4526
C. Mamat et al. / Tetrahedron 67 (2011) 4521e4529
ether/EtOAc¼5:1); 1H NMR (400 MHz, C6D6):
d
1.97 (s, 3H, CH3),
1.93 mmol), DCC (722 mg, 3.50 mmol), and DMAP (30 mg) in dry
THF (15 mL) yielded 3l as colorless oil (150 mg, 21%); Rf¼0.56
3
3
6.44 (t, J3,4¼7.8 Hz, 1H, H-4), 6.87 (t, J5,6¼7.0 Hz, 1H, H-5), 6.91
3
3
(d, Jo,m¼8.5 Hz, 2H, Hmeta), 6.99 (d, J5,6¼7.0 Hz, 1H, H-6), 7.54 (d,
(petroleum ether/EtOAc¼3:1); 1H NMR (400 MHz, C6D6):
d 6.07
3J3,4¼7.8 Hz, 1H, H-3), 8.26 (d, Jo,m¼8.5 Hz, 2H, Hortho); 13C NMR
(dd, 3JH,F¼3.1 Hz, 3J4 ,5 ¼8.6 Hz,1H, H-5 ), 6.84 (t, J3,4¼7.0 Hz,1H, H-
3
3
0
0
0
(101 MHz, C6D6):
d 21.5 (CH3), 91.1 (C-2), 123.7 (C-6), 127.3 (Cipso),
4), 6.95e7.03 (m, 7H, H-3, Hmeta, Hpara), 7.07 (t, 3J5,6¼7.8 Hz, 1H, H-
3
127.5 (C-4), 129.4 (C-5), 129.6 (Cmeta), 130.9 (Cortho), 139.6 (C-3),
144.6 (Cpara), 152.1 (C-1), 164.2 (C]O); MS (ESIþ): m/z 339
(MþHþ); Anal. Calcd for: C14H11IO2 (338.1): C 49.73, H 3.28;
found: C 50.32, H 3.45.
5), 7.22 (dd, J5,6¼7.8 Hz, 1H, H-6), 7.29e7.37 (m, 4H, Hortho), 7.79
4
4
(dd, 3J4 ,5 ¼8.6 Hz, J2 ,4 ¼2.3 Hz, 1H, H-4 ), 8.76 (d, J2 ,4 ¼2.3 Hz, H-
0
0
0
0
0
0
0
20); 13C NMR (101 MHz, C6D6):
d
¼109.2 (d, 2JC,F¼38.1, C-50), 123.0 (d,
3JC,P¼1.5 Hz, C-6), 123.9 (d, 4JC,F¼4.4 Hz, C-30), 128.9 (d, 3JC,P¼7.4 Hz,
2
Cmeta), 129.4 (Cpara), 130.1 (C-5), 131.4 (d, JC,P¼16.2 Hz, C-3), 134.1
3
2
6.2.2. 2-Iodophenyl 6-bromonicotinate (3f). 6-Bromonicotinic acid
(500 mg, 2.47 mmol), o-iodophenol (599 mg, 2.72 mmol), DCC
(1.02 g, 4.95 mmol), and DMAP (50 mg) in dry THF (30 mL) yielded
3f as colorless solid (584 mg, 58%); mp¼93 ꢁC; Rf¼0.49 (petroleum
(d, JC,P¼1.9 Hz, C-4), 134.4 (d, JC,P¼20.5 Hz, Cortho), 135.9 (d,
1JC,P¼10.8 Hz, Cipso), 142.7 (d, JC,F¼9.5 Hz, C-40), 151.1 (d,
3
3JC,F¼17.3 Hz, C-20), 153.0 (d, 2JC,P¼16.9 Hz, C-1), 162.0 (C]O), 166.3
(d, JC,F¼244.8 Hz, C-60); 19F NMR (376 MHz, C6D6):
d
ꢀ61.1; 31P
1
ether/EtOAc¼3:1); 1H NMR (400 MHz, C6D6):
d
6.43 (t, 3J3,4¼7.4 Hz,
NMR (162 MHz, C6D6):
d
ꢀ14.4; MS (ESIþ): m/z 424 (MþNaþ), 402
1H, H-4), 6.79e6.93 (m, 3H, H-3, H-5, H-6), 7.48 (d, 3J4 ,5 ¼8.6 Hz, H-
(MþHþ); Anal. Calcd for: C24H17FNO2P (401.4): C 71.82, H 4.27, N
0
0
3
50), 7.63 (d, J4 ,5 ¼8.6 Hz, H-4 ), 9.11 (s, 1H, H-2 ); 13C NMR
3.49; found: C 71.92, H 4.67, N 3.04.
0
0
0
0
(101 MHz, C6D6):
d
90.5 (C-2), 123.2 (C-6), 124.7 (C-30), 127.9 (C-50),
129.5 (C-5), 139.4 (C-40), 139.7 (C-3), 148.0 (C-60), 151.3 (C-1), 152.2
(C-20), 162.3 (C]O); MS (ESIþ): m/z 427 (MþNaþ); Anal. Calcd for:
C12H7BrINO2 (404.0): C 35.68, H 1.75, N 3.47; found: C 35.88, H 1.94,
N 3.41.
6.2.7. 2-(Diphenylphosphano)phenyl 2-bromonicotinate (3m). 2-
Bromonicotinic acid (279 mg, 1.38 mmol), phosphanol 2b (350 mg,
1.26 mmol), DCC (519 mg, 2.52 mmol), and DMAP (30 mg) in dry
THF (15 mL) yielded 3m as colorless solid (441 mg, 76%);
mp¼105 ꢁC; Rf¼0.69 (petroleum ether/EtOAc¼1:2); 1H NMR
3
3
0
0
0
0
0
6.2.3. 2-(Diphenylphosphano)phenyl 4-hydroxybenzoate (3i). 4-
Hydroxybenzoic acid (186 mg,1.35 mmol), phosphanol 2b (250 mg,
0.90 mmol), DCC (278 mg, 1.35 mmol), and DMAP (25 mg) in dry
THF (15 mL) yielded 3i as colorless solid (276 mg, 73%). Analytical
data are in accordance with the previously published.5a
(400 MHz, C6D6):
d
6.25 (dd, J4 ,5 ¼4.7 Hz, J5 ,6 ¼7.7 Hz, 1H, H-5 ),
3
6.83 (t, J4,5¼7.6 Hz, 1H, H-4), 6.99e7.02 (m, 7H, H-3, Hmeta, Hpara),
7.05 (t, 3J4,5¼7.6 Hz, 3J5,6¼8.0 Hz, 1H, H-5), 7.18 (dd, 3J5,6¼8.0 Hz, 1H,
3
0
0
H-6), 7.30e7.36 (m, 4H, Hortho), 7.65 (ddd, J5 ,6 ¼7.7 Hz,
4
3
4
0
0
0
0
0
0
0
J4 ,6 ¼2.0 Hz, 1H, H-6 ), 7.81 (d, J4 ,5 ¼4.7 Hz, J4 ,6 ¼2.0 Hz, 1H, H-
40); 13C NMR (101 MHz, C6D6):
d
121.8 (C-50), 123.1 (d, 3JC,P¼1.8 Hz,
3
6.2.4. 2-(Diphenylphosphano)phenyl 4-methylbenzoate (3j). p-Tol-
ylic acid (318 mg, 2.34 mmol), phosphanol 2b (591 mg, 2.12 mmol),
DCC (657 mg, 3.19 mmol), and DMAP (50 mg) in dry THF (15 mL)
yielded 3j as colorless solid (825 mg, 98%); mp¼144 ꢁC; Rf¼0.48
C-6), 126.8 (C-30), 129.0 (d, JC,P¼7.2 Hz, Cmeta), 129.3 (Cpara), 130.4
2
2
(C-5), 131.0 (d, JC,P¼16.0 Hz, C-3), 134.3 (d, JC,P¼20.5 Hz, Cortho),
134.4 (d, JC,P¼0.9 Hz, C-4), 136.1 (d, 1JC,P¼10.9 Hz, Cipso), 139.6 (C-
3
60), 141.7 (C-20), 152.0 (C-40), 153.5 (d, 2JC,P¼17.8 Hz, C-1), 162.6 (C]
(petroleum ether/EtOAc¼3:1); 1H NMR (400 MHz, C6D6):
d
1.91 (s,
O); 31P NMR (162 MHz, C6D6):
d
ꢀ15.5.; MS (ESIþ): m/z 485
3
3H, CH3), 6.80 (d, 3Jo,m¼8.6 Hz, 2H, Hmeta ), 6.84 (t, J3,4¼7.0 Hz, 1H,
(MþHþNaþ); Anal. Calcd for: C24H17BrNO2P (462.3): C 62.36, H
0
H-4), 6.98e7.08 (m, 8H, H-5, H-6, Hmeta
,
Hpara), 7.28 (dd,
3.71, N 3.03; found: C 62.81, H 4.07, N 2.93.
4
3J3,4¼7.8 Hz, JH,P¼4.7 Hz, 1H, H-3), 7.36e7.42 (m, 4H, Hortho), 8.01
(d, 3Jo,m¼8.6 Hz, 2H, Hortho ); 13C NMR (101 MHz, C6D6):
d
21.4 (CH3),
6.2.8. 2-(Diphenylphosphano)phenyl 2-fluoronicotinate (3n). 2-Flu-
oronicotinic acid (247 mg, 1.75 mmol), phosphanol 2b (536 mg,
1.93 mmol), DCC (722 mg, 3.50 mmol), and DMAP (30 mg) in dry
THF (15 mL) yielded 3n as colorless oil (280 mg, 36%); Rf¼0.20
0
3
0
0
123.3 (C-6), 127.4 (Cipso ), 128.8 (d, JC,P¼7.4 Hz, Cmeta), 129.1 (Cmeta ),
129.3 (C-5), 130.1 (Cortho ), 130.6 (Cpara), 131.4 (d, 2JC,P¼16.4 Hz, C-3),
0
2
1
134.0 (C-4), 134.5 (d, JC,P¼20.6 Hz, Cortho), 136.6 (d, JC,P¼11.8 Hz,
Cipso), 144.0 (Cpara ), 154.0 (d, JC,P¼17.6 Hz, C-1), 164.3 (C]O); 31P
(petroleum ether/EtOAc¼4:1); 1H NMR (400 MHz, C6D6):
d 6.25
2
0
3
3
5
¼ꢀ14.7; MS (ESIþ): m/z 397 (MþHþ); Anal.
(ddd, J4 ,5 ¼4.8 Hz, J5 ,6 ¼7.6 Hz, JH,F¼1.6 Hz, 1H, H-50), 6.84 (t,
0
0
0
0
NMR (162 MHz, C6D6):
d
Calcd for: C26H21O2P (396.4): C 77.78, H 5.34; found: C 77.74, H 5.47.
3J3,4¼7.5 Hz, 1H, H-4), 6.98e7.02 (m, 7H, H-3, Hmeta, Hpara), 7.05 (t,
3
3
3J4,5¼7.5 Hz, J5,6¼8.0 Hz, 1H, H-5), 7.18 (dd, J5,6¼8.0 Hz, 1H, H-6),
3
4
0
0
0
0
6.2.5. 2-(Diphenylphosphano)phenyl 6-bromonicotinate (3 k). 6-
Bromonicotinic acid (248 mg, 1.23 mmol), phosphanol 2b (310 mg,
1.11 mmol), DCC (460 mg, 2.23 mmol), and DMAP (30 mg) in dry
THF (15 mL) yielded 3k as colorless solid (446 mg, 87%);
7.31e7.37 (m, 4H, Hortho), 7.76 (ddd, J4 ,5 ¼4.8 Hz, J4 ,6 ¼2.0 Hz,
4
3
4
JH,F¼3.2 Hz, 1H, H-40), 7.89 (d, J5 ,6 ¼7.6 Hz, J4 ,6 ¼2.0 Hz,
0
0
0
0
4JH,F¼3.7 Hz, 1H, H-60); 13C NMR (101 MHz, C6D6):
d 113.1 (d,
2JC,F¼24.1, C-30), 121.0 (d, JC,F¼5.0 Hz, C-50), 123.2 (C-6), 128.9 (d,
3JC,P¼7.1 Hz, Cmeta), 129.2 (Cpara), 130.2 (C-5), 131.2 (d, 2JC,P¼16.5 Hz,
C-3), 133.9 (d, 1JC,P¼19.2 Hz, C-2), 134.3 (d, 3JC,P¼1.7 Hz, C-4), 134.4
4
mp¼105 ꢁC; Rf¼0.62 (petroleum ether/EtOAc¼3:1);0 1H NMR
3
0
0
(400 MHz, C6D6):
d
6.73 (d, J4 ,5 ¼8.7 Hz, 1H, H-5 ), 6.83 (t,
3J3,4¼7.7 Hz, 1H, H-4), 6.95e7.01 (m, 7H, H-3, Hmeta, Hpara), 7.05 (t,
(d, JC,P¼20.7 Hz, Cortho), 136.1 (d, JC,P¼11.1 Hz, Cipso), 143.6 (d,
2
1
3J5,6¼7.8 Hz, 1H, H-5), 7.19 (dd, 3J5,6¼7.8 Hz, 1H, H-6), 7.28e7.36 (m,
3JC,F¼15.8 Hz, C-40), 152.2 (d, JC,F¼15.9 Hz, C-60), 153.2 (d,
3
3
4
3
4H, Hortho), 7.48 (dd, J4 ,5 ¼8.7 Hz, J2 ,4 ¼2.4 Hz, 1H, H-4 ), 8.81 (d,
2JC,P¼17.7 Hz, C-1), 160.5 (d, JC,F¼8.7 Hz, C]O), 162.4 (d,
0
0
0
0
0
J2 ,4 ¼2.4 Hz, H-20); 13C NMR (101 MHz, C6D6):
d
3
122.9 (d,
1JC,F¼251.1 Hz, C-20); 19F NMR (376 MHz, C6D6):
d
ꢀ61.1; 31P NMR
4
0
0
3JC,P¼1.5 Hz, C-6), 124.8 (C-30), 127.9 (C-50), 129.0 (d, JC,P¼7.3 Hz,
(162 MHz, C6D6):
d
ꢀ14.7; MS (ESIþ): m/z 402 (MþHþ); Anal. Calcd
2
Cmeta), 129.4 (Cpara), 130.1 (C-5), 131.4 (d, JC,P¼16.2 Hz, C-3), 132.0
for: C24H17FNO2P (401.4): C 71.82, H 4.27, N 3.49; found: C 72.01, H
4.19, N 3.51.
1
3
(d, JC,P¼9.9 Hz, C-2), 134.1 (d, JC,P¼1.9 Hz, C-4), 134.4 (d,
2JC,P¼21.0 Hz, Cortho), 135.8 (d, 1JC,P¼10.9 Hz, Cipso), 139.2 (C-40), 147.6
(C-60), 152.0 (C-20), 153.0 (d, JC,P¼17.0 Hz, C-1), 162.4 (C]O); 31P
6.2.9. 4-(2-(Diphenylphosphano)phenoxy)carbonyl-N,N,N-trimethyl-
anilinium iodide borane adduct (5). Compound 4 (480 mg,
2
NMR (162 MHz, C6D6):
d
ꢀ14.5; MS (ESIþ): m/z 465 (MþHþ; 81Br),
463 (MþHþ; 79Br); Anal. Calcd for: C24H17BrNO2P (462.3): C 62.36,
1.09 mmol) was dissolved in methyl iodide (4 mL), and the mixture
was stirred for 7 days at room temperature. Afterward, the pre-
cipitate was filtered and washed with diethyl ether (3ꢂ10 mL) and
ethyl acetate (10 mL) to yield 5 as pale yellow solid (367 mg, 58%);
mp¼142 ꢁC (decomp.); 1H NMR (400 MHz, acetone-d6): 0.80e1.70
H 3.71, N 3.03; found: C 62.16H 3.91, N 2.94.
6.2.6. 2-(Diphenylphosphano)phenyl 6-fluoronicotinate (3l). 6-Flu-
oronicotinic acid (247 mg, 1.75 mmol), phosphanol 2b (536 mg,