816 J . Org. Chem., Vol. 64, No. 3, 1999
Spencer et al.
6 mL of THF, stirred for 19 h, and diluted with 200 mL of icy
H2O. Usual workup (ether) and NPC (6:94 Et2O/hexane) gave
1.89 g (72%) of 59: 1H; 13C; EI-HRMS.
of 3.81 g (18.0 mmol) of 67 in 50 mL of THF was added 1.55
mL (20.0 mmol) of freshly distilled methanesulfonyl chloride
and 2.80 mL (20.0 mmol) of Et3N at 0 °C under N2. The mixture
was stirred for 0.5 h, treated with 30.0 mL (90.0 mmol) of a
solution of 3.0 M PhMgBr in ether, stirred for 1 h, warmed to
room temperature, washed with 3 × 100 mL of 1.0 N HCl,
dried over MgSO4, filtered, and evaporated to give 8.0 g of oil.
NPC (1:1 EtOAc/hexane) gave 2.21 g (54%) of colorless oily
71: 1H; 13C; EI-HRMS.
3,7-Dim eth yl-8-p h en yl-2(E),7(E)-octa d ien ol (72). The
0.294 g of a mixture of 71 and 72 described above was
chromatographed on 10% AgNO3-impregnated silica gel25 (1:9
EtOAc/hexane) to give 0.103 g (35%) of oily colorless 72: 1H;
13C; EI-HRMS; C, H.
(E)-9-P h en yln on -2-en -1-ol (60). According to the method
of Nagaoka and Kishi,58 a solution of 0.51 g (1.96 mmol) of 59
in 13 mL of CH2Cl2 and 26 mL of hexane at -78 °C was slowly
treated with 7.87 mL (7.87 mmol) of a solution of DIBALH in
THF. The mixture was stirred for 4 h, treated with 2 mL of
MeOH, allowed to warm to room temperature, treated with 4
mL of brine and 10 g of MgSO4, stirred for 1 h, filtered, and
evaporated. NPC (3:7 ether/hexane) gave 0.26 g (61%) of 60:
1H; 13C; FAB-HRMS.
1-Br om o-9-p h en yln on -2-en e (61). As for 41, 0.25 g (1.15
mmol) of 60 was converted in 87% yield to 61: 1H; 13C; FAB-
HRMS.
(E)-N,N-Dim eth yl-9-p h en yln on -2-en -1-a m in e (62). As
for 42, 0.27 g (0.96 mmol) of 61 was converted in 93% yield to
62: 1H; 13C; FAB-HRMS.
N,N-Dim eth yl-N-1-(9-ph en yln on -2(E)-en yl)a m m on iu m -
1-(4-bu tylsu lfon a te) (63). As for 40, 0.21 g (0.86 mmol) of
62 was converted in 55% yield to 63: 1H; 13C; FAB-HRMS.
(1,1-Dim et h ylet h yl)[(3,7-d im et h yl-2(E),6-oct a d ien yl)-
oxy]d im eth ylsila n e (66). By the procedure of Corey and
Venkateswarlu,59 5.00 g (58.1 mmol) of geraniol was converted
in 83% yield to 66: 1H (lit.60 1H); 13C; C, H.
8-[[(1,1-Dim eth yleth yl)dim eth ylsilyl]oxy]-2,6-dim eth yl-
2(E),6(E)-octa d ien -1-ol (68). According to a procedure by
Umbreit and Sharpless,22 to a solution of 11.3 mL (0.113 mol)
of 90% tert-butyl hydroperoxide and 0.55 g (0.0050 mol) of
selenium dioxide in 100 mL of CH2Cl2 was added 4.60 g (14.4
mol) of 66. The mixture was stirred at room temperature for
8 h, stored over 11 g of activated alumina for 24 h, filtered,
and evaporated to give 16.1 g of oil, which was diluted with
100 mL of ether, washed with 3 × 50 mL of 1 N NaOH and 2
× 50 mL of brine, dried over MgSO4, filtered, and evaporated
to give 12.4 g of colorless oil. NPC (1:19 EtOAc/hexane) gave
3.09 g (19%) of oily 68: 1H; 13C; C, H.
N,N-Dim eth yl-1-(3,7-d im eth yl-8-p h en yl-2(E),6(E)-octa -
d ien yl)a m m on iu m -1-(4-bu tylsu lfon a te) (64). As for 13,
1.04 g (4.70 mmol) of 71 afforded 81% of 3,7-dimethyl-8-phenyl-
2(E),6(E)-octadienyl bromide: 1H; 13C. As for 14, 1.46 g (5.00
mmol) of this bromide afforded 73% of N,N,3,7-tetramethyl-
8-phenyl-2(E),6(E)-octadienylamine: 1H; 13C. As for 20, 0.824
g (3.21 mmol) of this amine was converted to crude 64. RPC
(90:9.5:0.5 MeOH/H2O/NH4OH) gave 0.274 g (22%) of 64: mp
1
286-289 °C; H; 13C; FAB-HRMS.
N,N-Dim eth yl-1-(3,7-d im eth yl-8-p h en yl-2(E),7(E)-octa -
d ien yl)a m m on iu m -1-(4-bu tylsu lfon a te) (73). As for 13,
0.126 g (0.538 mmol) of 72 afforded 92% of 3,7-dimethyl-8-
phenyl-2(E),7(E)-octadienyl bromide: 1H; 13C. As for 14, 0.146
g (0.495 mmol) of this bromide afforded 97% of N,N,3,7-
tetramethyl-8-phenyl-2(E),7(E)-octadienylamine: 1H; 13C. As
for 20, 0.124 g (0.480 mmol) of this amine afforded crude 73.
RPC (90:9.5:0.5 MeOH/H2O/NH4OH) gave 0.274 g (22%) of
1
73: mp 281-282 °C; H; 13C; FAB-HRMS.
3,7-Dim eth yl-9-p h en yl-2(E),6(E)-n on a d ien ol (74). As for
71, a solution of 0.36 g (1.7 mmol) of 67 in 20 mL of THF was
treated with 0.151 mL (1.95 mmol) of methanesulfonyl chloride
and 0.273 mL (1.96 mmol) of Et3N and then with 6.8 mL (6.8
mmol) of a 1.0 M solution of PhCH2MgCl to give 0.4 g of oil.
NPC (1:4 EtOAc/hexane) gave 0.251 g (61%) of colorless viscous
oily 74: 1H; 13C; EI-HRMS.
8-Acetoxy-3,7-d im eth yl-2(E),6(E)-octa d ien a l (69). Simi-
lar oxidation22 of 65 prepared in 94% yield from geraniol by
treatment with Ac2O in pyridine gave 40% of 67: 1H; 13C.
According to a procedure of Mashraqui and Keehn,61 0.072 g
(0.34 mmol) of 67 was converted in 96% yield to 69: 1H (lit.62
1H); 13C.
N,N,3,7-Tetr a m eth yl-9-p h en yl-(2(E),6(E)-n on a d ien yl)-
a m in e (75). As for 13, 1.30 g (5.32 mmol) of 74 afforded 92%
of 3,7-dimethyl-9-phenyl-2(E),6(E)-nonadienyl bromide: 1H;
13C. As for 14, 1.30 g (4.23 mmol) of this bromide afforded 57%
of 75: 1H; 13C; EI-HRMS.
1,8-Dih yd r oxy-2,6-d im eth yl-1-p h en yl-2(E),6(E)-octa d i-
en e (70). To a solution of 4.32 g (20.6 mmol) of 69 in 50 mL of
THF at 0 °C was added 35.0 mL (0.098 mol) of a 2.8 M solution
of PhMgBr in ether. The mixture was stirred at 0 °C for 1 h
under N2, treated with 200 mL of 1.0 N HCl, and extracted
with 3 × 75 mL of Et2O. The organic layer was washed with
3 × 100 mL of 1.0 N HCl, dried over MgSO4, filtered, and
evaporated to give 7.26 g of yellow/orange oil. NPC (2:3 EtOAc/
hexane) gave 4.87 g (96%) of yellow oily 70: 1H; 13C; C, H.
3,7-Dim eth yl-8-p h en yl-2(E),6(E)-octa d ien ol (71) a n d
3,7-Dim eth yl-8-p h en yl-2(E),7(E)-octa d ien ol (72). Accord-
ing to a procedure by Lau et al.63 to a solution of 0.323 g (1.31
mmol) of 70 in 30 mL of 1,2-dichloroethane was added 0.627
g (1.97 mmol) of ZnBr2 and 0.438 g (9.38 mmol) of NaBH3CN.
The mixture was stirred at room temperature, and when 70
was no longer detected by TLC, the mixture was filtered
through Celite that was then was washed with 150 mL of
CH2Cl2. The filtrate was dried over MgSO4, filtered, and
evaporated to give 0.294 g (96%) of a mixture of 71 and 72:
1H; 13C; EI-HRMS.
N,N,3,7-Tetr a m eth yl-9-p h en yl-(2(E),6(E)-n on a d ien yl)-
a m m on iu m -1-(4-bu tylsu lfon a te) (76). As for 20, 0.508 g
(1.86 mmol) of 75 afforded 0.155 g (21%) of hygroscopic
1
colorless 76: mp 273-275 °C; H; 13C; FAB-HRMS.
7-Acet oxy-9-p h en yl-1-[[(1,1-d im et h ylet h yl)d im et h yl-
silyl]oxy]-n -n on a n e (78). A solution of 2.63 g (14.5 mmol) of
6-bromo-1-hexanol in 182 mL of CH2Cl2 at 0 °C was treated
with 2.30 mL (16.7 mmol) of Et3N, 2.40 g (16.0 mmol) of tert-
butyldimethylsilyl chloride, and 70.9 mg (0.58 mmol) of DMAP.
The mixture was stirred at 0 °C for 20 min and at room
temperature for 8 h and evaporated. The residue was treated
with 50 mL of Et2O and extracted with 3 × 20 mL of 10%
aqueous HCl solution, followed by 30 mL of brine, and the
organic layer was dried (MgSO4) and evaporated. NPC (2.5:
97.5 EtOAc/hexane) gave 3.83 g (89%) of 77:27 1H; 13C. A
suspension of 0.41 g (17.1 mmol, 1.4 equiv) of Mg turnings
and 5.05 g (17.1 mmol) of 77 in 70 mL of THF was heated at
90 °C until all the Mg was consumed (3.5 h). A solution of 1.96
g (14.6 mmol) of 3-phenylpropanal in 10 mL of THF was added,
and the mixture was stirred at 70 °C for 3 h and diluted with
30 mL of 5% aqueous HCl. Usual workup (ether) gave a
residue that was treated with 30 mL of Et2O, 16 mL of Ac2O,
32 mL of pyridine, and 47 mg of DMAP. The mixture was
stirred at room temperature for 17 h and diluted with 50 mL
of saturated aqueous NaHCO3 solution. Usual workup (ether)
and NPC (1:9 EtOAc/hexane) gave 4.42 g (92%) of 78: 1H; 13C;
FAB-HRMS.
3,7-Dim et h yl-8-p h en yl-2(E),6(E)-oct a d ien ol (71). Ac-
cording to a procedure by Raucher and Klein,64 to a solution
(58) Nagaoka, H.; Kishi, Y. Tetrahedron 1981, 37, 3873.
(59) Corey, E. J .; Venkateswarlu, A. J . Am. Chem. Soc. 1972, 94,
6190.
(60) Scheller, M. E.; Frie, B. Helv. Chim. Acta 1985, 68, 44.
(61) Mashraqui, S.; Keehn, P. Tetrahedron Lett. 1982, 637.
(62) Meinwald, J .; Opheim, K.; Eisner, T. Tetrahedron Lett. 1973,
281.
(63) Lau, K. C.; Dufresne, C.; Belanger, P. C.; Pietre, S.; Scheigetz,
J . J . Org. Chem. 1986, 51, 3038.
(64) Raucher, S.; Klein, P. J . Org. Chem. 1986, 51, 124.
7-Acetoxy-9-p h en yl-n -n on a n -1-ol (79). A solution of 1.49
g (3.80 mmol) of 78 in 48 mL of THF at 0 °C was slowly treated
with 4.2 mL (4.18 mmol) of a 1.0 M solution of (nBu)4NF in
THF, stirred at 0 °C for 20 min, allowed to warm to room