petrol–Et2O (9:1), to give the imine 4 (454 mg, 95%) as orange
needles, mp 69–73 ЊC; Rf 0.64 (9:1, petrol–EtOAc); [α]D24 ϩ18.6
(c 1.0 in CHCl3); νmax(neat)/cmϪ1 1685 (C᎐N); δ (400 MHz,
(53, M Ϫ C5H9), 229 (18, M Ϫ C10H17), 77 (54, Ph), 69 (100,
C5H9).
᎐
H
CDCl3) 0.99 (3H, m, CH3), 1.12 (3H, m, CH3), 1.30–1.36 (1H,
N-(6,7-Epoxygeranyl)-N-phenyl-2-exo-bornylamine 7
m, 5-Hendo), 1.73 (1H, d, J 17, 3-Hendo), 1.83–1.99 (3H, m, 5-Hexo
,
To a solution of the amine 6 (128 mg, 0.35 mmol) in CH2Cl2 (5
cm3) was added MCPBA (76 mg, 0.35 mmol) at room temper-
ature. After 16 h the solvent was removed in vacuo and the
residue was purified by flash chromatography, eluting with
petrol–Et2O (19:1), to give the epoxide 7 (45 mg, 34%) as an oil
(as a 1:1 mixture of diastereomers); [α]D25 ϩ26.8 (c 0.5 in CHCl3);
νmax(neat)/cmϪ1 1595 (Ar); δH(400 MHz, CDCl3) 0.81 (3H, s,
CH3), 0.84 (3H, s, CH3), 0.96 (3H, s, CH3), 1.10–1.20 (2H, m,
5-Hendo and 6-Hendo), 1.24 (3H, s, CH3), 1.26–1.29 (5H, m, CH3,
3-Hendo and 6-Hexo), 1.45 (3H, s, CH3), 1.47–1.77 (5H, m,
6-Hendo and 6-Hexo), 2.08–2.17 (2H, m, 3-Hexo and 4-H), 3.39
(1H, d, J 10, 10-CHAHB), 3.66 (1H, d, J 10, 10-CHAHB), 6.66
(1H, dd, J 8 and 2, ArH), 6.75 (1H, td, J 8 and 2, ArH), 7.25
(1H, td, J 8 and 2, ArH), 7.75 (1H, dd, J 8 and 2, ArH); δC(100
MHz, CDCl3) 3.57 (10-CH2I), 18.12 (CH3), 20.27 (CH3), 26.98
(5-C), 32.28 (6-C), 36.41 (3-C), 45.24 (4-C), 49.07 (7-C), 55.37
(1-C), 89.26 (ArCI), 118.99 (ArCH), 124.87 (ArCH), 128.96
(ArCH), 139.05 (ArCH), 152.44 (ArCN), 182.34 (C᎐N)
᎐
(Found: Mϩ 478.9626. C16H19NI2 requires M, 478.9607); m/z
479 (8%, Mϩ), 352 (100, M Ϫ I), 224 (19, M Ϫ I2).
OCHCH2, 3-Hexo, 4-H, 5-Hexo), 2.00–2.10 (2H, m, NCH CH᎐
᎐
2
CMeCH2), 2.63 (0.5H, dd, J 6 and 2, Me2CCHA), 2.64 (0.5H,
dd, J 6 and 2, Me2CCHB), 3.42 (1H, t, J 7, 2-H), 3.71 (2H, br s,
NCH2CH), 5.15 (1H, br s, NCH2CH), 6.89–6.93 (3H, m, ArH),
7.20 (2H, t, J 8, ArH); δC(100 MHz, CDCl3) 13.50 (CH3), 16.03
and 16.04 (CH3), 18.68 (CH3), 20.30 (CH3), 21.16 (CH3), 24.85
(CH3), 27.24 and 27.30 (5-C), 36.18 (CH2), 36.63 (CH2), 36.66
(CH2), 36.82 (CH2), 44.83 (4-C), 46.94 (7-C), 50.22 (1-C), 50.72
and 50.77 (NCH2), 58.24 and 58.26 (Me2CO), 63.93 and 63.98
(2-C), 67.68 and 67.73 (Me2CCO), 120.76 and 120.80 (ArCH),
122.63 and 122.70 (ArCH), 123.46 and 123.50 (NCH2CH),
Imine 5
tert-Butyllithium (0.9 in pentane, 0.35 cm3, 0.30 mmol) was
added to the diiodide 4 (129 mg, 0.27 mmol) in dry Et2O (5 cm3)
at Ϫ90 ЊC under argon. The mixture was allowed to warm to
room temperature and was stirred for 16 h before being
quenched with saturated NH4Cl solution. The mixture was
extracted with Et2O (3 × 5 cm3), washed with H2O (5 cm3) and
brine (5 cm3) and dried (Na2SO4). The solvent was removed in
vacuo and the residue was purified by flash chromatography,
eluting with petrol–EtOAc (3:1), to give the imine 5 (9 mg, 0.04
mmol, 15%) as an oil; Rf 0.21 (3:1, petrol–EtOAc); [α]D24 Ϫ92.5
(c 1.2 in CHCl3); νmax(neat)/cmϪ1 1660 (C᎐N); δ (400 MHz,
128.29 (ArCH), 135.44 and 135.47 (NCH CH᎐C), 151.53 and
᎐
2
151.55 (ArCN) (Found: Mϩ 381.3025. C26H39NO requires M,
381.3032); m/z 381 (58%, Mϩ), 95 (100), 77 (83, Ph).
᎐
H
CDCl3) 0.96 (3H, s, CH3), 1.01 (3H, s, CH3), 1.28–1.36 (1H, m,
5-Hendo), 1.51–1.64 (2H, m, 6-Hendo and 6-Hexo), 1.90–1.99 (1H,
m, 5-Hexo), 2.05 (1H, t, J 5, 4-H), 2.16 (1H, d, J 18, 3-Hendo), 2.60
(1H, d, J 17, 10-HAHB), 2.78 (1H, dt, J 18 and 4, 3-Hexo), 2.90
(1H, d, J 17, 10-HAHB), 7.07–7.15 (2H, m, ArH), 7.19–7.23
(1H, m, ArH), 7.29–7.31 (1H, m, ArH); δC(100 MHz, CDCl3)
18.44 (CH3), 20.97 (CH3), 26.42 (10-C), 26.93 (5-C), 30.93
(6-C), 40.03 (3-C), 43.23 (4-C), 48.01 (7-C), 50.93 (1-C), 124.63
(ArC), 126.54 (ArCH), 126.56 (ArCH), 127.19 (ArCH), 128.96
1,7,7-Trimethyl-2-(pent-2-enyl)-2-azabicyclo[2.2.1]heptan-3-
one 9a
To a solution of 2-azabornan-3-one 816 (765 mg, 5 mmol) in
THF (30 cm3) was added NaH (60% dispersion in mineral oil,
800 mg, 20 mmol). After 1 h, pent-2-enyl bromide (0.95 cm3,
8 mmol) was added. After a further 16 h, saturated NH4Cl
solution was added dropwise. The mixture was extracted with
Et2O (3 × 10 cm3), washed with H2O (2 × 10 cm3) and brine (10
cm3) and dried (Na2SO4). The solvent was removed in vacuo and
the residue was purified by flash chromatography, eluting with
Et2O, to give the lactam 9a (1.06 g, 96%) as an oil (E:Z, 6:1 by
NMR); Rf 0.50 (Et2O); [α]D24 ϩ0.8 (c 1.5 in CHCl3); νmax(neat)/
(ArCH), 143.52 (ArCN), 183.14 (C᎐N) (Found: Mϩ 225.1523.
᎐
C16H19N requires M, 225.1518); m/z 225 (87%, Mϩ), 210 (22,
M Ϫ Me), 182 (100, M Ϫ H Ϫ CMe2).
N-Geranyl-N-phenyl-2-exo-bornylamine 6
cmϪ1 1695s (C᎐O); δ (400 MHz, CDCl ) (E isomer only) 0.82
᎐
H
3
To a solution of the amine 2 (R = H)11 (110 mg, 0.48 mmol) in
acetone (15 cm3) was added Hünig’s base (132 µl, 0.76 mmol)
and geranyl bromide (142 µl, 0.72 mmol) and the mixture was
heated under reflux for 16 h. The solvent was removed in vacuo,
the residue was extracted with EtOAc (2 × 10 cm3), washed
with H2O (3 × 5 cm3), brine (5 cm3) and was dried (Na2SO4).
The residue was purified by flash chromatography, eluting with
petrol–CH2Cl2 (19:1), to give the amine 6 (71 mg, 40%) as an
oil; Rf 0.51 (petrol–CH2Cl2, 9:1); [α]D26 ϩ42.7 (c 0.75 in CHCl3);
νmax(neat)/cmϪ1 1595 and 1500 (Ar); δH(400 MHz, CDCl3) 0.83
(3H, s, CH3), 0.85 (3H, s, CH3), 0.98 (3H, s, CH3), 1.12–1.21
(1H, m, 5-Hendo), 1.27–1.34 (1H, m, 3-Hendo), 1.45 (3H, s, CH3),
1.49–1.58 (2H, m, 3-Hexo and 5-Hexo), 1.59 (3H, s, CH3), 1.64
(3H, s, CH3), 0.91 (3H, t, J 4, CH2CH3), 0.95 (3H, s, CH3), 1.26
(3H, s, 10-CH3), 1.40–1.47 (1H, m, 5-Hendo), 1.51–1.58 (1H, m,
6-Hendo), 1.71 (1H, ddd, J 12, 10 and 4, 6-Hexo), 1.85–1.93 (1H,
m, 5-Hexo), 1.93–2.01 (2H, m, CH2CH3), 2.24 (1H, d, J 4, 4-H),
3.65 (1H, ddd, J 15, 6 and 1, NCHAHB), 3.74 (1H, ddd, J 15,
6 and 1, NCHAHB), 5.29–5.37 (1H, m, NCH2CH), 5.56–5.64
(1H, m, NCH CH᎐CH); δ (100 MHz, CDCl ) 12.04 and 12.16
᎐
2
C
3
(10-CH3, Z and E), 13.34 and 13.94 (CH2CH3, E and Z), 18.06
(CH3), 18.41 (CH3), 23.47 (5-C), 20.56 and 25.13 (CH2CH3, Z
and E), 33.70 and 33.73 (6-C, E and Z), 35.38 and 40.54
(NCH2, Z and E), 49.78 and 49.83 (7-C, E and Z), 55.10 and
55.12 (4-C, E and Z), 70.52 and 70.67 (1-C, Z and E), 125.07
and 125.15 (NCH2CH, E and Z), 133.63 and 134.91 (NCH2-
CH᎐CH, Z and E), 177.64 (3-C᎐O) (Found: Mϩ 221.1784.
(1H, t, J 4, 4-H), 1.68 (3H, d, J 2, NCH CH᎐CCH ), 1.69–1.77
᎐
2
3
᎐
᎐
C14H23NO requires M, 221.1780); m/z 221 (75%, Mϩ), 193 (84,
MH Ϫ Et), 178 (100), 110 (96, M Ϫ CON Ϫ C5H9), 69 (89,
C5H9).
(2H, m, 6-CH ), 1.89–1.96 (2H, m, CH CH CH᎐CMe ), 1.99–
᎐
2
2
2
2
2.05 (2H, m, CH CH᎐CMe ), 3.46 (1H, dd, J 9 and 7, 2-Hendo),
᎐
2
2
3.73 (2H, d, J 5, NCH CH), 5.05 (1H, tt, J 7 and 1, CH᎐CMe ),
᎐
2
2
5.09–5.15 (1H, m, NCH2CH), 6.89 (1H, td, J 7 and 2, ArH),
6.94 (2H, d, J 7, ArH), 7.22 (2H, td, J 7 and 2, ArH); δC(100
MHz, CDCl3) 13.44 (10-CH3), 16.02 (CH3), 17.67 (CH3), 20.36
1,7,7-Trimethyl-2-(pent-2-enyl)-2-azabicyclo[2.2.1]heptane 3a
(CH ), 21.22 (CH ), 25.68 (CH ), 26.41 (5-C), 27.26 (CH CH᎐
To a suspension of LiAlH4 (616 mg, 16.2 mmol) in THF (25
cm3) at 0 ЊC was added the lactam 9a (717 mg, 3.24 mmol) in
THF (10 cm3). The mixture was heated under reflux for 24 h,
before being quenched by the dropwise addition of NaOH (4
). EtOAc (30 cm3) and Na2SO4 were added and the mixture
was filtered, evaporated and purified by flash chromatography,
eluting with Et2O–MeOH (9:1), to give the amine 3a (586 mg,
᎐
3
3
3
2
CMe ), 36.56 (6-C), 36.83 (3-C), 39.53 (CH CH CH᎐CMe ),
᎐
2
2
2
2
44.85 (4-C), 46.94 (7-C), 50.25 (NCH2), 50.28 (1-C), 67.45
(2-C), 120.36 (ArCH), 122.13 (ArCH), 122.98 (NCH CH᎐),
᎐
2
124.29 (CH᎐CMe ), 128.27 (ArCH), 131.25 (CH᎐CMe ),
᎐
᎐
2
2
136.21 (NCH CH᎐C), 151.63 (ArCN) (Found: Mϩ 365.3073.
᎐
2
C26H39N requires M, 365.3086); m/z 365 (15%, Mϩ), 296
J. Chem. Soc., Perkin Trans. 1, 1999, 2327–2334
2331