B. H. Lipshutz et al. / Tetrahedron 56 (2000) 2139±2144
2143
4-Carboxaldehydebiphenyl (Table 1, entry A). The
general procedure above was followed using the same
reagents and relative amounts with the exception of
4-chlorobenzaldehyde (101 mg, 0.72 mmol). The crude
product was subjected to the standard workup and chroma-
tography using 10% EtOAc/hexanes. The product was
isolated as an off-white solid (112 mg, 85%).18
subjected to the standard workup and chromatography using
10% EtOAc/hexanes. The product was isolated as a white
solid (327 mg, 88%).22
4-Naphthylbenzophenone (Table 1, entry H). The general
procedure above was followed using 4-chloroacetophenone
(108 mg, 0.5 mmol), naphthylboronic acid (129 mg,
0.75 mmol), Ni/C (40 mg, 0.75 mmol Ni/g, 0.03 mmol),
triphenylphosphine (32 mg, 0.12 mmol), n-butyllithium,
(2.55 M, 47 mL, 0.12 mmol), lithium bromide (65 mg,
0.75 mmol), potassium phosphate (130 mg, 1.5 mmol),
and dioxane (1.5 mL). The crude product was subjected to
the standard workup and chromatography eluting with 5%
EtOAc/hexanes. The product was isolated as a clear oil
(154 mg, 78%); Rf0.5 (hexanes/ethyl acetate, 10/1); IR
(CH2Cl2) 3058, 2951, 2924, 2854, 1930, 1817, 1721,
1658, 1604, 1579, 1447, 1397, 1177, 1149, 938, 924, 858,
30-Tri¯uoromethyl-4-carboxaldehydebiphenyl (Table 1,
entry B). The general procedure above was followed using
the same reagents and relative amounts with the exception
of 4-chlorobenzaldehyde (101 mg, 0.72 mmol) and
3-tri¯uoromethylphenylboronic acid (205 mg, 1.08 mmol).
The crude product was subjected to the standard workup and
chromatography using 10% EtOAc/hexanes. The product
was isolated as an oil (120 mg, 67%).19
1
4-Methylbiphenyl-2-carbonitrile; `OTBN' (Table 1, entry
C). The general procedure above was followed using 2-
methylbenzonitrile (138 mg, 1.0 mmol), tolylboronic acid
(136 mg, 1.5 mmol), Ni/C (100 mg, 0.5 mmol Ni/g,
0.05 mmol), triphenylphosphine (52 mg, 0.20 mmol),
n-butyllithium (74 mL, 2.70 M, 0.20 mmol), lithium
bromide (217 mg, 2.5 mmol), and potassium phosphate
(636 mg, 3 mmol). The crude product was subjected to the
standard workup and chromatography eluting with 5%
EtOAc/hexanes. The product was isolated as a white
crystalline solid (162 mg, 84%); Rf0.5 (hexanes/ethyl
acetate, 10/1); IR (CH2Cl2) 3047, 3027, 2950, 2921,
2863, 2224, 1596, 1517, 1478, 1443, 1285, 1266, 1186,
778, 702, 671, 633; H NMR (400 MHz) d 7.97±7.88 (m,
7H), 7.64±7.59 (m, 3H), 7.57±7.44 (m, 6H); 13C NMR
(100 MHz) d 196.7, 145.4, 139.3, 137.9, 136.6, 134.0,
132.7, 131.4, 130.4, 130.3, 130.3, 128.6, 128.6, 128.5,
127.2, 126.6, 126.2, 125.8, 125.6; LREIMS 309.04(22),
308(100), 232(6), 231(51), 203(16), 202(34), 105(28.7),
77(28); HREIMS calcd for C23H16O, 308.1201, found
308.1203.
3-Methyl-40methoxybiphenyl (Table 1, entry I). The
general procedure above was followed using the same
reagents and relative amounts with the exception of
3-chlorotoluene (88 mL, 0.72 mmol) and 4-methoxyphenyl-
boronic acid (164 mg, 1.08 mmol). The crude product was
subjected to the standard workup and chromatography using
2% EtOAc/hexanes. The product was isolated as a white
solid (101 mg, 71%).23
1
1107, 1047, 1006, 947, 821, 762; H NMR (400 MHz)
d 7.77±7.74 (m, 1H), 7.65±7.61 (m, 1H), 7.53±7.40
(m, 4H), 7.32±7.29 (m, 21H), 2.43 (s, 3H); 13C NMR
(100 MHz) d(145.7, 138.9, 135.4, 133.9, 133.0,
130.2, 129.6, 128.8, 127.5, 119.1, 111.4, 21.5; LREIMS
194(14), 193(100), 192(32), 191(5), 190(7), 165(21),
82(5); HREIMS calcd for C14H11N, 193.0892, found
193.0893.
5-Methoxy-8-phenylquinoline (Table 1, entry J). The
general procedure above was followed using the same
reagents and relative amounts with the exception of
8-chloro-5-methoxyquinoline (139 mg, 0.72 mmol). The
crude product was subjected to the standard workup and
chromatography, eluting with 50% EtOAc/hexanes. The
4-Phenylacetophenone (Table 1, entry E). The general
procedure above was followed using the same reagents
and relative amounts with the exception of 4-chloroaceto-
phenone (93 mL, 0.72 mmol). The crude product was
subjected to the standard workup and chromatography
using 10% EtOAc/hexanes. The product was isolated as a
white solid (129 mg, 92%).20
1
product was isolated as a white solid (143 mg, 85%); H
NMR (400 MHz) d 8.70 (dd, J4.2, 1.7 Hz, 1H), 8.51
(dd, J8.4, 1.7 Hz, 1H), 7.50 (dd, J8.4, 4.03 Hz, 1H),
7.51 (d, J8.4 Hz, 1H), 7.50±7.38 (m, 5H), 6.95 (d,
J8.4 Hz, 1H), 4.08 (s, 3H); 13C NMR (100 MHz) d
154.7, 149.8, 140.7, 133.1, 130.2, 128.6, 127.5, 127.4,
127.0, 126.5, 122.5, 122.2, 107.5, 56.3; IR (KBr) 3061,
3016, 2941, 1597, 1502, 1308, 1097, 924, 782; LREIMS
235(9), 206(16), 195(22), 194(75), 192(88), 164(100),
128(62), 63(21); HREIMS calcd for C16H12NO (M1±H)
234.0921, found 234.0919.
3-(4-Acetylphenyl)thiophene (Table 1, entry F). The
general procedure above was followed using the same
reagents and relative amounts with the exception of 4-
chloroacetophenone (93 mL, 0.72 mmol) and thiophene-
3-boronic acid (138 mg, 1.08 mmol). The crude product
was subjected to the standard workup and chromatography
using 10% EtOAc/hexanes. The product was isolated as a
white solid (127 mg, 88%).21
2-Phenyl-6-tri¯uoromethylpyridine (Table 1, entry K).
The general procedure above was followed using the same
reagents and relative amounts with the exception of
2-chloro-5-tri¯uoromethylpyridine (131 mg, 0.72 mmol).
The crude product was subjected to the standard workup
and chromatography eluting with 5% EtOAc/hexanes. The
4-Phenylbenzophenone (Table 1, entry G). The general
procedure above was followed using 4-chlorobenzophenone
(312 mg, 1.44 mmol), phenylboronic acid (264 mg,
2.16 mmol), K3PO4 (1.09 g, 5.16 mmol, 3.6 equiv.), LiBr
(150 mg, 1.73 mmol), PPh3 (90 mg, 0.35 mmol,
0.12 equiv.) and 0.66 mmol/g Ni/C (130 mg, 0.09 mmol,
0.06 equiv.) and dioxane (3.0 mL). The crude product was
1
product was isolated as a white solid (142 mg, 89%); H
NMR (400 MHz) d 8.96 (s, 1H), 8.04 (d, J8.1 Hz, 1H),
8.00 (d, J8.4 Hz, 1H), 7.86 (d, J8.2 Hz, 1H), 7.50 (m,
2H), 7.30 (m, 2H); 13C NMR (100 MHz)( d(146.6, 134.4,