A R T I C L E S
Pawlas et al.
N-Butyl-(2-cyclohexen-1-yl)amine (Entry 5). Using the general
procedure and a 7 h reaction time, the product from reaction on a 2
mmol scale was isolated by Ku¨gelrohr distillation (40 mT, 35 °C) to
N-Benzyl-(2-cyclopenten-1-yl)methylamine (Entry 12). Product
from reaction for 43 h on a 2 mmol scale using the general procedure
and freshly cracked cyclopentadiene was isolated by Ku¨gelrohr
distillation (40 mT, 62 °C) to give 341 mg (91% yield) of colorless
oil. 1H NMR (CDCl3) δ 7.40-7.11 (m, 5Η), 5.92-5.72 (m, 2H), 3.90
(m, 1H), 3.56 (d, J ) 12.9 Hz, 1H), 3.39 (d, J ) 12.9 Hz, 1H), 2.45-
2.20 (m, 2H), 2.10 (s, 3H), 2.02-1.75 (m, 2H). 13C{1H} NMR (CDCl3)
δ 139.95, 135.56, 131.46, 129.04, 128.26, 126.85, 70.40, 58.37, 38.09,
31.91, 23.70. HRMS Calcd for C13H17N+ 187.1361; Found 187.1360.
N-Benzyl-(2-cyclohepten-1-yl)methylamine (Entry 13). Product
from reaction for 60 h on a 2 mmol scale using the general procedure
was isolated by Ku¨gelrohr distillation (50 mT, 85 °C) to give 404 mg
1
give 273 mg (89% yield) of colorless oil. H NMR (CDCl3) δ 5.76-
5.58 (m, 2H), 3.10 (m, 1H), 2.59 (m, 2H), 1.95 (m, 2H), 1.82 (m, 1H),
1.68 (m, 1H), 1.50 (m, 1H), 1.41 (m, 3H), 1.32 (m, 2H), 0.85 (t, J )
7.2 Hz, 3H). 13C{1H} NMR (CDCl3) δ 130.25, 128.68, 53.16, 46.78,
32.79, 29.68, 25.41, 20.66, 20.39, 14.10. GC/MS(EI); m/z 153. Anal.
Calcd for C10H19N: C, 78.37; H, 12.50; N, 9.14. Found: C, 78.28; H,
12.59; N, 9.16.
N-Benzyl-(2-cyclohexen-1-yl)amine (Entry 6).45 Product from
reaction for 6 h on a 2 mmol scale using the general procedure was
isolated by Ku¨gelrohr distillation (35 mT, 95 °C) to give 348 mg (93%
yield) of colorless oil. 1H NMR (CDCl3) δ 7.36-7.20 (m, 5H), 5.78-
5.65 (m, 2H), 3.87 (d, J ) 13.0 Hz, 1H), 3.83 (d, J ) 13.0 Hz, 1H),
3.22 (m, 1H), 1.99 (m, 2H), 1.89 (m, 1H), 1.72 (m, 1H), 1.48 (m, 2H),
1.31 (br s, 1H). 13C{1H} NMR (CDCl3) δ 140.87, 130.03, 129.03,
128.46, 128.24, 126.92, 52.48, 51.10, 29.59, 25.45, 20.33.
1
(94% yield) of colorless oil. H NMR (C6D6) δ 7.47 (d, J ) 8.0 Hz,
2H), 7.32 (t, J ) 7.7 Hz, 2H), 7.19 (t, J ) 7.3 Hz, 1H), 6.08-6.02 (m,
1H), 5.92-5.82 (m, 1H), 3.62 (d, J ) 13.5 Hz, 1H), 3.55 (d, J ) 13.5
Hz, 1H), 3.39 (d, J ) 10.1 Hz, 1H), 2.25 (s, 3H), 2.10 (m, 1H), 2.00-
1.84 (m, 3H) 1.61 (m, 1H), 1.52-1.25 (m, 3H). 13C{1H} NMR (C6D6)
δ 141.22, 136.43, 131.28, 129.26, 128.86, 127.41, 64.53, 58.59, 37.95,
29.45, 29.27, 29.18, 27.53. Anal. Calcd for C15H21N: C, 83.67; H, 9.83;
N, 6.50. Found: C, 83.53; H, 9.90; N, 6.50.
(2-Cyclohexen-1-yl)cyclohexylamine (Entry 7).46 Product from
reaction for 37 h on a 2 mmol scale using the general procedure was
isolated by Ku¨gelrohr distillation (50 mT, 140 °C) to give 292 mg (82%
(2-Cyclohepten-1-yl)morpholine (Entry 14).50 Product from reac-
tion for 60 h on a 2 mmol scale using the general procedure was isolated
by Ku¨gelrohr distillation (50 mT, 85 °C) to give 404 mg (94% yield)
1
yield) of clear oil. H NMR (CDCl3) δ 5.78-5.65 (m, 2H), 3.22 (m,
1H), 2.55 (m, 1H), 1.93 (m, 2H), 1.80 (m, 3H), 1.67 (m, 3H), 1.45-
1.60 (m, 2H), 1.32 (m, 1H), 1.30-1.00 (m, 5H), 0.81 (br m, 1H). 13C-
{1H} NMR (CDCl3) δ 130.83, 128.46, 53.49, 49.31, 34.41, 33.94, 30.27,
26.27, 25.43, 25.33, 25.28, 20.39.
1
of colorless oil. H NMR (CDCl3) δ 5.92-5.75 (m, 2H), 3.72-3.65
(m, 4H), 3.20 (d, J ) 11.5 Hz, 1H), 2.65-2.50 (m, 4H), 2.16 (m, 1H),
2.01 (m, 2H), 1.84 (m, 1H), 1.66 (m, 1H), 1.43 (m, 3H). 13C{1H} NMR
(CDCl3) δ 134.39, 131.64, 67.66, 65.09, 49.23, 29.01, 28.98, 28.51,
26.72. Anal. Calcd for C11H19N: C, 72.88; H, 10.56; N, 7.73. Found:
C, 72.42; H, 10.61; N, 7.72.
(2-Cyclohexen-1-yl)-4-methoxybenzylamine (Entry 8).47 Product
from reaction for 30 h on a 2 mmol scale using the general procedure
was isolated by chromatography using 10 g silica gel and 1/3 EtOAc-
hexanes as the eluent to give 378 mg (87% yield) of the purified product
N-Benzyl-(2-cycloocten-1-yl)methylamine (Entry 15). Product
from reaction for 84 h on a 2 mmol scale at 60 °C using the general
procedure was isolated by Ku¨gelrohr distillation (50 mT, 78 °C) to
give 176 mg (38% yield) of colorless oil as a mixture of three
1
as a thick oil. H NMR (CDCl3) δ 7.28 (d, J ) 8.7 Hz, 2H), 6.86 (d,
J ) 8.7 Hz, 2H), 5.80-5.68 (m, 2H), 3.81 (d, J ) 10.5 Hz, 1H), 3.77
(s, 3H), 3.70 (overlapped d, J ) 10.5 Hz, 1H), 3.18 (m, 1H), 1.98 (m,
2H), 1.88 (m, 1H), 1.72 (m, 1H), 1.48 (m, 2H), 1.22 (br s, 1H). 13C-
{1H} NMR (CDCl3) δ 158.71, 133.07, 130.13, 129.51, 129.11, 113.94,
55.47, 52.49, 50.59, 29.69, 25.54, 20.45. Anal. Calcd for C14H19NO:
C, 77.38; H, 8.81; N, 6.45. Found: C, 77.57; H, 8.74; N, 6.38.
(2-Cyclohexen-1-yl)diphenylmethylamine (Entry 9).48 Product
from reaction for 60 h on a 2 mmol scale using the general procedure
was isolated by Ku¨gelrohr distillation (0.01 mmHg, 175 °C) to give
1
cyclooctenyl regioisomers that were not separated. H NMR (CDCl3)
δ 7.30-7.10 (m, 7.9 H), 5.80-5.48 (m, 3.3 H), 3.70 (d, J ) 20.4 Hz,
1.0 H), 3.60-3.40 (m, 3.2 H), 2.70-2.20 (m, 2.2 H), 2.20 (s, 3.0 H),
2.17 (s, 1.3 H), 2.11 (s, 1.1 H), 2.15-2.00 (m, 2.8 H), 1.90-1.25 (m,
12.4 H). 13C{1H} NMR (CDCl3) δ 140.36, 139.78, 130.91, 130.22,
130.13, 129.94, 129.76, 129.00, 128.71, 128.63, 128.47, 128.14, 128.10,
126.69, 126.65, 126.64, 64.45, 63.01, 60.17, 59.15, 58.04, 57.31, 38.48,
38.13, 37.71, 33.42, 30.56, 29.69, 29.52, 29.36, 28.14, 27.86, 26.90,
26.85, 26.77, 25.68, 25.03, 24.84, 23.91, 23.66. GC/MS 10.71 min
(50.1%) m/z 229, 10.76 min (16.4%) m/z 229, 10.97 min (30.2%) m/z
229. Anal. Calcd for C15H23N: C, 83.79; H, 10.11; N, 6.11. Found:
C, 83.74; H, 10.16; N, 6.08.
N-Benzyl-(1-buten-3-yl)methylamine (Entry 16).51 Under a nitro-
gen atmosphere, butadiene (216 mg, 4 mmol, 2 equiv) was condensed
into a preweighed, flame-dried Schlenk flask at -78 °C. The flask was
then allowed to warm to room temperature, the exact weight of the
diene was determined, and the excess of diene was removed. The flask
was then cooled to -78 °C, and a solution of DPPF (55.4 mg, 0.100
mmol, 0.0500 equiv), Ni(COD)2 (27.5 mg, 0.100 mmol, 0.0500 equiv),
N-benzylmethylamine (242 mg, 2.00 mmol, 1.00 equiv), and TFA (30.8
µL, 0.400 mmol, 0.200 equiv) in 2 mL of toluene was added by syringe.
The reaction was allowed to warm to room temperature, and after 0.5
h it was filtered through a pad of silica gel and concentrated in vacuo.
The product was isolated by Ku¨gelrohr distillation (40 mT, 30 °C) to
give 291 mg (83% yield) of colorless oil as a mixture of three butenyl
regioisomers in a 10:1:1 ratio. 1H NMR (CDCl3) δ 7.40-7.15 (m, 6.1H),
6.00-5.83 (m, 1.0 H), 5.62-5.50 (m, 0.4H), 5.15-5.00 (m, 2.0H),
3.55 (d, J ) 13.3 Hz, 1.1H), 3.40 (d, J ) 13.3 Hz, 1.1 H), 3.32-3.15
(m, 1.0H), 3.08 (d, J ) 6.4 Hz, 0.2H), 2.95 (d, J ) 5.7 Hz, 0.2H), 2.15
1
448 mg (85% yield) of colorless oil. H NMR (CDCl3) δ 7.45-7.10
(m, 10H), 5.85-5.68 (m, 2H), 5.05 (s, 1H), 3.05 (m, 1H), 1.96 (m,
2H), 1.88 (m, 1H), 1.69 (m, 1H), 1.50 (m, 2H), 1.42 (br s, 1H). 13C-
{1H} NMR (CDCl3) δ 144.79, 144.47, 130.46, 128.85, 128.65, 128.62,
127.64, 127.60, 127.12, 127.10, 64.21, 50.37, 29.82, 25.55, 20.36. Anal.
Calcd for C19H21N: C, 86.65; H, 8.04; N, 5.32. Found: C, 86.89;
H,8.16; N, 5.33.
(2-Cyclohexen-1-yl)dibenzylamine (Entries 10 and 11).49 Using
the general procedure, allowing the reagents to react for 113 h at room
temperature, the product from reaction on a 2 mmol scale was isolated
by Ku¨gelrohr distillation (60 mT, 116 °C) to give 310 mg (56% yield)
1
of colorless oil. H NMR (CDCl3) δ 7.40-7.10 (m, 10H) 5.82-5.65
(m, 2H), 3.68 (d, J ) 14.1 Hz, 2H), 3.50 (d, J ) 14.1 Hz, 2H), 3.31
(m, 1H), 1.93 (m, 3H), 1.76 (m, 1H), 1.53 (m, 2H). 13C{1H} NMR
(CDCl3) δ 141.10, 131.08, 130.26, 128.69, 128.32, 126.81, 54.72, 54.05,
25.58, 23.40, 22.07. Using the general procedure, but allowing the
reagents to react at 60 °C for 72 h, the product from reaction on a 2
mmol scale was isolated by Ku¨gelrohr distillation (60 mT, 116 °C) to
give 392 mg (71% yield) of colorless oil.
(45) Guy, A.; Barbetti, J. F. Synth. Commun. 1992, 22, 853-857.
(46) Toulgui, C.; Chaabouni, M. M.; Baklouti, A. J. Fluorine Chem. 1990, 46,
385-391.
(47) Ikeda, M.; Hamada, M.; Yamashita, T. Y., T.; Matsui, K.; Sato, T.; Ishibashi,
H. J. Chem. Soc., Perkin Trans. 1 1999, 1949-1956.
(48) Blond, A.; Platzer, N.; Guy, A.; Dhotel, H.; Serva, L. Bull. Soc. Chim. Fr.
1996, 133, 283-293.
(50) Tomioka, H.; Oishi, T.; Takahashi, J.; Sasaki, M.; Hirata, N. Jpn. Kokai
Tokkyo Koho, Japan, JP 60248648 A2 19851209, 1985.
(51) Nakanishi, S.; Okamoto, K.; Yamaguchi, H.; Takata, T. Synthesis 1998,
1735-1741.
(49) Oh, J. S.; Hong, Y. S.; Kim, Y. G. J. Ind. Eng. Chem. 1997, 3, 326-334.
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3676 J. AM. CHEM. SOC. VOL. 124, NO. 14, 2002