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4.3.13. 3-Bromo-N-(2-(tert-butyldimethylsilyloxy)ethyl)-
aniline (Table 1, entry 7)
123.0, 120.6, 119.1, 115.1, 51.6, 30.0 (3C). HRMS (ESI): m/z
calcd for C10H15BrN (MHþ) 228.0382, found 228.0381.
Starting from 1,3-dibromobenzene (472 mg, 2 mmol) and 2-
(tert-butyldimethylsilyloxy)ethylamine (351 mg, 2 mmol), gen-
eral procedure A (8 h) afforded the title compound as a colorless
4.3.18. N-Allyl-3-bromoaniline (Table 1, entry 9)
Starting from 1,3-dibromobenzene (472 mg, 2 mmol) and
allylamine (114 mg, 2 mmol), general procedure A (5 h) af-
forded the title compound as a slightly tan oil (209 mg,
1
oil (388 mg, 58%). Rf¼0.27 (heptane/(i-Pr)2O 40:3). H NMR
(500 MHz, CDCl3) d 7.00 (dd, 1H, J¼8.0, 8.0 Hz), 6.81 (ddd,
1H, J¼7.9, 1.8, 0.7 Hz), 6.76 (dd, 1H, J¼2.1, 2.0 Hz), 6.53 (ddd,
1H, J¼8.1, 2.2, 0.6 Hz), 4.11 (br s, 1H), 3.80 (t, 2H, J¼5.4 Hz),
3.18 (td, 2H, J¼5.4, 5.4 Hz), 0.91 (s, 9H), 0.07 (s, 6H); 13C
NMR (125 MHz, CDCl3) d 149.9, 130.6, 123.4, 120.4, 115.8,
112.1, 61.6, 45.9, 26.0 (3C), 18.5, ꢂ5.2 (2C). HRMS (ESI): m/z
calcd for C14H25BrNOSi (MHþ) 330.0883, found 330.0889.
1
49%). Rf¼0.26 (heptane/(i-Pr)2O 40:3). H NMR (500 MHz,
CDCl3) d 7.00 (dd, 1H, J¼8.0, 8.0 Hz), 6.81 (ddd, 1H,
J¼7.8, 1.8, 0.8 Hz), 6.74 (dd, 1H, J¼2.1, 2.1 Hz), 6.51 (ddd,
1H, J¼8.2, 2.3, 0.8 Hz), 5.91 (ddt, 1H, J¼17.2, 10.3,
5.3 Hz), 5.27 (ddt, 1H, J¼17.2, 3.2, 1.7 Hz), 5.18 (ddt, 1H,
J¼10.3, 3.0, 1.5 Hz), 3.87 (br s, 1H), 3.74 (ddd, 2H, J¼5.3,
1.6, 1.6 Hz); 13C NMR (125 MHz, CDCl3) d 149.4, 134.8,
130.6, 123.4, 120.3, 116.7, 115.6, 111.8, 46.4. HRMS (ESI):
m/z calcd for C9H11BrN (MHþ) 212.0069, found 212.0070.
4.3.14. 1-(3-Bromophenyl)pyrrolidine (Table 1, entry 8)
Starting from 1,3-dibromobenzene (472 mg, 2.0 mmol) and
pyrrolidine (171 mg, 2.4 mmol, 1.2 equiv), general procedure
A (4.5 h) afforded the title compound as a colorless oil
(353 mg, 78%). Rf¼0.47 (heptane/(i-Pr)2O 40:3). 1H NMR
(500 MHz, CDCl3) and 13C NMR (125 MHz, CDCl3) in agree-
ment with the literature.30
4.3.19. N-(3-Bromophenyl)-2,6-di-iso-propylaniline (Table
1, entry 10)
Starting from 1,3-dibromobenzene (472 mg, 2 mmol) and
2,6-di-iso-propylaniline (355 mg, 2 mmol), general procedure
A (5 h) afforded the title compound as a colorless oil (570 mg,
1
4.3.15. 1-(3-Bromo-2-methylphenyl)pyrrolidine (Table 1,
entry 8)
86%). Rf¼0.39 (heptane/(i-Pr)2O 40:3). H NMR (500 MHz,
CDCl3) d 7.30 (dd, 1H, J¼8.1, 7.2 Hz), 7.22 (d, 2H,
J¼7.9 Hz), 6.97 (t, 1H, J¼8.0 Hz), 6.81 (ddd, 1H, J¼7.9, 1.8,
0.9 Hz), 6.63 (br s, 1H), 6.37 (d, 1H, J¼7.8 Hz), 5.15 (br s,
1H), 3.15 (septet, 2H, J¼6.9 Hz), 1.14 (d, 12H, J¼6.9 Hz);
13C NMR (125 MHz, CDCl3) d 149.6, 147.7 (2C), 134.3,
130.7, 127.8, 124.2 (2C), 123.4, 120.7, 115.8, 111.6, 28.4
(2C), 24.0 (4C). HRMS (ESI): m/z calcd for C18H23BrN
(MHþ) 332.1008, found 332.1000.
Starting from 2,6-dibromotoluene (2) (5.00 g, 20 mmol) and
pyrrolidine (1.42 g, 20 mmol), general procedure A (2.5 h) af-
forded the title compound as a colorless oil (3.01 g, 68%).
Rf¼0.72 (heptane). 1H NMR (500 MHz, CDCl3) d 7.16 (d, 1H,
J¼7.8 Hz), 6.94 (t, 1H, J¼8.0 Hz), 6.88 (d, 1H, J¼8.0 Hz),
3.13e3.07 (m, 4H), 2.37 (s, 3H), 1.96e1.88 (m, 4H); 13C
NMR (125 MHz, CDCl3) d 151.4, 129.7, 127.1, 127.0, 125.2,
115.6, 51.6 (2C), 24.9 (2C), 20.2. Anal. Calcd for C11H14BrN:
C, 55.02; H, 5.88; N, 5.83. Found: C, 55.26; H, 5.87; N, 5.72.
4.3.20. 3-Bromo-N,N-di-n-propylaniline (Table 1, entry 11)
Starting from 1,3-dibromobenzene (472 mg, 2 mmol) and
dipropylamine (202 mg, 2 mmol), general procedure A (20 h)
afforded the title compound as a pale yellow oil (261 mg,
51%). Rf¼0.68 (heptane/EtOAc 6:1). 1H NMR (500 MHz,
CDCl3) d 7.02 (dd, 1H, J¼8.3, 7.9 Hz), 6.75e6.69 (m, 2H),
6.53 (ddd, 1H, J¼8.3, 2.5, 0.5 Hz), 3.20 (t, 4H, J¼7.7 Hz),
1.59 (tq, 4H, J¼7.7, 7.4 Hz), 0.92 (t, 6H, J¼7.4 Hz); 13C
NMR (125 MHz, CDCl3) d 149.6, 130.5, 123.7, 118.0, 114.4,
110.4, 52.9 (2C), 20.4 (2C), 11.5 (2C). HRMS (ESI): m/z calcd
for C12H19BrN (MHþ) 256.0695, found 256.0697.
4.3.16. 3-Bromo-N-iso-propylaniline (Table 1, entry 9)
Starting from 1,3-dibromobenzene (472 mg, 2 mmol) and
isopropylamine (118 mg, 2 mmol), general procedure A (4 h)
afforded the title compound as a slightly tan oil (288 mg, 67%).
Rf¼0.44 (heptane/EtOAc 6:1). 1H NMR (500 MHz, CDCl3)
d 6.99 (dd, 1H, J¼8.0, 8.0 Hz), 6.76 (ddd, 1H, J¼7.8, 1.8,
0.9 Hz), 6.70 (dd, 1H, J¼2.1, 2.0 Hz), 6.47 (ddd, 1H, J¼8.2,
2.3, 0.8 Hz), 3.58 (septet, 1H, J¼6.3 Hz), 3.30 (very br s, 1H),
1.20 (d, 6H, J¼6.3 Hz); 13C NMR (125 MHz, CDCl3) d 148.9,
130.6, 123.4, 119.6, 115.6, 112.0, 44.2, 22.9 (2C). HRMS
(ESI):m/zcalcdforC9H13BrN(MHþ) 214.0226, found 214.0225.
4.3.21. 1-(3-Bromo-2-methylphenyl)piperidine (Table 1,
entry 12)
4.3.17. 3-Bromo-N-tert-butylaniline (Table 1, entry 9)
Starting from 1,3-dibromobenzene (472 mg, 2 mmol) and
tert-butylamine (146 mg, 2 mmol), general procedure A (23 h)
afforded the title compound as a pale yellow oil (231 mg,
Starting from 2,6-dibromotoluene (2) (5.00 g, 20 mmol) and
piperidine (1.70 g, 20 mmol), general procedure A (3.5 h) af-
forded the title compound as a colorless oil (4.26 g, 84%).
1
Rf¼0.52 (heptane/EtOAc 50:1). H NMR (500 MHz, CDCl3)
1
51%). Rf¼0.21 (heptane/(i-Pr)2O 40:3). H NMR (500 MHz,
d 7.24 (dd, 1H, J¼7.8, 1.1 Hz), 6.99 (t, 1H, J¼7.9 Hz), 6.94
(dd, 1H, J¼7.9, 1.0 Hz), 2.80 (br s, 4H), 2.37 (s, 3H), 1.71 (pen-
tet, 4H, J¼5.5 Hz), 1.57 (br s, 2H); 13C NMR (125 MHz,
CDCl3) d 154.7, 133.0, 127.3, 126.9, 126.5, 118.2, 53.8 (2C),
26.6 (2C), 24.4, 18.4. Anal. Calcd for C12H16BrN: C, 56.71;
H, 6.35; N, 5.51. Found: C, 56.57; H, 6.23; N, 5.47.
CDCl3) d 6.98 (dd, 1H, J¼8.0, 8.0 Hz), 6.86 (dd, 1H, J¼2.1,
2.0 Hz), 6.82 (ddd, 1H, J¼7.9, 1.8, 0.8 Hz), 6.61 (ddd, 1H,
1
J¼8.2, 2.3, 0.8 Hz), 3.58 (br s, 1H), 1.34 (s, 9H); H NMR in
agreementwithpreviouslyreported31 datarunatlowerspectrom-
eter frequency; 13C NMR (125 MHz, CDCl3) d 148.4, 130.3,