8298
T. Takahashi et al. / Tetrahedron 68 (2012) 8293e8299
þ
þ
1
13.6; MS (EI) m/z 197 (M , 69%), 120 (100%), 105 (5%), 92 (15%), 77
136.5, 128.8, 115.1, 27.9, 15.8; MS (EI) m/z 122 (M , 32%), 107 (100%),
(10%), 65 (9%).
91 (19%), 77 (45%).
0
4
.3.9. 4 -Cyanoacetophenone (Table 1, entries 17 and 18). No re-
4.3.20. 4-Hydroxystyrene (Table 2, entry 14). No reaction took
action took place. Starting material was recovered in 95% (34.5 mg)
entry 17) and 92% (33.3 mg) yields (entry 18).
place. Starting material was recovered in 95% yield (28.6 mg).
(
1
0
4
.3.21. 4-Bromoethylbenzene (Table 2, entry 15). Yield 33.2 mg
.3.10. 4-Ethylanisole (Table 2, entry 1).10 Yield 28.2 mg (83%). H
1
(72%). H NMR
(q, J¼7.6 Hz, 2H), 1.21 (t, J¼7.6 Hz, 3H); C NMR
1
d
7.39 (d, J¼8.4 Hz, 2H), 7.06 (d, J¼8.4 Hz, 2H), 2.60
4
13
NMR
d
7.11 (d, J¼8.5 Hz, 2H), 6.83 (d, J¼8.5 Hz, 2H), 3.78 (s, 3H), 2.59
d 143.1, 131.3, 129.6,
13
þ
(
q, J¼7.6 Hz, 2H),1.21 (t, J¼7.6 Hz, 3H); C NMR
d
157.6, 136.4, 128.7,
119.2, 28.3, 15.4; MS (EI) m/z 184 (M , 76%), 169 (100%), 105 (84%),
þ
113.7, 55.2, 28.0, 15.9; MS (EI) m/z 136 (M , 20%), 121 (100%), 91
90 (21%), 77 (24%), 63 (12%), 51 (17%).
(
10%), 77 (8%).
1
8
4
.3.22. 1-tert-Butyl-4-ethylbenzene(Table 2, entries 17 and 18). Yields
.3.11. 4-Methoxystyrene (Table 2, entry 2).12 Yield 31.8 mg (95%).
38.1 mg (94%) (entry 17) and 37.3 mg (92%) (entry 18). H NMR
1
d 7.30
4
1
H NMR
d
7.35 (d, J¼9.0 Hz, 2H), 6.86 (d, J¼9.0 Hz, 2H), 6.66 (dd,
(d, J¼8.2 Hz, 2H), 7.13 (d, J¼8.2 Hz, 2H), 2.62 (q, J¼7.6 Hz, 2H), 1.31 (s,
13
J¼17.6, 10.9 Hz 1H), 5.62 (dd, J¼17.6, 0.6 Hz, 1H), 5.12 (dd, J¼10.9,
9H), 1.23 (t, J¼7.6 Hz, 2H); C NMR
d 148.2, 141.0, 127.4, 125.1, 34.4,
13
þ
0
1
.6 Hz, 1H), 3.81 (s, 3H); C NMR
11.8, 55.5; MS (EI) m/z 134 (M , 100%),119 (56%) 103 (5%), 91 (85%),
d
159.6, 136.4, 130.7, 127.6, 114.1,
31.5, 28.3, 15.6; MS (EI) m/z 162 (M , 26%), 147 (100%), 131 (5%), 119
þ
(29%), 105 (6%), 91 (31%), 79 (14%), 51 (4%).
6
5 (46%), 51 (10%).
2
4
.3.23. 4-Ethylnitrobenzene (Table 2, entries 19 and 20).1 Yields
1
2
1
4.3.12. 4-Ethylaniline (Table 2, entries 3 and 4). Yields 27.2 mg
35.5 mg (94%) (entry 19) and 34.7 mg (92%) (entry 20). H NMR
1
(
90%) (entry 3) and 28.5 mg (94%) (entry 4). H NMR
d
7.00 (d,
d
8.14 (d, J¼8.4 Hz, 2H), 7.34 (d, J¼8.4 Hz, 2H), 2.76 (q, J¼7.2 Hz,
13
J¼8.2 Hz, 2H), 6.64 (d, J¼8.2 Hz, 2H), 3.54 (br s, 2H), 2.54 (q, J¼7.7 Hz,
2H), 1.29 (t, J¼7.2 Hz, 3H); C NMR
d 152.0, 146.3, 128.6, 123.7,
13
þ
2
H), 1.19 (t, J¼7.7 Hz, 3H); C NMR
d
144.1, 134.4, 128.6, 115.3, 28.0,
28.9, 15.1; MS (EI) m/z 122 (M , 32%), 107 (100%), 91 (19%),
þ
15.9; MS (EI) m/z 121 (M , 42%), 106 (100%) 91 (7%), 77 (24%).
77 (45%).
4
6
.3.13. Benzyl N-(4-ethylphenyl)carbamate (Table 2, entries 5 and
4.3.24. 2-Methoxy-4-vinylphenol (Table 2, entries 21 and 22) No
reaction took place. Starting material was recovered in 98%
(36.8 mg) (entry 21) and 95% (35.7 mg) (entry 22).
10
1
). Yields 61.9 mg (97%) (entry 5) and 60.6 mg (95%) (entry 6). H
7.24e7.40 (m, 7H), 7.12 (d, J¼8.5 Hz, 2H), 6.67 (br s, 1H), 5.18
NMR
s, 2H), 2.59 (q, J¼7.6 Hz, 2H),1.20 (t, J¼7.6 Hz, 3H); C NMR
39.6, 136.1, 135.3, 128.6, 128.3, 128.3, 118.9, 66.9, 28.2, 15.6; MS (EI)
d
13
(
1
d 153.4,
4.3.25. 2-Phenyl-2-butanol (Table 2, entries 23 and 24).1 Yields
9
þ
1
m/z 255 (M , 40%), 211 (15%) 196 (22%),132 (8%), 91 (100%), 65 (5%).
35.6 mg (95%) (entry 23) and 36.0 mg (96%) (entry 24). H NMR
d
7.44 (t, J¼7.2 Hz, 2H), 7.34 (dd, J¼7.7, 7.2 Hz, 2H), 7.24 (t, J¼7.7 Hz,
1
6
13
4
3
.3.14. 2-Ethylbenzaldehyde (Table 2, entries 7 and 8). Yields
1H), 2.06 (m, 2H), 1.55 (s, 3H), 0.81 (t, J¼7.2 Hz, 3H); C NMR
1
þ
1.2 mg (93%) (entry 7) and 30.8 mg (92%) (entry 8). H NMR
d
10.30
d
147.5, 128.2, 126.6, 125.1, 74.8, 36.6, 29.5, 8.2; MS (EI) m/z 150 (M ,
(
s, 1H), 7.83 (dd, J¼7.5, 1.2 Hz, 1H), 7.52 (td, J¼7.5, 1.5 Hz, 1H), 7.37 (t,
5%), 121 (100%).
J¼7.5 Hz, 1H), 7.30 (d, J¼7.8 Hz, 1H), 3.08 (q, J¼7.5 Hz, 2H), 1.28 (t,
13
12
J¼7.5 Hz, 3H); C NMR
d
192.4, 147.0, 133.9, 133.4, 131.7, 130.2,
4.3.26. Benzyl propionate (Table 2, entries 25 and 26). Yields
37.3 mg (91%) (entry 25) and 36.1 mg (88%) (entry 26). H NMR
þ
1
1
26.3, 25.7, 16.3; MS (EI) m/z 133 (M , 100%), 115 (22%), 105 (63%),
9
1 (69%), 77 (42%), 51 (21%).
d
7.30e7.37(m, 5H), 5.12(s, 2H), 2.38(q, J¼7.6 Hz,2H),1.16(t, J¼7.6 Hz,
13
3
H); CNMRd174.3,136.0,128.5,128.1, 50.7, 27.5, 9.0;MS(EI)m/z164
.3.15. 4-Benzyloxy-3-methoxyethylbenzene (Table 2, entry 9).10
(M , 55%), 108 (100%), 91 (85%), 79 (12%), 65 (10%), 57 (22%).
þ
4
1
Yield 59.1 mg (98%). H NMR
1
2
d
7.27e7.45 (m, 5H), 6.80 (d, J¼8.0 Hz,
4.3.27. Benzyl isobutylate (Table 2, entries 27 and 28).1 Yields
40.1 mg (90%) (entry 27) and 40.9 mg (92%) (entry 28). H NMR
d
13
0
H), 6.75 (s, 1H), 6.66 (d, J¼8.0 Hz, 1H), 5.12 (s, 2H), 3.88 (s, 3H),
13
1
.58 (q, J¼7.6 Hz, 2H), 1.21 (t, J¼7.6 Hz); C NMR
d
149.6, 146.2,
137.6, 137.5, 128.4, 127.7, 127.2, 119.5, 114.4, 111.9, 71.3, 55.9, 28.4,
7.29e7.39 (m, 5H), 5.11 (s, 2H), 2.60 (m, 1H), 1.19 (d, J¼7.1 Hz, 6H);
þ
15.7; MS (EI) m/z 242 (M , 55%), 151 (44%), 123 (5%), 91 (100%), 77
C NMR
d
176.9, 136.2, 128.5, 128.1, 127.9, 66.0, 34.0, 18.9; MS (EI)
þ
(
6%), 65 (8%).
m/z 178 (M , 38%), 108 (27%), 91 (100%), 71 (10%), 43 (11%).
4
.3.16. 4-Benzyloxy-3-methoxystyrene(Table 2, entry 10). No reaction
4.3.28. Hexyl 4-(benzyloxycarbonylamino)benzoate (Table 2, entries
7
c
took place. Starting material was recovered in 97% yield (58.3 mg).
29 and 30). Yields83.4 mg (94%) (entry 29) and 87.0 mg (98%) (entry
1
3
0). H NMR
d
7.99 (d, J¼8.8 Hz, 2H), 7.47e7.34 (m, 7H), 6.86 (br s, 1H),
4
.3.17. 1,2-Dimethoxy-4-ethylbenzene (Table 2, entry 11).17 Yield
5.22 (s, 2H), 4.29 (t, J¼7.0 Hz, 2H), 1.78e1.71 (m, 2H), 1.43e1.32 (m, 6H),
1
13
41.1 mg (99%). H NMR
d
6.80 (d, J¼7.8 Hz, 1H), 6.74 (d, J¼7.8 Hz,
0.90 (t, J¼7.0 Hz, 3H); C NMR
d 166.2, 152.8, 141.9, 135.7, 130.9, 128.7,
1
H), 6.73 (s, 1H), 3.88 (s, 3H), 3.86 (s, 3H), 2.60 (q, J¼7.4 Hz, 2H), 1.23
128.5,128.4,125.4,117.6, 67.4, 65.0, 31.5, 28.7, 25.7, 22.5,14.0; MS (EI) m/
13
þ
(
5
t, J¼7.4 Hz, 3H); C NMR
d
148.7, 146.9, 136.9, 119.4, 111.2, 111.1,
z 355 (M , 18%), 311 (11%), 163 (44%), 146 (44%), 91 (100%).
þ
5.9, 55.7, 28.4, 15.8; MS (EI) m/z 166 (M , 76%), 151 (100%), 135
4.3.29. 4-Propoxybenzaldehyde (Table 2, entries 31 and 32).1 Yields
2
(
11%), 123 (6%), 108 (12%), 95 (20%), 77 (24%), 65 (10%), 51 (7%).
1
4
0.1 mg (98%) (entry 31) and 37.8 mg (92%) (entry 32). H NMR
4
.3.18. 1,2-Dimethoxy-4-styrene (Table 2, entry 12) No reaction took
d
9.88 (s, 1H), 7.83 (d, J¼8.8 Hz, 2H), 7.00 (d, J¼8.8 Hz, 2H), 4.02 (t,
13
place. Starting material was recovered in 94% yield (38.5 mg).
J¼6.6 Hz, 2H), 1.80e1.87 (m, 2H), 1.06 (t, J¼7.6 Hz, 3H); C NMR
d
190.8, 164.2, 132.0, 129.7, 114.7, 69.9, 22.3, 10.7; MS (EI) m/z 164
12
þ
4.3.19. 4-Ethylphenol (Table 2, entry 13). Yield 28.4 mg (93%)
(M , 30%), 138 (23%), 122 (30%), 121 (100%).
1
(
entry 13). H NMR
d
7.06 (d, J¼7.1 Hz, 2H), 6.78 (d, J¼7.1 Hz, 2H),
13
5
.57 (s, 1H), 2.59 (q, J¼6.5 Hz, 2H), 1.21 (t, J¼6.5 Hz, 3H); C NMR
4.3.30. Propyl 3-(4-nitrophenyl)acetate (Table 3, entries
2). Yields 52.9 mg (95%) (entry 1) and 52.3 mg (94%) (entry 2).
1
and
153.2, 136.5, 128.8, 115.1, 27.9, 15.8; 13C NMR
d
153.2,
10
(
100 MHz)
d