Direct Arylation Reactions Catalyzed by Pd(OH)2/C
2.88 (3H, s), 3.07 (1H, dd, J ) 3.0, 14.1 Hz), 4.37 (2H, s), 5.04
(1H, dd, J ) 3.0, 9.9 Hz), 6.99 (1H, t, J ) 7.5 Hz), 7.25 (6H,
m), 7.49 (1H, d, J ) 7.8 Hz), 7.82 (1H, d, J ) 8.0 Hz); 13C NMR
(75 MHz, CDCl3, 293 K, TMS) δ 43.8, 55.7, 82.5, 94.8, 98.8,
126.7, 127.8, 128.5, 128.9, 129.7, 130.0, 139.0, 139.7, 144.5;
HRMS calcd for C16H17IO2 (M+ C14H12I) 306.9984, found
307.0012.
1-(2-Iodophenoxy)benzene (22). Prepared according to
literature procedure (87%):25 mp 53-54 °C; IR (νmax/cm-1) 3062,
2923, 1573, 1234, 748; 1H NMR (300 MHz, CDCl3, 293 K, TMS)
δ 6.87 (2H, m), 6.94 (2H, m), 7.11 (1H, td, J ) 0.9, 7.5 Hz),
7.30 (3H, m), 7.86 (1H, dd, J ) 1.5, 7.8 Hz); 13C NMR (75 MHz,
CDCl3, 293 K, TMS) δ 88.9, 118.4, 119.4, 123.4, 125.3, 129.6,
129.7, 139.8, 156.4, 156.8; HRMS calcd for C12H9IO (M+)
295.9698, found 295.9690.
Products. General Procedure for Intramolecular Di-
rect Arylation Reactions. To a mixture of potassium acetate
(2 equiv), Pd(OH)2/C (0.1 equiv), and substrate (1 equiv), under
nitrogen atmosphere, was added DMA (0.2 M) in a 2 mL screw
cap vial equipped with a mechanical stir bar. The reaction
mixture was then heated overnight at 145 °C. After the
reaction was judged complete by TLC or GC/MS analysis, the
heat source was removed and the reaction mixture was allowed
to cool. The crude mixture was then purified via silica gel
column chromatography using ethyl acetate/hexanes mixtures.
The substrates were reacted under the general procedure
for intramolecular direct arylation reactions. Compounds 21
(91%), 519 (95%), 2126 (80%), 2327 (92%), 2528 (84%), and 2729
(84%) exhibited spectral data identical to those reported in the
literature.
J ) 8.2 Hz); 13C NMR (75 MHz, CDCl3, 293 K, TMS) δ 46.8,
123.3, 124.2, 125.5, 126.4, 127.3, 128.0, 128.1, 128.2, 128.5,
129.0, 130.1, 131.7, 134.3, 135.1, 138.2, 169.1; HRMS calcd
for C20H15NO (M+) 285.1154, found 285.1162.
N-(2,2-Dimethylpropanoyl)-(6H)-phenanthridine (15).
The substrate was treated under the general procedure for
intramolecular direct arylation reactions (98%): mp 114-116
1
°C; IR (νmax/cm-1) 3068, 2973, 1650, 1358, 1168, 764, 738; H
NMR (300 MHz, CDCl3, 293 K, TMS) δ 1.34 (9H, s), 4.82 (2H,
s), 7.28 (4H, m), 7.39 (1H, t, J ) 7.4 Hz), 7.55 (1H, d, J ) 7.5
Hz), 7.76 (2H, m); 13C NMR (75 MHz, CDCl3, 293 K, TMS) δ
28.9, 39.8, 49.1, 123.5, 124.0, 125.3, 125.8, 126.3, 127.3, 127.7,
128.3, 132.5, 134.4, 138.9, 177.4; HRMS calcd for C18H19NO
(M+) 265.1467, found 265.1451.
N-(4-Hydroxybenzoyl)-(6H)-phenanthridine (17). The
substrate was treated under the general procedure for in-
tramolecular direct arylation reactions (83%): mp 142-144
°C; IR (νmax/cm-1) 3259, 2926, 1608, 1495, 1390, 1230, 757; 1H
NMR (300 MHz, DMSO, 293 K) δ 4.90 (2H, s), 6.66 (2H, d, J
) 8.3 Hz), 6.77 (1H, d, J ) 8.3 Hz), 7.10 (3H, m), 7.21 (1H, t,
J ) 7.4 Hz), 7.30-7.48 (3H, m), 7.91 (1H, d, J ) 7.7 Hz), 7.97
(1H, d, J ) 5.4 Hz), 10.00 (1H, s); 13C NMR (75 MHz, DMSO,
293 K) δ 46.6, 114.8, 123.3, 124.3, 125.1, 125.1, 125.2, 126.1,
127.3, 127.7, 128.0, 128.2, 130.8, 131.2, 134.1, 138.4 159.5,
168.1; HRMS calcd for C20H15NO2 (M+) 301.1103, found
301.1095.
9,10-Dihydro-9-(methoxymethoxy)phenanthrene (19).
The substrate was treated under the general procedure for
intramolecular direct arylation reactions (86%): IR (νmax/cm-1
)
1
3067, 3033, 2941, 2887, 1327, 1147, 1096, 1041, 755, 740; H
NMR (300 MHz, CDCl3, 293 K, TMS) δ 3.15 (2H, dd, J ) 3.5,
4.6 Hz), 3.36 (3H, s), 4.65 (2H, dd, J ) 7.0, 11.8 Hz), 4.82 (1H,
t, J ) 4.8 Hz), 7.22-7.33 (4H, m), 7.41 (2H, m), 7.80 (2H, t, J
) 7.0 Hz); 13C NMR (75 MHz, CDCl3, 293 K, TMS) δ 35.2,
55.3, 71.7, 94.1, 123.5, 124.1, 127.2, 127.4, 127.9, 128.3, 128.9,
129.2, 133.7, 133.7, 133.9, 134.9; HRMS calcd for C16H16O2
(M+) 240.1150, found 240.1150.
6H-Benzo[c]chromene-2-carbonitrile (7). The substrate
was treated under the general procedure for intramolecular
direct arylation reactions (92%): mp 85-87 °C; IR (νmax/cm-1
)
2224, 1609, 1493, 1248, 1011, 824; 1H NMR (300 MHz, CDCl3,
293 K, TMS) δ 5.16 (2H, s), 6.98 (1H, d, J ) 7.8 Hz), 7.13 (1H,
d, J ) 7.3 Hz), 7.35 (2H, m), 7.45 (1H, dd, J ) 8.2, 1.9 Hz),
7.61 (1H, d, J ) 7.3 Hz), 7.94 (1H, d, J ) 2.1 Hz); 13C NMR
(75 MHz, CDCl3, 293 K, TMS) δ 68.6, 105.5, 118.5, 119.1,
122.1, 123.7, 124.9, 127.6, 127.8, 128.9, 129.0, 130.6, 133.1,
158.1; HRMS calcd for C14H9NO (M+) 207.0684, found 207.0697.
1,3-Dimethyl-6H-benzo[c]chromene (9). The substrate
was treated under the general procedure for intramolecular
Procedure for the Intermolecular Direct Arylation of
Imidazo[1,2-a]pyrimidine. To a mixture of potassium ac-
etate (3 equiv), Pd(OH)2/C (0.1 equiv), imidazo[1,2-a]pyrimi-
dine (1 equiv), and the appropriate aryl halide (1.1 equiv),
under nitrogen atmosphere, was added DMA (0.2 M) in a 2
mL screw cap vial equipped with a mechanical stir bar. The
reaction mixture was then heated overnight at 145 °C. After
the reaction was judged complete by TLC or GC/MS analysis,
the heat source was removed and the reaction mixture was
allowed to cool. The crude mixture was then purified via silica
gel column chromatography using ethyl acetate/hexanes mix-
tures. Compounds 2812 (75%), 2912 (76%), and 3012 (81%)
exhibited spectral data identical to that reported in the
literature.
Procedure for the Intermolecular Direct Arylation of
Thiazole. To a mixture of potassium acetate (3 equiv), Pd-
(OH)2/C (0.1 equiv), thiazole (1 equiv), and the appropriate aryl
halide (3 equiv), under nitrogen atmosphere, was added DMA
(0.2 M) in a 2 mL screw cap vial equipped with a mechanical
stir bar. The reaction mixture was then heated overnight at
145 °C. After the reaction was judged complete by TLC or GC/
MS analysis, the heat source was removed and the reaction
mixture was allowed to cool. The crude mixture was then
purified via silica gel column chromatography using ethyl
acetate/hexanes mixtures. Compounds 3130 (82%), 3231 (73%),
and 3332 (71%) (81%) exhibited spectral data identical to those
reported in the literature.
direct arylation reactions (92%): mp 76-77 °C; IR (vmax/cm-1
)
2855, 1453, 1065, 747; 1H NMR (300 MHz, CDCl3, 293 K, TMS)
δ 2.30 (3H, s), 2.63 (3H, s), 4.91 (2H, s), 6.74 (2H, d, J ) 6.6
Hz), 7.21 (2H, m), 7.35 (1H, td, J ) 1.2, 7.5 Hz), 7.72 (1H, d,
J ) 7.8 Hz); 13C NMR (75 MHz, CDCl3, 293 K, TMS) δ 21.1,
22.5, 69.0, 115.4, 124.7, 125.9, 126.4, 126.6, 126.7, 127.7, 130.8,
133.4, 135.2, 138.6, 156.3; HRMS calcd for C15H14O (M+)
210.1045, found 210.1056.
8-Methoxy-6H-benzo[c]chromene (11). The substrate
was treated under the general procedure for intramolecular
direct arylation reactions (69%): mp 71-73 °C; IR (νmax/cm-1
)
1
3066, 2936, 2836, 1605, 1408, 1321, 1277, 1168, 846, 748; H
NMR (300 MHz, CDCl3, 293 K, TMS) δ 3.81 (3H, s), 5.07 (2H,
s), 6.66 (1H, d, J ) 2.5 Hz), 6.88 (1H, dd, J ) 2.6, 8.5 Hz),
6.99 (2H, m), 7.17 (1H, td, J ) 1.5, 7.7 Hz), 7.63 (2H, m); 13C
NMR (75 MHz, CDCl3, 293 K, TMS) δ 55.3, 68.4, 110.0, 113.9,
117.2, 122.1, 122.6, 122.9, 122.9, 123.4, 128.4, 133.0, 153.9,
159.3; HRMS calcd for C14H12O2 (M+) 212.0837, found 212.0842.
N-Benzoyl-(6H)-phenanthridine (13). The substrate was
treated under the general procedure for intramolecular direct
arylation reactions (81%): mp 115-117 °C; IR (νmax/cm-1) 3064,
2851, 1650, 1374, 1350, 761, 736; 1H NMR (300 MHz, CDCl3,
293 K, TMS) δ 5.02 (2H, s), 6.72 (1H, s), 6.97 (1H, t, J ) 8.2
Hz), 7.11-7.48 (9H, m), 7.78 (1H, d, J ) 7.5 Hz), 7.84 (1H, d,
5-Phenyl-2-furaldehyde (34). To a mixture of potassium
acetate (3 equiv), Pd(OH)2/C (0.1 equiv), 2-furaldehyde (3
equiv), and phenyl bromide (1 equiv) under nitrogen atmo-
(25) Liu, Z.; Larock, R. C. Org. Lett. 2004, 6, 99.
(26) Parham, W. E.; Jones, L. D.; Sayed, Y. A. J. Org. Chem. 1976,
41, 1184.
(30) Pavlik, J. W.; Tongcharoensirikul, P.; Bird, N. P.; Day, A. C.;
Barltrop, J. A. J. Am. Chem. Soc. 1994, 116, 2292.
(27) CAS Registry No.: 132-64-9.
(31) Oscarson, K.; Oscarson, S.; Vrang, L.; Hamelink, E.; Hallberg,
A.; Samuelsson, B. Bioorg. Med. Chem. 2003, 11, 1235.
(28) CAS Registry No.: 86-74-8.
(29) CAS Registry No.: 86-73-7.
(32) Jenson, J.; Skjaerbaek, N.; Vesdo, P. Synthesis 2001, 1, 128.
J. Org. Chem, Vol. 70, No. 19, 2005 7583