ortho-Alkylation of Aromatic Ketimines or Ketones
485 492
Characterization data. 1-[2-(3,3-dimethylbutyl)phenyl]-ethanone (4a):
1H NMR (250 MHz, CDCl3, 258C): d 7.6 (dd, 3J(H,H) 8.8 Hz, 1H;
Ar), 7.4 (m, 1H; Ar), 7.2 (m, 2H; Ar), 2.8 (m, 2H; ArCH2), 2.6 (s, 3H; CH3
to CO), 1.4 (t, 3J(H,H) 7.5 Hz, 2H; CH2), 1.0 (s, 9H; CH3); 13C NMR
1-(2-Pentyl-phenyl)-ethanone (4n): 1H NMR (250 MHz, CDCl3, 258C):
d 7.6 (m, 1H; Ar), 7.4 (m, 1H; Ar), 7.2 (m, 2H; Ar), 2.8 (t, 3J(H,H)
7.8 Hz, 2H; ArCH2), 2.6 (s, 3H; CH3 to CO), 1.6 (m, 2H), 1.3 (m, 4H), 0.9
3
(t, J(H,H) 6.8 Hz, 3H; CH3); 13C NMR (62.9 MHz, CDCl3, 258C): d
(62.9 MHz, CDCl3, 258C): d 202 (C O), 144 125 (Cs in phenyl group),
203 (CO), 143 125 (Cs in phenyl group), 34, 32, 31.7, 30, 23, 14.2; IR (neat):
46.6, 30.8, 30.4, 29.6, 29.4; MS: m/z (%): 204 (16) [M] , 189 (13), 148 (11),
nÄ 2952, 2927, 2857, 1688 (CO), 1456, 1354, 1247, 1071, 800, 758 cmÀ1; MS:
147 (100), 133 (22), 131 (23), 129 (18), 119 (14); IR (neat): nÄ 2954, 2866,
m/z (%): 190 (18) [M] , 175 (100), 147 (20), 143 (12), 133 (14), 129 (27), 119
1688 (CO), 1599, 1571, 1476, 1364, 1247, 950, 757 cmÀ1; HRMS calcd for
(26), 117 (13), 91 (30), 77 (11), 43 (26); HRMS calcd for C13H18O [M]
C14H20O [M] 204.151415; found: 204.151783.
190.135765; found: 190.135876.
1-[2-(2-Methyl-butyl)-phenyl]-ethanone (4p): 1H NMR (250 MHz, CDCl3,
1-(2-Hexyl-phenyl)-ethanone (4b): 1H NMR (250 MHz, CDCl3, 258C):
d 7.6 (d, 3J(H,H) 9.3 Hz, 1H; Ar), 7.4 (m, 1H; Ar), 7.2 (m, 2H; Ar), 2.9
3
258C): d 7.6 (d, J(H,H) 7.6 Hz, 1H; Ar), 7.4 (m, 1H; Ar), 7.2 (m, 2H;
3
Ar), 2.9 (m, 2H; ArCH2), 2.6 (s, 3H; CH3 to CO), 1.6 (m, 2H), 1.2 (m, 1H),
1.0 0.9 (m, 6H; CH3); 13C NMR (62.9 MHz, CDCl3, 258C): d 203 (CO),
141 126 (Cs in phenyl group), 40.1, 30, 30.3, 29.6, 19, 11.6; IR (neat): nÄ
(t, J(H,H) 7.6 Hz, 2H; ArCH2), 2.6 (s, 3H; CH3 to CO), 1.5 (m, 2H; b-
CH2 in hexyl group), 1.4 1.2 (m, 6H), 1.0 (t, 3J(H,H) 6.5 Hz, 3H; CH3);
13C NMR (62.9 MHz, CDCl3, 258C): d 202 (CO), 143 125 (Cs in phenyl
group), 34, 32, 31.8, 30, 29.6, 22.8, 14.2; IR (neat): nÄ 2927, 2856, 1687 (CO),
1600, 1571, 1484, 1459, 1355, 1252, 954, 908, 759, 734, 598 cmÀ1; MS: m/z
1688 cmÀ1 (CO); MS: m/z (%): 190 (14) [M] , 175 (100); HRMS calcd for
C13H18O [M] 190.135765; found: 190.136532.
1-(2-Bicyclo[2.2.1]hept-2-yl-phenyl)-ethanone (4q): 1H NMR (250 MHz,
CDCl3, 258C): d 7.5 (dd, 3J(H,H) 8.1 Hz, 1H; Ar), 7.4 (m, 2H; Ar), 7.2
(m, 1H; Ar), 3.2 (m, 1H(2); endo-CH), 2.6 (s, 3H; CH3 to CO), 2.3 (m, 2H;
CH(1), CH(4), in norbornyl group), 1.9 (m, 1H(3); exo-CH), 1.6 (m, 4H;
(%): 204 (16) [M] , 189 (100), 147 (23), 143 (17), 133 (16), 131 (11), 119
(49), 117 (14), 91 (31).
1
1-(2-Dodecyl-phenyl)-ethanone (4d): H NMR (250 MHz, CDCl3, 258C):
d 7.6 (dd, 3J(H,H) 7.5 Hz, 1H; Ar), 7.4 (m, 1H; Ar), 7.2 (m, 2H; Ar), 2.9
(t, 3J(H,H) 7.6 Hz, 2H; a-CH2 in dodecyl group), 2.6 (s, 3H; CH3 to CO),
1.6 (m, 2H; b-CH2 in dodecyl group), 1.3 (m, 18H), 0.9 (t, 3J(H,H) 6.2 Hz,
3H; CH3); 13C NMR (62.9 MHz, CDCl3, 258C): d 202 (CO), 143 125
(Cs in phenyl group), 34, 32.1, 32, 30, 29.9, 29.8, 29.7, 29.6, 29.5, 22.8, 14.2;
IR (neat): nÄ 2925, 2854, 1688 (CO), 1600, 1571, 1484, 1354, 1249, 954, 758,
CH2 in norbornyl group), 1.4 (m, 1H(3); endo-CH), 1.2 (m, 2H; CH2 in
13
norbornyl group); C NMR (62.9 MHz, CDCl3, 258C): d 204 (C O),
146 125 (Cs in phenyl group), 53.6, 43.7, 42.8, 40.4, 37.2, 36.8, 30.8, 28.9; IR
(neat): nÄ 2953, 2870, 1689 (CO), 1598, 1570, 1475, 1354, 1246, 955,
759 cmÀ1; MS: m/z (%): 214 (52) [M] , 199 (27), 181 (14), 167 (14), 145
597 cmÀ1; MS: m/z (%): 288 (14) [M] , 274 (22), 273 (100), 147 (24), 143
(100), 132 (14), 129 (15), 119 (14), 103 (12), 77 (15), 43 (22); HRMS calcd
for C15H18O [M] 214.135765; found: 214.135607.
(24), 134 (17), 129 (18), 119 (39), 117 (13), 91 (18), 43 (31); HRMS calcd for
1-[2-(3,3-Dimethyl-butyl)-4-trifluoromethyl-phenyl]-ethanone (4r): 1H NMR
(250 MHz, CDCl3, 258C): d 7.7 (d, 3J(H,H) 8.5 Hz, 1H; Ar), 7.5 (m,
2H; Ar), 2.8 (m, 2H; ArCH2), 2.6 (s, 3H; CH3 to CO), 1.5 (m, 2H; CH2), 1.0
(s, 9H; CH3); 13C NMR (62.9 MHz, CDCl3, 258C): d 201.7 (CO), 144
122 (Cs in phenyl group), 111.6 (CF3), 46.4, 30.8, 30.3, 29.4, 29.4; IR (solid):
nÄ 2987, 2869, 1697 (CO), 1473, 1412, 1364, 1333, 1170, 1131, 1090, 958,
C20H32O [M] 288.245316; found: 288.245239.
1-[2-(2-Cyclohexyl-ethyl)-phenyl]-ethanone (4e): 1H NMR (250 MHz,
3
CDCl3, 258C): d 7.6 (d, J(H,H) 7.4 Hz, 1H; Ar), 7.4 (m, 1H; Ar), 7.2
(m, 2H; Ar), 2.9 (t, 3J(H,H) 7.9 Hz, 2H; ArCH2), 2.6 (s, 3H; CH3 to CO),
1.8 1.6 (m, 5H), 1.5 1.4 (m, 2H), 1.3 1.1 (m, 4H), 1.0 (m, 2H); 13C NMR
(62.9 MHz, CDCl3, 258C): d 202.5 (CO), 143 125 (Cs in phenyl group),
39.9, 38.1, 33.4, 31.6, 30.1, 26.8, 26.5; IR (neat): nÄ 2923, 2850, 1687 (CO),
1600, 1571, 1484, 1445, 1354, 1250, 953, 758 cmÀ1; MS: m/z (%): 230 (22)
830 cmÀ1; MS: m/z (%): 272 (12) [M] , 216 (13), 215 (100), 201 (18), 199
(12), 187 (21), 59 (26), 57 (25), 43 (21); HRMS calcd for C15H19F3O [M]
272.138800; found: 272.139267.
[M] , 215 (46), 147 (54), 143 (24), 134 (79), 133 (28), 129 (22), 119 (100), 91
1-[2-(3,3-Dimethyl-butyl)-4-methoxy-phenyl]-ethanone (4s): 1H NMR
(250 MHz, CDCl3, 258C): d 7.7 (d, 3J(H,H) 9.3 Hz, 1H; Ar), 6.7 (m,
2H; Ar), 3.8 (s, 3H; CH3O), 2.9 (m, 2H; ArCH2), 2.6 (s, 3H; CH3 to CO),
1.4 (m, 2H; CH2), 1.0 (s, 9H; CH3); 13C NMR (62.9 MHz, CDCl3, 258C):
d 202 (CO), 162 110 (Cs in phenyl group), 55.5 (CH3O), 46.3, 30.8, 30.4,
29.4, 29.4; IR (neat): nÄ 2954, 2866, 1678 (CO), 1603, 1566, 1465, 1355,
(20), 43 (19); HRMS calcd for C16H22O [M] 230.167066; found:
230.167183.
1-[2-(2-Pentafluorophenyl-ethyl)phenyl]-ethanone
(4 f):
1H
NMR
(250 MHz, CDCl3, 258C): d 7.8 (dd, 3J(H,H) 8.8 Hz, 1H; Ar), 7.4 (m,
2H; Ar), 7.1 (dd, 3J(H,H) 7.8 Hz, 1H; Ar), 3.2 (m, 2H), 3.1 (m, 2H), 2.6
(s, 3H; CH3 to CO); 13C NMR (62.9 MHz, CDCl3, 258C): d 202 (CO),
141 127 (Cs in phenyl group and pentafluorophenyl group), 30.1, 29.6,
24.2; IR (solid): nÄ 3019, 1684 (CO), 1519, 1503, 1357, 1252, 1216, 1120,
1249, 1069, 962, 874 cmÀ1; MS: m/z (%): 234 (11) [M] , 219 (14), 178 (13),
177 (100), 163 (11), 161 (15), 91 (5), 43 (13); HRMS calcd for C15H22O2 [M]
234.161980; found: 234.161819.
1024, 966, 946, 765, 669 cmÀ1; MS: m/z (%): 314 (22) [M] , 299 (46), 134
8-(3,3-Dimethyl-butyl)-3,4-dihydro-2H-naphthalen-1-one (13): 1H NMR
(250 MHz, CDCl3, 258C): d 7.3 (t, 3J(H,H) 7.5 Hz, 1H; Ar) 7.1 (dd,
3J(H,H) 7.9 Hz, 2H; Ar) 3.0 (m, 4H), 2.6 (t, 3J(H,H) 6.4 Hz, 2H; a-CH2
(11), 133 (100), 105 (18), 103 (18), 90 (11), 79 (12), 77 (13), 43 (11); HRMS
calcd for C16H11F5O [M] 314.073006; found: 314.072807.
1-(2-Phenethyl-phenyl)-ethanone (4g): 1H NMR (250 MHz, CDCl3,
258C): d 7.7 7.1 (m, 9H; Ar), 3.2 (m, 2H), 2.9 (t, 3J(H,H) 7.6 Hz,
2H; CH2), 2.6 (s, 3H; CH3 to CO); 13C NMR (62.9 MHz, CDCl3, 258C):
d 202 (CO), 143 125 (Cs in phenyl group), 38.1, 36.2, 29.5; IR (neat): nÄ
3
to CO), 2.1 (qt, J(H,H) 6.4 Hz, 2H; b-CH2 to CO), 1.4 (m, 2H), 1.0 (s,
9H; CH3); 13C NMR (62.9 MHz, CDCl3, 258C): d 200 (CO), 147 126
(Cs in phenyl group), 46.2, 41.4, 31.4, 31.0, 30.9, 29.6, 23.2; IR (neat): nÄ
2950, 2866, 1679 (CO), 1591, 1462, 1364, 1321, 1272, 1237, 1212, 760 cmÀ1
MS: m/z (%): 230 (18) [M] , 174 (15), 173 (100), 159 (5), 155 (6), 117 (5),
;
1691 cmÀ1 (CO); MS: m/z (%): 224 (6) [M] , 210 (13), 209 (76), 133 (52),
105 (15), 103 (16), 91 (100), 90 (10), 89 (10), 79 (11), 77 (16).
115 (7), 91 (5).
1-[2-(2-Trimethylsilanyl-ethyl)-phenyl]-ethanone
(4h):
1H
NMR
Typical procedure for o-alkylation of ketone with olefin: A screw-capped
pressure vial (1 mL) was charged with acetophenone (5a, 38.9 mg,
0.324 mmol), tert-butylethylene (2a, 81.6 mg, 0.972 mmol), [RhCl(PPh3)3]
(3, 15 mg, 0.0162 mmol), benzylamine (17.4 mg, 0.162 mmol), and toluene
(0.2 g), and then the mixture was stirred in an oil bath at 1508C for 6 h.
After the resulting ketimine was hydrolyzed by using a HCl solution (1n),
the reaction mixture was purified by column chromatography (SiO2,
hexanes:ethyl acetate 5:2) to yield 62.8 mg (95%) of 4a.
(250 MHz, CDCl3, 258C): d 7.6 (dd, 3J(H,H) 7.6 Hz, 1H; Ar), 7.4 (m,
1H; Ar) 7.2 (m, 2H; Ar), 2.8 (m, 2H; ArCH2), 2.6 (s, 3H; CH3 to CO), 0.8
(m, 2H), 0.1 (s, 9H; CH3); 13C NMR (62.9 MHz, CDCl3, 258C): d 202
(C O), 132 125 (Cs in phenyl group), 30.0, 28.4, 19.6, À1.7 (CH3); IR
(neat): nÄ 2953, 1687, 1599, 1570, 1446, 1355, 1246, 1175, 1095, 954, 910,
860, 841, 757 cmÀ1; MS: m/z (%): 220 (8) [M] , 205 (100), 147 (17), 115 (18),
75 (95), 73 (74), 45 (11), 43 (25).
1-(2-Pentyl-phenyl)-ethanone (4m): 1H NMR (250 MHz, CDCl3, 258C):
d 7.6 (m, 1H; Ar), 7.4 (m, 1H; Ar), 7.2 (m, 2H; Ar), 2.8 (t, 3J(H,H)
7.7 Hz, 2H; ArCH2), 2.6 (s, 3H; CH3 to CO), 1.5 (m, 2H), 1.3 (m, 4H), 0.9
3
(t, J(H,H) 6.8 Hz, 3H; CH3); 13C NMR (62.9 MHz, CDCl3, 258C): d
Acknowledgements
203 (CO), 143 125 (Cs in phenyl group), 34, 32.1, 32, 30, 29.9, 29.8, 29.7,
29.5, 22.8, 14.2; IR (neat): nÄ 2925, 2854, 1688 (CO), 1466, 1354, 1251, 950,
758, 600 cmÀ1; MS: m/z (%): 260 (14) [M] , 245 (100), 147 (28), 143 (26),
This work was supported by the National Research Laboratory (2000-N-
NL-01-C-271) Program administered by the Ministry of Science and
Technology. The authors acknowledge the Brain Korea21 project.
134 (18), 129 (22), 119 (50), 117 (15), 91 (24), 43 (38); HRMS calcd for
C13H18O [M] 260.214016; found: 260.214069.
Chem. Eur. J. 2002, 8, No. 2
¹ WILEY-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002
0947-6539/02/0802-0491 $ 17.50+.50/0
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