, 106.7, 114.7, 124.3, 137.7, 155.8; HRMS
(ESI) Calcd for C7H8NS [M+H]+ = 138.0372, Found = 138.0376.
1
393.4 mg (74%); yellow liquid; IR (neat) 2226 cm-1; H-NMR
(400 MHz, CDCl3): δ = 2.31 (s, 3H), 3.52 (s, 3H), 5.26 (s, 2H),
7.12 (d, 1H, J = 8.6 Hz), 7.31 (dd, 1H, J = 8.6, 1.6 Hz), 7.37 (d,
1H, J = 1.6 Hz); 13C{1H}NMR (100 MHz, CDCl3): δ = 20.2, 56.5,
94.8, 102.5, 114.9, 116.5, 131.6, 133.5, 135.0, 157.0; HRMS
(ESI) Calcd for C10H12NO2 [M+H]+ = 178.0863, Found =
178.0859.
4.4 Procedure for Transformation of 4-Cyanobiphenyl 2a into
4-(Aminomethyl)biphenyl 3a: To a solution of 4-cyanobiphenyl
2a (1.0 mmol, 179.2 mg) in THF (8.0 mL) were slowly added
LiAlH4 (1.5 mmol, 56.9 mg) at 0 °C. The obtained mixture was
stirred for 4 h at 70 °C. Water (5 mL) and aq. NaOH 1 M, 10.0
mL) were added to the reaction mixture. The aqueous layer was
extracted with CHCl3 (5.0 mL × 3). The organic layer was
washed with brine, dried over Na2SO4, and filtered through celite.
The solvent was removed under reduced pressure to give
4-(aminomethyl)biphenyl 3a (179.6 mg, 98%).
4.3.6 2-Phenoxybenzonitrile (2F): Yield: 468.5 mg (80%);
1
yellow liquid; IR (neat) 2230 cm-1; H-NMR (400 MHz, CDCl3):
δ = 6.86 (dd, 1H, J = 7.6, 1.6 Hz), 7.09 (dd, 2H, J = 7.6, 1.1 Hz),
7.13 (td, 1H, J = 8.5, 7.6 Hz), 7.22 (tt, 1H, J = 7.6, 1.1 Hz), 7.41 (t,
2H, J = 7.6 Hz), 7.47 (td, 1H, J = 8.5, 7.7 Hz), 7.66 (dd, 1H, J =
7.7, 1.6 Hz); 13C{1H}NMR (100 MHz, CDCl3): δ = 103.6, 116.0
116.9, 120.0, 122.7, 125.0, 130.1, 133.8, 134.2, 154.9, 159.7;
HRMS (ESI) Calcd for C13H10NO [M+H]+ = 196.0757 Found =
196.0753.
4.4.1 4-(Aminomethyl)biphenyl (3a): Yield: 179.6 mg (98%);
white solid; Mp 128-129 °C: IR (neat) 3269 (br), 2630, 1586,
1485, 1396, 1304, 1245, 1131, 986 cm-1; 1H-NMR (400 MHz,
CDCl3): δ = 3.93 (s, 2H), 7.34 (t, 1H, J = 7.4 Hz), 7.39 (d, 2H, J =
8.2 Hz), 7.44 (dd, 2H, J = 7.7, 7.4 Hz), 7.57-7.61 (m, 4H);
13C{1H}NMR (100 MHz, CDCl3): δ = 46.2, 127.0, 127.2, 127.3,
127.5, 128.7, 139.8, 140.9, 142.4; HRMS (ESI) Calcd for
C13H14N [M+H]+ = 184.1121, Found = 184.1120.
4.3.7 3-Methoxy-2-naphthonitrile (2G): Yield: 472.7 mg (86%);
1
white solid; Mp: 123-124 °C; IR (neat) 2224 cm-1; H-NMR (400
MHz, CDCl3): δ = 4.03 (s, 3H), 7.19 (s, 1H), 7,43 (dd, 1H, J = 8.3,
7.5 Hz), 7.58 (dd, 1H, J = 8.3, 7.5 Hz), 7.76 (d, 1H, J = 8.3 Hz)
7.80 (d, 1H, J = 8.3 Hz), 8.15 (s, 1H); 13C{1H}NMR (100 MHz,
CDCl3): δ = 56.0, 103.4, 106.2, 116.5, 125.1, 126.8, 127.4, 128.2,
129.4, 136.0, 136.2, 156.2; HRMS (ESI) Calcd for C12H10ON
[M+H]+ = 184.0757, Found = 184.0760.
4.5 Procedure for Transformation of 4-Cyanobiphenyl 2a into
4-Biphenylcarboxamide 4a: To a solution of 4-cyanobiphenyl 2a
(1.0 mmol, 179.2 mg) in THF (8.0 mL) were added aq. NH3 (28%,
10.0 mL) and KI (3.0 mmol, 498.0 mg) at 0 °C. Aq. H2O2 (30%,
10.0 mL) was added dropwise to the mixture. The obtained
4.3.8 2-Benzofurancarbonitrile (2H): Yield: 365.02 mg (85%);
1
yellow solid; Mp: 34-35°C; IR (neat) 2234 cm-1; H-NMR (400