Pd-Catalyzed Addition of Boronic Acids to Aldehydes
2-Methoxyphenyl(2-nitrophenyl)methanol (3ek): mp 81-
82 °C; IR (KBr, cm-1) 3502(-OH), 3009, 2939, 2834, 1597, 1490,
1461, 1286, 1242, 1161, 1286, 1242, 1164, 1108, 1021, 934, 863,
4-Nitrophenyl(3-(trifluoromethyl)phenyl)methanol (3le): oil;
IR (KBr, cm-1) 3438 (-OH), 3076, 2927, 1602, 1522, 1448, 1179,
1328, 1249, 1166, 1126, 1070, 1045, 908, 855, 796, 766, 704;
1H NMR (CDCl3, 300 MHz) δ 3.13 (d, J ) 2.8 Hz, 1H), 5.95 (d,
J ) 2.3 Hz, 1H), 7.44-7.66 (m, 6H), 8.12-8.17 (d, J ) 13.3 Hz,
2H); 13C NMR (75 MHz) δ 74.7, 123.09, 123.14, 123.19, 123.24,
123.8, 124.89, 124.94, 124.99, 125.04, 127.1, 129.3, 129.9, 143.5,
147.2, 150.0; MS (EI) m/z 297 (M+). Anal. Calcd for C14H10F3-
NO3: C, 56.57; H, 3.39; N, 4.71. Found: C, 56.87; H, 3.62;
N, 4.56.
1
789, 754, 646, 608, 574; H NMR (CDCl3, 300 MHz) δ 3.21 (m,
1H), 3.74 (s, 3H), 6.64 (d, J ) 4.4 Hz, 1H), 6.85-7.24 (m, 2H),
7.25-7.61 (m, 3H), 7.87-7.89 (d, J ) 8.1 Hz, 1H); 13C NMR (75
MHz) δ 55.3, 66.6, 110.5, 120.6, 124.1, 126.7, 128.0, 129.1, 129.3,
130.2, 132.9, 137.8, 148.7, 156.3; MS (EI) m/z 279 (M+). Anal.
Calcd for C14H13NO4: C, 64.86; H, 5.05; N, 5.40. Found: C, 64.91;
H, 4.87; N, 5.66.
Naphthalen-1-yl(2-nitrophenyl)methanol (3fk): mp 68-70 °C;
IR (KBr, cm-1) 3290 (-OH), 3010, 1486, 1344, 801, 783, 724;
1H NMR (CDCl3, 300 MHz) δ 3.46 (d, J ) 4.2 Hz, 1H, -OH),
7.04 (d, J ) 3.9 Hz, 1H), 7.37-7.48 (m, 7H), 7.78-7.89 (m, 3H),
7.98 (d, J ) 8.1 Hz, 1H); 13C NMR (75 MHz) δ 68.4, 123.4, 124.4,
124.9, 125.3, 125.9, 126.6, 128.7, 128.9, 120.0, 129.6, 130.8, 133.5,
133.9, 136.9, 138.1, 148.5; MS (EI) m/z 279 (M+). Anal. Calcd
for C17H13NO3: C, 73.04; H, 5.06; N, 4.65. Found: C, 73.11; H,
4.69; N, 5.02.
1-(4-(Hydroxy(4-nitrophenyl)methyl)phenyl)ethanone (3me):
oil; IR (KBr, cm-1) 3482 (-OH), 3075, 2924, 1675, 1602, 1518,
1412, 1346, 1270, 1181, 1115, 1050, 960, 832, 799, 711, 598,
506; 1H NMR (CDCl3, 300 MHz) δ 2.54 (s, 3H), 3.37 (d, J ) 3.6
Hz, 1H), 5.96 (d, J ) 2.7 Hz, 1H), 7.44 (d, J ) 8.1 Hz, 2H), 7.54
(d, J ) 8.4 Hz, 2H), 7.87 (d, J ) 8.4 Hz, 2H), 8.14 (d, J ) 8.7 Hz,
2H); 13C NMR (75 MHz) δ 26.5, 74.8, 123.7, 126.6, 127.1, 128.8,
136.5, 147.1, 147.7, 150.1, 198.0; MS (EI) m/z 271 (M+). Anal.
Calcd for C15H13NO4: C, 66.41; H, 4.83; N, 5.16. Found: C, 66.40;
H, 4.82; N, 5.17.
4-Nitrophenyl(thiophen-3-yl)methanol (3ie): mp 88-90 °C;
IR (KBr, cm-1) 3413 (-OH), 3012, 1604, 1515, 1345, 1149, 1109,
3-Nitrophenyl(4-nitrophenyl)methanol (3ne): mp 118-119 °C;
1
IR (KBr, cm-1) 3468 (-OH), 3009, 2924, 1602, 1516, 1346, 1182,
1033, 1013, 858, 835, 783, 761, 720, 699; H NMR (CDCl3, 300
1
MHz) δ 2.97 (s, 1H), 5.95 (s, 1H), 6.94-6.96 (m, 1H), 7.18-7.19
(m, 1H), 7.29-7.30 (m, 1H), 7.54 (d, J ) 8.7 Hz, 2H), 8.14 (d, J
) 8.7 Hz, 2H); 13C NMR (75 MHz) δ 71.5, 122.4, 123.6, 125.9,
126.9, 143.8, 147.1, 150.3; MS (EI) m/z 235 (M+). Anal. Calcd
for C11H9NSO3: C, 56.13; H, 3.92; N, 5.88. Found: C, 56.16; H,
3.86; N, 5.95.
1083, 1046, 860, 802, 735, 706; H NMR (CDCl3, 300 MHz) δ
2.72 (d, J ) 3.2 Hz, 1H), 6.03 (d, J ) 2.1 Hz, 1H), 7.52-7.60
(m, 3H), 7.69 (d, J ) 7.6 Hz, 1H), 8.15-8.28 (m, 4H); 13C NMR
(75 MHz) δ 74.4, 121.3, 123.1, 124.0, 127.1, 129.8, 132.4, 144.5,
147.5, 148.4, 149.3; MS (EI) m/z 274 (M+). Anal. Calcd for
C13H10N2O5: C, 56.94; H, 3.68; N, 10.22. Found: C, 57.16; H,
3.94; N, 9.84.
4-Chlorophenyl(4-nitrophenyl)methanol (3ke): mp 133-134
°C; IR (KBr, cm-1) 3420 (-OH), 3019, 1605, 1518, 1489, 1374,
1345, 1185, 1109, 1089, 1041, 1027, 1013, 867, 827, 198, 722,
4-(Hydroxy(4-nitrophenyl)methyl)benzoic acid (3oe): mp 153-
156 °C; IR (KBr, cm-1) 3430 (-OH), 3114, 2927, 2854, 1726,
1603, 1520, 1447, 1349, 1275, 1114, 1007, 849, 788, 717, 505; 1H
NMR (CDCl3, 300 MHz) δ 5.50 (s, 2H), 7.62 (d, J ) 8.6 Hz, 2H),
8.23-8.33 (m, 6H); 13C NMR (75 MHz) δ 66.1, 123.7, 124.0,
128.7, 130.9, 134.8, 142.3, 147.9, 150.8, 164.3; MS (EI) m/z 273
(M+). Anal. Calcd for C14H11NO5: C, 61.54; H, 4.06; N, 5.13.
Found: C, 61.86; H, 4.48; N, 5.44.
1
711, 685, 682; H NMR (CDCl3, 300 MHz) δ 2.37 (d, J ) 4.3
Hz), 5.91 (d, J ) 3.3 Hz), 7.27-7.36 (m, 4H), 7.56 (d, J ) 8.7
Hz, 2H), 8.21 (d, J ) 8.7 Hz, 2H); 13C NMR (75 MHz) δ 74.8,
123.8, 127.1, 128.0, 129.1, 134.3, 141.1, 147.4, 150.2; MS (EI)
m/z 263 (M+). Anal. Calcd for C13H10ClNO3: C, 59.22; H, 3.93;
N, 5.22. Found: C, 59.22; H, 3.82; N, 5.31.
2-Methoxyphenyl(2-(trifluoromethyl)phenyl)methanol (3em):
oil; IR (KBr, cm-1) 3483 (-OH), 3024, 1601, 1521, 1490, 1423,
1313, 1163, 1128, 1037, 929, 849, 627; 1H NMR (CDCl3, 300 MHz)
δ 3.17 (d, J ) 2.5 Hz, 1H), 3.83 (s, 3H), 6.54 (s, 1H), 6.89-6.94
(m, 2H), 6.99 (d, J ) 7.5 Hz, 1H), 7.27-7.32 (t, 1H), 7.42-7.44
(t, 1H), 7.54-7.59 (t, 1H), 7.69 (d, J ) 7.0 Hz, 1H); 13C NMR (75
MHz) δ 55.2, 67.1, 76.5, 76.9, 77.4, 110.3, 110.6, 114.4, 120.0,
120.3, 121.3, 122.5, 125.4, 125.5, 125.6, 125.7, 126.1, 127.2, 127.4,
127.5, 127.6, 128.0, 128.8, 129.2, 131.2, 131.9, 140.9, 156.5; MS
(EI) m/z 282 (M+). Anal. Calcd for C15H13F3O2: C, 63.83; H, 4.64.
Found: C, 64.07; H, 4.66.
Acknowledgment. We thank the National Natural Science
Foundation of China (Nos. 20476098 and 20504023) and the
Natural Science Foundation of Zhejiang Province (Nos. Y405015,
Y404039, and Y405113) for financial support.
Supporting Information Available: Experimental procedures
along with copies of spectra. This material is available free of charge
JO070267H
J. Org. Chem, Vol. 72, No. 11, 2007 4107