diisopropylamine (0.11 mL, 0.76 mmol). The heterogeneous
mixture was deoxygenated with argon for 20 min, trimethylsi-
lylacetylene (0.11 mL, 0.76 mmol) was added dropwise, and the
reaction was stirred at ambient temperature overnight (14 h).
The reaction mixture was filtered though silica gel, and the filter
cake was washed with Et2O (10 mL). The resulting organic layer
was separated, washed with water and brine, dried (MgSO4),
and concentrated in vacuo to give a crude solid. The desired
compound 10 (156 mg, 74%) was isolated after purification via
radial PLC (silica gel, ethyl acetate/hexanes, 5:95) as an orange
solid (156 mg, 74%): mp 97-98 °C; 1H NMR (300 MHz, CDCl3)
δ 0.33 (s, 9H), 2.54 (t, 1H, J ) 6.9 Hz), 5.22 (d, 2H, J ) 6.9 Hz),
7.64 (t, 1H, J ) 6.9 Hz), 7.75 (t, 1H, J ) 6.9 Hz), 8.08 (d, 1H,
J ) 8.4 Hz), 8.20 (d, 1H, J ) 8.4 Hz); 13C NMR (75 MHz, CDCl3)
δ -0.6, 63.7, 100.4, 101.9, 127.5, 127.6, 129.1, 129.9, 131.1, 134.7,
136.4, 143.1, 147.9; FTIR (film) 1547, 1566, 2897, 2958, 3382
cm-1; exact mass for C15H16NOBrSi (M + 1H) requires m/z
334.0263, found m/z 334.0268.
reaction mixture was stirred at ambient temperature overnight
(15 h). The reaction mixture was filtered though silica gel, and
the filtrate was extracted with Et2O. The combined organic
extracts were washed with water and brine and then dried
(MgSO4) and concentrated in vacuo to give a crude mixture of
product and starting material. The crude mixture was purified
first by Kugerohr distillation (140 °C) to remove palladium
residue and then by radial PLC (silica gel, hexanes) to afford
13b as a colorless oil (507 mg, 46%): 1H NMR (400 MHz, CDCl3)
δ 0.30 (s, 9H), 7.63 (t, 1H, J ) 7.2 Hz), 7.75 (t, 1H, J ) 6.8 Hz),
7.84 (s, 1H), 8.09 (d, 1H, J ) 8.4 Hz), 8.14 (d, 1H, J ) 8.0 Hz);
13C NMR (100 MHz, CDCl3) δ -0.3, 96.9, 103.0, 126.4, 126.8,
127.9, 128.3, 129.8, 130.8, 133.7, 142.8, 148.3; FTIR (film) 1572,
2355, 2964 cm-1; exact mass for C14H14NBrSi (M + 1H) requires
m/z 304.0157, found m/z 304.0143.
4-Br om o-2-(p h en yleth yl)qu in olin e (14a ). To a solution of
13a (78 mg, 0.253 mmol) and potassium azodicarboxalate (737
mg, 3.80 mmol) in dioxane (5 mL) at 60 °C was added glacial
AcOH (0.61 mL, 10.63 mmol, in 5 mL dioxane) over 24 h using
a syringe pump. After complete addition of AcOH, the solution
was allowed to stir for an additional 8 h at 60 °C. The reaction
mixture was extracted with Et2O, and the extracts were washed
with water and brine. The organic layer was dried (MgSO4) and
concentrated in vacuo. Purification by radial PLC (silica gel,
hexanes, then ethyl acetate/hexanes, 5:95) provided 14a as a
colorless oil (67 mg, 85%): 1H NMR (400 MHz, CDCl3) δ 3.16
(m, 2H), 3.26 (m, 2H), 7.20-7.33 (m, 5H), 7.55 (s, 1H), 7.74 (t,
1H, J ) 7.6 Hz), 8.07 (d, 1H, J ) 8.4 Hz), 8.14 (d, 1H, J ) 8.0
Hz); 13C NMR (100 MHz, CDCl3) δ 35.8, 40.7, 125.6, 126.3, 126.5,
126.8, 127.2, 128.7, 129.5, 130.5, 134.3, 141.3, 148.7, 161.8; FTIR
[4-Br om o-2-(2-tr im eth ylsila n yleth yl)qu in olin -3-yl]m eth -
a n ol (11). To a solution of 10 (94 mg, 0.28 mmol) in dioxane (5
mL) was added potassium azodicarboxalate (818 mg, 4.22 mmol)
followed by the slow addition of glacial AcOH (0.70 mL, 11.81
mmol, in 2 mL dioxane) over 24 h using a syringe pump at
ambient temperature. After complete addition of AcOH, the
solution was warmed to 80 °C for 4 h during which time the
reaction color changed from yellow to white. The reaction
mixture was extracted with Et2O (10 mL), and the combined
extracts were washed with water and brine. The solution was
dried (MgSO4) and concentrated in vacuo. Purification by radial
PLC (silica gel, ethyl acetate/hexanes, 5:95) provided 11 as a
white solid (84 mg, 88%). Recrystallization from hexanes gave
(film) 1586, 2855, 2924, 3025, 3060 cm-1; exact mass for C17H14
-
1
an analytically pure sample: mp 105-106.5 °C; H NMR (400
NBr requires m/z 311.0310, found m/z 311.0301.
MHz, CDCl3) δ 0.08 (s, 9H), 1.04 (m, 2H), 2.27 (t, 1H, J ) 6.8
Hz), 3.12 (m, 2H), 5.05 (d, 2H, J ) 6.4 Hz), 7.56 (t, 1H, J ) 8.0
Hz), 7.70 (t, 1H, J ) 8.0 Hz), 8.01 (d, 1H, J ) 8.4 Hz), 8.16 (d,
1H, J ) 8.4 Hz); 13C NMR (100 MHz, CDCl3) δ -1.5, 17.5, 31.6,
62.4, 126.9, 127.3, 127.5, 129.2, 130.5, 131.5, 137.5, 148.1, 164.8;
4-Br om o-2-(2-tr im eth ylsila n yleth yl)qu in olin e (14b). To
a solution of 13b (105 mg, 0.35 mmol) and potassium azodicar-
boxalate (1.0 g, 5.18 mmol) in dioxane (10 mL) at ambient
temperature was added glacial AcOH (0.83 mL, 14.49 mmol, in
5 mL dioxane) over 24 h using a syringe pump. After complete
addition of AcOH, the solution was warmed to 80 °C for 4 h
during which time the reaction color changed from yellow to
white. The reaction mixture was extracted with Et2O, and the
extracts were washed with water and brine. The organic layer
was dried (MgSO4) and concentrated in vacuo. Purification by
radial PLC (silica gel, hexanes, then ethyl acetate/hexanes, 5:95)
provided the desired product as a colorless oil (67 mg, 63%): 1H
NMR (400 MHz, CDCl3) δ 0.06 (s, 9H), 1.03 (m, 2H), 2.92 (m,
2H), 7.54 (t, 1H, J ) 7.6 Hz), 7.63 (s, 1H), 7.70 (t, 1H, J ) 6.8
Hz), 8.01 (d, 1H, J ) 8.4 Hz), 8.15 (d, 1H, J ) 8.4 Hz); 13C NMR
(100 MHz, CDCl3) δ -1.5, 17.1, 33.5, 124.9, 126.4, 126.7, 127.0,
129.3, 130.4, 134.3, 148.6, 165.1; FTIR (film) 1586, 1614, 2895,
2951, 3062 cm-1; exact mass for C14H18NBrSi (M + 1H) requires
m/z 308.0470, found m/z 308.0488.
FTIR (film) 1614, 2894, 2951, 3356 cm-1; exact mass for C15H20
-
NOBrSi (M + 1H) requires m/z 338.0584, found m/z 338.0584.
4-Br om o-2-(p h en yleth yn yl)qu in olin e (13a ). To 2,4-dibro-
moquinoline (109 mg, 0.380 mmol), Pd(PPh3)2Cl2 (27 mg, 0.038
mmol), and CuI (7 mg, 0.038 mmol) in a flame-dried round-
bottomed flask were added dioxane (3 mL) and diisopropylamine
(0.064 mL, 0.456 mmol), and the heterogeneous mixture was
deoxygenated with argon for 20 min. Phenylacetylene (0.042 mL,
0.380 mmol) was added dropwise, and the reaction was stirred
at ambient temperature overnight (15 h). The reaction mixture
was filtered though silica gel, and the filtrate was extracted with
Et2O. The combined organic extracts were washed with satu-
rated NH4Cl, brine, and water and then dried (MgSO4) and
concentrated in vacuo to give a crude mixture of product and
starting material. The residue was purified by radial PLC (silica
gel, hexanes, then ethyl acetate/hexanes, 5:95) to afford starting
material (27 mg, 25%) and 13a as a yellow solid (51 mg, 44%):
Ack n ow led gm en t. NMR and mass spectra were
obtained at NCSU instrumentation laboratories, which
were established by grants from the North Carolina
Biotechnology Center and the National Science Founda-
tion (Grant Nos. CHE-9509532 and CHE-0078253).
1
mp 96-97 °C; H NMR (400 MHz, CDCl3) δ 7.39 (m, 3H), 7.64
(m, 3H), 7.76 (t, 1H, J ) 7.6 Hz), 7.91 (s, 1H), 8.11 (d, 1H, J )
8.4 Hz), 8.15 (d, 1H, J ) 8.4 Hz); 13C NMR (100 MHz, CDCl3) δ
88.4, 91.1, 121.9, 126.8, 127.0, 128.2, 128.5, 128.7, 129.6, 130.0,
131.1, 132.5, 134.0, 143.5, 148.7.
Su p p or tin g In for m a tion Ava ila ble: General experimen-
1
4-Br om o-2-(tr im eth ylsila n yleth yn yl)qu in olin e (13b). To
2,4-dibromoquinoline (1.037 g, 3.61 mmol), Pd(PPh3)2Cl2 (254
mg, 0.36 mmol), and CuI (688 mg, 0.36 mmol) in a flame-dried
round-bottomed flask were added dioxane (10 mL) and diiso-
propylamine (0.61 mL, 4.34 mmol), and the heterogeneous
mixture was deoxygenated with argon for 20 min. Trimethylsi-
lylacetylene (0.61 mL, 4.34 mmol) was added dropwise, and the
tal information, characterization data, and copies of H and
1
13C NMR spectra for 8, 9, 10, 11, 13b, and 14a ,b, 2D H-13C
HMBC spectra for 11 and 14a ,b, and a comparison table of
NMR data for 13a . This material is available free of charge
J O034122W
3738 J . Org. Chem., Vol. 68, No. 9, 2003