Palladium-Catalyzed Amination of Aryl Nonaflates
mL, 20.2 mmol), and diethyl ether (40 mL) were used. The
crude material was purified by column chromatography on
silica gel (eluting with pentanes) to give the title compound
as a colorless oil (2.5 g, 62%). 1H NMR (300 MHz, CDCl3) δ
7.25-7.29 (m, 4H), 2.40 (s, 3H). 13C NMR (125 MHz, CDCl3) δ
148.7, 132.2, 131.0, 128.3, 127.7, 121.3, 109.4-118.3 (m, 4C),
16.4.
1202, 1146, 889, 847. Anal. Calcd for C11H4F9O3NS: C, 32.93;
H, 1.00. Found: C, 33.09; H, 1.00.
4-(Acetylp h en yl) Non a fla te. With Method 2, 4-acetylphe-
nol (1.36 g, 10.0 mmol), i-Pr2NEt (2.10 mL, 12.0 mmol),
nonafluorobutanesulfonic fluoride (1.90 mL, 11.0 mmol), DMAP
(60 mg, 0.50 mmol), and dichloromethane (20 mL) were used.
The crude material was purified by column chromatography
on silica gel (eluting with ethyl acetate/hexanes, 1:4) to give
the title compound as a white solid (3.9 g, 92%), mp 38-40
°C. 1H NMR (300 MHz, CDCl3) δ 8.06 (d, J ) 8.5 Hz, 2H),
7.39 (d, J ) 8.5 Hz, 2H), 2.63 (s, 3H). 13C NMR (125 MHz,
CDCl3) δ 196.1, 152.7, 136.7, 130.6, 121.6, 96.7-118.1 (m, 4C),
26.7. IR (neat, cm-1) 1694, 1594, 1422, 1356, 1265, 1203. Anal.
Calcd for C10H7F9O4S: C, 34.46; H, 1.69. Found: C, 34.36; H,
1.70.
2,6-(Dim eth ylp h en yl) Non a fla te. With Method 2, 2,6-
dimethylphenol (1.899 g, 15.55 mmol), i-Pr2NEt (3.25 mL, 18.7
mmol), nonafluorobutanesulfonic fluoride (3.07 mL, 17.1 mmol),
DMAP (95 mg, 0.70 mmol), and dichloromethane (25 mL) were
used. The crude material was purified by column chromatog-
raphy on silica gel (eluting with ethyl acetate/hexanes, 1:9) to
give the title compound as a colorless oil (3.7 g, 58%). 1H NMR
(400 MHz, CDCl3) δ 7.18-7.12 (m, 3H), 2.4 (s, 6H). 13C NMR
(125 MHz, CDCl3) δ 146.9, 131.9, 130.2, 128.3, 109.3-118.4
(m, 4C), 17.4. IR (neat, cm-1) 1475, 1406, 1353, 1202, 1144,
1079, 1034, 887, 776. Anal. Calcd for C12H9F9O3S: C, 35.65;
H, 2.24. Found: C, 35.68; H, 2.23.
4-Ch lor op h en yl Non a fla te.26 With Method 1, 4-chlorophe-
nol (1.285 g, 10.00 mmol), sodium hydride (520 mg, 13.0 mmol,
60% dispersion), nonafluorobutanesulfonic fluoride (3.60 mL,
20.0 mmol), and diethyl ether (40 mL) were used. The crude
material was purified by column chromatography on silica gel
(eluting with ethyl acetate/hexanes, 1:4) to give the title
Meth yl 4-[(Non a flu or obu ta n esu lfon yl)oxy] Ben zoa te.
With Method 1, methyl (4-hydroxy) benzoate (1.520 g, 10.00
mmol), sodium hydride (520 mg, 13.0 mmol, 60% dispersion),
nonafluorobutanesulfonic fluoride (3.60 mL, 20.0 mmol), and
diethyl ether (40 mL) were used. The crude material was
purified by column chromatography on silica gel (eluting with
ethyl acetate/hexanes, 1:10) to give the title compound as a
colorless oil (3.6 g, 83%). 1H NMR (500 MHz, CDCl3) δ 7.20
(dd, J ) 9.2, 1.2 Hz, 2H), 6.92 (dd, J ) 9.2, 1.2 Hz, 2H), 3.93
(s, 3H). 13C NMR (125 MHz, CDCl3) δ 159.1, 143.3, 122.4,
1
compound as a colorless oil (3.0 g, 73%). H NMR (300 MHz,
CDCl3) δ 7.42 (d, J ) 9.1 Hz, 2H), 7.23 (d, J ) 9.1 Hz, 2H). 13
C
NMR (125 MHz, CDCl3) δ 148.1, 134.3, 130.4, 122.7, 108.5-
118.2 (m, 4C).
2-Ch lor op h en yl Non a fla te. With Method 2, 2-chlorophe-
nol (1.29 g, 10.0 mmol), i-Pr2NEt (2.10 mL, 12.0 mmol),
nonafluorobutanesulfonic fluoride (1.90 mL, 11.0 mmol), DMAP
(60 mg, 0.50 mmol), and dichloromethane (20 mL) were used.
The crude material was purified by column chromatography
on silica gel (eluting with ethyl acetate/hexanes, 1:10) to give
the title compound as a colorless oil (3.9 g, 95%). 1H NMR (300
MHz, CDCl3) δ 7.51-7.55 (m, 3H), 7.31-7.38 (m, 1H). 13C
NMR (125 MHz, CDCl3) δ 145.9, 131.3, 129.2, 128.3, 127.5,
123.0, 107.7-118.2 (m, 4C). IR (neat, cm-1) 1430, 1240, 1203,
1144, 890, 768. Anal. Calcd for C10H4F9O3SCl: C, 29.25; H,
0.98. Found: C, 29.05; H, 0.98.
4-Br om op h en yl Non a fla te. With Method 2, 4-bromophe-
nol (2.238 g, 12.94 mmol), i-Pr2NEt (2.70 mL, 15.5 mmol),
nonafluorobutanesulfonic fluoride (2.60 mL, 14.2 mmol), DMAP
(79 mg, 0.60 mmol), and dichloromethane (25 mL) were used.
The crude material was purified by column chromatography
on silica gel (eluting with ethyl acetate/hexanes, 1:10) to give
the title compound as a colorless oil (5.6 g, 96%). 1H NMR (300
MHz, CDCl3) δ 7.17 (d, J ) 9.1 Hz, 2H), 7.59 (d, J ) 9.3 Hz,
2H). 13C NMR (125 MHz, CDCl3) δ 148.6, 133.3, 123.0, 121.9,
103.3-118.5 (m, 4C). IR (neat, cm-1) 1481, 1430, 1240, 1204,
1146, 890. Anal. Calcd for C10H4F9O3SBr: C, 26.39; H, 0.89.
Found: C, 26.19; H, 0.97.
2-Br om op h en yl Non a fla te. With Method 2, 2-bromophe-
nol (2.238 g, 12.94 mmol), i-Pr2NEt (2.70 mL, 15.5 mmol),
nonafluorobutanesulfonic fluoride (2.60 mL, 14.2 mmol), DMAP
(79 mg, 0.60 mmol), and dichloromethane (25 mL) were used.
The crude material was purified by column chromatography
on silica gel (eluting with ethyl acetate/hexanes, 1:10) to give
the title compound as a colorless oil (5.7 g, 98%). 1H NMR (500
MHz, CDCl3) δ 7.51-7.54 (m, 1H), 7.25-7.37 (m, 3H). 13C
NMR (125 MHz, CDCl3) δ 147.3, 134.5, 129.5, 129.1, 122.9,
107.7-118.2 (m, 4C). IR (neat, cm-1) 2926, 1431, 1240, 1202,
1144, 1033, 890. Anal. Calcd for C10H4F9O3SBr: C, 26.39; H,
0.89. Found: C, 26.61; H, 0.89.
114.8-118.3 (m, 3C), 115.0, 109.7 (m), 55.8. IR (neat, cm-1
1732, 1601, 1434, 1285, 1203, 1145, 893. Anal. Calcd for
)
C
12H7F9O5S: C, 33.19; H, 1.62. Found: C, 33.40; H, 1.61.
Meth yl 2-[(Non a flu or obu ta n esu lfon yl)oxy] Ben zoa te.
With Method 1, methyl (2-hydroxy) benzoate (1.30 mL, 10.0
mmol), sodium hydride (520 mg, 13.0 mmol, 60% dispersion),
nonafluorobutanesulfonic fluoride (3.60 mL, 20.0 mmol), and
diethyl ether (40 mL) were used. The crude material was
purified by column chromatography on silica gel (eluting with
ethyl acetate/hexanes, 1:10) to give the title compound as a
white solid (3.2 g, 74%), mp 40-42 °C. 1H NMR (300 MHz,
CDCl3) δ 8.01 (d, J ) 7.7 Hz, 1H), 7.64 (ddd, J ) 8.2, 7.4, 1.9
Hz, 1H), 7.40 (td, J ) 7.4, 1.1 Hz, 1H), 7.24 (d, J ) 8.1 Hz,
1H), 3.89 (s, 3H). 13C NMR (125 MHz, CDCl3) δ 164.2, 148.5,
134.3, 132.7, 128.4, 124.6, 122.8, 107.9-118.2 (m, 4C), 52.6.
IR (neat, cm-1) 1732, 1606, 1430, 1240, 1190, 1135, 895. Anal.
Calcd for C12H7F9O5S: C, 33.19; H, 1.62. Found: C, 33.20; H,
1.60.
2-(Nitr op h en yl) Non a fla te. With Method 2, 2-nitrophenol
(1.30 g, 10.0 mmol), i-Pr2NEt (2.10 mL, 12.0 mmol), nonafluo-
robutanesulfonic fluoride (1.90 mL, 11.0 mmol), DMAP (60 mg,
0.50 mmol), and dichloromethane (20 mL) were used. The
crude material was purified by column chromatography on
silica gel (eluting with ethyl acetate/hexanes, 1:6) to give the
title compound as a white solid (2.7 g, 64%), mp 33-35 °C. 1H
NMR (300 MHz, CDCl3) δ 8.18 (dd, J ) 8.0, 1.7 Hz, 1H), 7.67
(ddd, J ) 8.2, 7.4, 1.9 Hz, 1H), 7.60 (td, J ) 7.7, 1.4 Hz, 1H),
7.50 (d, J ) 7.7 Hz, 1H). 13C NMR (125 MHz, CDCl3) δ 141.7,
135.2, 129.2, 126.7, 124.2, 109.0-118.4 (m, 4C), 99.3. IR (neat,
cm-1) 2921, 1601, 1538, 1434, 1235, 1200, 1142. Anal. Calcd
for C10H4F9O5NS: C, 28.52; H, 0.96. Found: C, 28.49; H, 0.97.
4-(Non aflu or obu tan esu lfon yl)-ben zon itr ile. With Method
2, 4-cyanophenol (1.852 g, 15.55 mmol), i-Pr2NEt (3.25 mL,
18.7 mmol), nonafluorobutanesulfonic fluoride (3.07 mL, 17.1
mmol), DMAP (95 mg, 0.70 mmol), and dichloromethane (25
mL) were used. The crude material was purified by column
chromatography on silica gel (eluting with ethyl acetate/
hexanes, 1.5:8.5) to give the title compound as a white solid
(5.5 g, 88%), mp 111-112 °C. 1H NMR (400 MHz, CDCl3) δ
7.80 (d, J ) 8.9 Hz, 2H), 7.44 (d, J ) 8.8 Hz, 2H). 13C NMR
(100 MHz, CDCl3) δ 152.4, 134.7, 122.8, 117.3, 113.1, 109.2-
18.7 (m, 4C). IR (neat, cm-1) 2235, 1599, 1498, 1430, 1237,
Gen er a l P r oced u r e for Ca ta lytic Am in a tion of Ar yl
Non a fla tes. An oven-dried resealable Schlenk flask was
charged with Pd2dba3 (1 mol %, 2 mol % of Pd) or Pd(OAc)2 (2
mol % of Pd), ligand (2-4 mol %), and base (1.4 equiv). The
flask was evacuated and backfilled with argon; this sequence
was repeated two additional times. The flask was capped with
a rubber septum and toluene (1.5 mL/mmol of nonaflate), the
nonaflate (1.0 equiv), and the amine (1.2 equiv.) were added
through the septum via syringe (aryl nonaflates or amines that
were solids at room temperature were added prior to addition
of the base). The septum was replaced with a Teflon screwcap,
J . Org. Chem, Vol. 68, No. 25, 2003 9569