Aluminium Powder-Catalyzed Regio- and Stereoselective Aminobromination
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solid; yield: 2585 mg (99.8%) from 2a (1340 mg, 5 mmol);
112.39, 111.72, 59.4, 55.7, 55.4, 42.4, 20.9; MS: m/z (% rel.
intensity)=77 (40), 91 (30), 105 (100), 155 (15), 399 (55),
1
mp 1758C (EtOH); H NMR (300 MHz, CDCl ): d=7.77
3
+
(
4
d, J=8.40 Hz, 2H), 7.59 (d, J=7.50 Hz, 2H), 7.12–7,07 (m,
H), 6.87–6.81 (m, 2H), 6.65 (d, J=7.80 Hz, 2H), 5.36 (d,
J=3.90 Hz, 1H), 5.03–5.01 (m, 1H), 3.82 (d, J=12.3 Hz,
597 (M , 5); anal. calcd. for C H Br NO S: C 48.26, H
2
4
23
2
5
3.88, N 2.34; found: C 48.30, H 3.92, N 2.41.
(Æ)-trans-2-Bromo-1-phenyl-3-(3,4,5-trimethoxyphenyl)-3-
1
3
3
H), 3.70–3.67 (d, J=9.90 Hz, 3H), 2.34 (s, 3H); C NMR
(p-toluenesulfonamido)propan-1-one (7c): White solid;
(
75.45 MHz, CDCl ): d=192.5, 164.5, 159.3, 142.8, 138.0,
yield: 1721 mg (62.8%) from 7a (1490 mg, 5 mmol); mp
3
1
1
(
7
31.2 (3), 129.1 (3), 128.6 (2), 127.2, 127.1, 114.0 (2), 113.9
2), 60.5, 55.6, 55.2, 45.9, 21.4; MS: m/z (% rel. intensity)=
7 (15), 91 (30), 135 (100), 154 (15), 290 (45), 438 (25); anal.
calcd. for C H BrNO S: C 55.60, H 4.63, N 2.70; found: C
167–1688C (EtOH); H NMR (300 MHz, CDCl ): d=7.79
3
(d, J=7.80 Hz, 2H), 7.57 (d, J=7.80 Hz, 2H), 7.42–7.37 (m,
2H), 7.09 (d, J=7.8 Hz, 2H), 6.85 (d, J=8.70 Hz, 1H), 6.31
(s, 2H), 5.42 (d, J=4.50 Hz, 1H), 5.08–5.05 (m, 1H), 3.72–
24
24
5
1
3
5
5.67, H 4.58, N 2.75.
Æ)-trans-2-Bromo-3-(4-methoxyphenyl)-1-phenyl-3-(p-
toluenesulfonamido)propan-1-one (3c): White solid; yield:
3.67 (m, 9H), 2.33 (s, 3H); C NMR (75.45 MHz, CDCl ):
3
(
d=193.7, 152.8, 142.7, 137.6, 137.4, 134.1, 134.0, 131.9, 128.8
(2), 128.5 (2), 128.4 (2), 127.0 (2), 126.8 (2), 104.4, 60.7, 60.4,
55.7, 45.6, 21.1; MS: m/z (% rel. intensity)=65 (5), 77 (25),
2
1
7
7
5
396 mg (98.2%) from 3a (1190 mg, 5 mmol); mp 155–
1
+
568C (EtOH); H NMR (300 MHz, CDCl ): d=7.78 (d, J=
91 (25), 105 (100), 155 (5), 195 (30), 350 (80), 549 (M +1,
3
.50 Hz, 2H), 7.60–7.53 (m, 2H), 7.42–7.38 (m, 2H), 7.12–
5); anal. calcd. for C H BrNO S: C 54.74, H 4.75, N 2.56;
2
5
26
6
.07 (m, 4H), 6.71–6.64 (m, 3H), 5.40 (d, J=4.20 Hz, 1H),
found: C 54.62, H 4.79, N 2.60.
1
3
.06–5.02 (m, 1H), 3.70 (s, 3H), 2.34 (s, 3H); C NMR
75.45 MHz, CDCl ): d=193.7, 159.0, 142.6, 137.6, 134.1,
(Æ)-trans-2-Bromo-1-(4’-nitrophenyl)-3-(3,4,5-trimethoxy-
(
phenyl)-3-(p-toluenesulfonamido)propan-1-one (8c): White
3
1
1
7
33.9, 128.8 (2), 128.5 (3), 128.4 (2), 128.3 (2), 126.8 (2),
13.7 (2), 59.9, 54.90, 46.0, 21.1; MS: m/z (% rel intensity)=
7 (35), 91 (45), 105 (100), 155 (15), 290 (50), 408 (15); anal.
solid; yield: 1379 mg (46.5%) from 8a (1715 mg, 5 mmol);
1
mp 194–1968C (EtOH); H NMR (300 MHz, CDCl ): d=
3
8.25 (d, J=8.40 Hz, 2H), 7.99–7.94 (m, 2H), 7.64–7.5 (m,
2H), 7.15–7.09 (m, 2H), 6.70–6.59 (m, 1H), 6.31 (s, 1H),
5.62 (d, J=4.50 Hz, 1H), 5.42–5.38 (m, 1H), 3.73 (s, 9H);
calcd. for C H BrNO S: C 56.56, H 4.54, N 2.87; found: C
23
22
4
56.60, H 4.58, N 2.97.
1
3
(
Æ)-trans-2-Bromo-1-(4’-chlorophenyl)-3-(4-methoxy-
C NMR (75.45 MHz, CDCl ): d=191.9, 152.6, 150.5, 143.1,
3
phenyl)-3-(p-toluenesulfonamido)propan-1-one (4c): White
solid; yield: 2516 mg (96.2%) from 4a (1365 mg, 5 mmol);
mp 162–1638C (EtOH); H NMR (300 MHz, CDCl ): d=
7
138.5, 136.8, 131.4, 130.0, 129.5, 128.9 (2), 128.8 (2), 126.9
(2), 123.7 (2), 108.4, 60.6, 60.2, 55.8, 46.1, 43.5, 21.1; MS: m/
z (% rel. intensity)=65 (25), 91 (100), 105 (40), 150 (80),
192 (25), 195 (10), 207 (50), 350 (35), 357 (60), 428 (70), 512
1
3
.73 (d, J=8.10 Hz, 2H), 7.57 (d, J=9.00 Hz, 2H), 7.37 (d,
+
J=8.40 Hz, 2H), 7.12–7.05 (m, 3H), 6.67–6.58 (m, 3H), 5.34
(60), 592 (M À1, 5); anal. calcd. for C H BrN O S: C
2
5
25
2
8
(
d, J=4.80 Hz, 1H), 5.05–5.01 (m, 1H), 3.71 (s, 3H), 2.34 (s,
50.59, H 4.21, N 4.72; found: C 50.56, H 4.12, N 4.91.
13
3
1
1
H); C NMR (75.45 MHz, CDCl ): d=193.7, 159.0, 142.6,
(Æ)-trans-3-Bromo-3-(4-fluorophenyl)-1-(4’-methoxyphen-
3
37.6, 134.1, 133.9, 128.8 (2), 128.5 (3), 128.4 (2), 128.3 (2),
26.8 (2), 113.7 (2), 59.9, 54.9, 46.0, 21.1; MS: m/z (% rel. in-
yl)-2-(p-toluenesulfonamido)propan-1-one (9b): White solid;
yield: 1763 mg (69.7%) from 9a (1280 mg, 5 mmol); mp
1
tensity)=65 (15), 91 (57), 111 (25), 139 (70), 155 (25), 290
164–1658C (EtOH); H NMR (300 MHz, CDCl ): d=7.81
3
(
4
100), 442 (15); anal. calcd. for C H BrClNO S: C 52.84, H
.05, N 2.68; found: C 52.97, H 4.02, N 2.60.
(d, J=8.70 Hz, 2H), 7.45 (d, J=7.50 Hz, 2H), 7.29 (d, J=
9.9 Hz, 2H), 7.15 (s, 2H), 7.02 (d, J=7.50 Hz, 2H), 6.94–
6.85 (m, 2H), 5.48–5.42 (m, 2H), 5.06 (d, J=6.60 Hz, 1H),
2
3
21
4
(
Æ)-trans-2-Bromo-3-(4-methoxyphenyl)-1-(4’-nitrophen-
1
3
yl)-3-(p-toluenesulfonamido)propan-1-one (5c): White solid;
3.92 (s, 3H), 2.33 (s, 3H); C NMR (75.45 MHz, CDCl ):
3
yield: 2444 mg (91.7%) from 5a (1415 mg, 5 mmol); mp
d=194.2, 164.3, 142.8, 136.5, 132.4 (2), 131.1 (2), 130.1 (2),
129.1, 128.9, 127.4, 126.7 (2), 115.3, 115.0, 113.8 (2), 60.1,
55.3, 45.4, 21.0; anal. calcd. for C H BrFNO S: C 54.55, H
1
1
56–1578C (EtOH); H NMR (300 MHz, CDCl ): d=8.24
3
(
2
d, J=8.10 Hz, 2H), 8.01–7.94 (m, 2H), 7.55 (d, J=7.50 Hz,
H), 7.12–7.06 (m, 3H), 6.67 (d, J=8.10 Hz, 2H), 6.40 (d,
J=9.00 Hz, 1H), 5.39 (d, J=5.10 Hz, 1H), 5.08–5.04 (m,
2
3
21
4
4.15 N, 2.77; found: C 54.59, H 4.10, N 2.88.
(Æ)-trans-3-Bromo-1-(4’-chlorophenyl)-3-(4-fluorophen-
1
3
1
H), 3.71 (s, 3H), 2.35 (s, 3H); C NMR (75.45 MHz,
yl)-2-(p-toluenesulfonamido)propan-1-one (10b): White
CDCl ): d=191.9, 159.2, 150.4, 142.9, 138.7, 137.2, 132.2,
solid; yield: 1131 mg (44.3%) from 10a (1304 mg, 5 mmol);
3
1
129.85, 129.4 (2), 129.2, 128.9, 128.2, 126.8 (2), 123.6 (2),
113.8 (2), 59.3, 54.9, 46.60, 21.1; MS: m/z (% rel. intensity)=
65 (30), 77 (25), 91 (100), 107 (30), 150 (70), 290 (10), 297
mp: 140–1418C (EtOH); H NMR (300 MHz, CDCl ): d=
3
7.780 (d, J=8.40 Hz, 2H), 7.42–7.39 (m, 2H), 7.11 (d, J=
7.82 Hz, 2H), 6.82–7.02 (m, 2H), 5.58 (d, J=6.00 Hz, 1H),
5.43–5.32 (m, 1H), 4.13–4.08 (m, 1H), 2.34 (s, 3H);
(
15), 363 (20), 452 (35); anal. calcd. for C H BrN O S: C
23 21 2 6
1
3
51.78, H 3.94, N 4.50; found: C 51.76, H 3.96, N 4.53.
C NMR (75.45 MHz, CDCl ): d=195.6, 164.0, 160.7, 143.3,
3
(
Æ)-trans-2-Bromo-3-(2-bromo-4,5-dimethoxyphenyl)-1-
140.5, 136.2, 133.2, 132.1 (2), 129.9 (2), 129.0 (2), 128.9 (2),
126.5 (2), 115.3, 115.0, 59.7, 49.8, 20.8; anal. calcd. for
C H BrClFNO S: C 57.13, H 3.55, N 2. 74; found: C 57.18,
phenyl-3-(p-toluenesulfonamido)propan-1-one (6c): White
solid; yieled: 2331 mg (78.1%) from 6a (1735 mg, 5 mmol);
mp 152–1538C (EtOH); H NMR (300 MHz, CDCl ): d=
2
2
18
3
1
H 3.52, N 2.81.
3
7
.77–7.53 (m, 5H), 7.42–7.37 (dd, J=7.2 Hz, 2H), 7.15 (d,
(Æ)-trans-3-Bromo-1-(4’-methoxyphenyl)-3-phenyl-2-(p-
J=7.5 Hz, 2H), 6.93 (d, J=8.70 Hz, 2H), 6.86 (s, 1H), 5.58
toluenesulfonamido)propan-1-one (11b): White solid; yield:
(
3
d, J=6.00 Hz, 1H), 5.32 (dd, J=4.2 Hz, 1H), 3.78 (s, 3H),
622 mg (25.5%) from 11a (1190 mg, 5 mmol); mp 159–
1
3
1
.65 (s, 3H), 2.35 (s, 3H); C NMR (75.45 MHz, CDCl ):
159.58C (EtOH); H NMR (300 MHz, CDCl ): d=7.78 (d,
3
3
d=193.74, 148.97, 147.96, 142.72, 137.08, 133.90, 133.83,
28.70 (2), 128.36 (2), 128.15 (2), 127.20 (2), 126.67, 114.82,
J=8.40 Hz, 2H), 7.46 (d, J=7.95 Hz, 2H), 7.01 (d, J=
7.80 Hz, 2H), 6.90 (d, J=8.40 Hz, 2H), 5.53–5.42 (m, 2H),
1
Adv. Synth. Catal. 2009, 351, 2358 – 2368
ꢁ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
2365