Notes
J . Org. Chem., Vol. 61, No. 8, 1996 2883
129.1, 127.4, 127.3, 72.5, 66.5, 53.7, 39.7, 33.6, 30.4, 24.1. Anal.
Calcd for C13H18O2Se: C, 54.54; H, 6.34. Found: C, 54.61; H,
6.31.
Sch em e 1
(1R,2R,4R)-1-Meth yl-2-(p h en ylselen yl)cycloh exa n e-1,4-
d iol (6a ): 42%; 1H NMR δ 1.38 (s, 3 H), 3.20 (dd, 1 H, J ) 13.0,
4.0 Hz), 3.65 (m, 1 H), 7.20-7.70 (m, 5 H); 13C NMR δ 132.8,
127.5, 126.6, 126.1, 70.7, 68.2, 54.1, 39.8, 35.1, 30.4, 21.6. Anal.
Calcd for C13H18O2Se: C, 54.54; H, 6.34. Found: C, 54.58; H,
6.32.
(1S,2S,4R)-1-Meth yl-2-(p h en ylselen yl)-4-a cetylcycloh ex-
1
a n -1-ol (11): 87%; H NMR δ 1.41 (s, 3 H), 1.98 (m, 1 H), 2.18
(s, 3 H), 2.41 (m, 1 H), 2.74 (m, 1 H), 3.46 (dd, 1 H, J ) 6.8, 3.8
Hz), 7.21-7.71 (m, 5 H); 13C NMR δ 210.8, 133.8, 129.6, 129.1,
127.4, 71.7, 53.6, 46.4, 34.9, 30.8, 27.9, 27.6, 23.3. Anal. Calcd
for C15H20O2Se: C, 57.68; H, 6.46. Found: C, 57.71; H, 6.44.
P r ep a r a tion of Aceta tes. To a solution of the alcohol (1
mmol) in 5 mL of CH2Cl2 were added NEt3 (1.5 mmol), Ac2O
(1.5 mmol), and a catalytic amount of 4-pyrrolidinopyridine were
added. The solution was stirred at room temperature for 1 h
and then diluted with water (10 mL). The combined organic
layers were washed with water, dried, and evaporated to yield
the acetate as a yellow oil.
(1S,2S,4R)-4-Acet oxy-1-m et h yl-2-(p h en ylselen yl)cyclo-
h exa n -1-ol (5b): 97%; 1H NMR δ 1.31 (s, 3 H), 1.93 (s, 3 H),
3.51 (dd, 1 H, J ) 13.0, 4.0 Hz), 4.93 (m, 1 H), 7.18-7.72 (m, 5
H); 13C NMR δ 169.9, 133.8, 129.1, 128.7, 127.2, 71.7, 69.3, 53.0,
35.9, 33.9, 27.0, 24.0, 20.8. Anal. Calcd for C15H20O3Se: C,
54.87; H, 6.14. Found: C, 54.84; H, 6.18.
properties of 2. The olefin 7 was readily obtained from
11 via epoxide 128 which in turn was secured by alkaline
treatment of selenoxide of 11 in methanol.9 m-CPBA
oxidation of 12 afforded 13,8 and SN2 displacement at C(2)
of the epoxide ring with the phenylselenenyl anion10
yielded the selenide 5b, easily transformed into the
pheromone (S)-1 following the above procedure.
(1R,2R,4R)-4-Acetoxy-1-m eth yl-2-(p h en ylselen yl)cyclo-
h exa n -1-ol (6b): 98%; 1H NMR δ 1.32 (s, 3 H), 2.05 (s, 3 H),
3.21 (dd, 1 H, J ) 12.0, 4.0 Hz), 4.79 (m, 1 H), 7.2-7.7 (m, 5 H);
13C NMR δ 170.1, 134.1, 129.0, 128.8, 127.5, 71.7, 71.4, 55.3,
37.4, 36.0, 28.1, 23.2, 21.0. Anal. Calcd for C15H20O3Se: C,
54.87; H, 6.14. Found: C, 54.84; H, 6.16.
P r ep a r a tion of Olefin es fr om Selen id es. To a stirred
solution of the selenide (1 mmol) in THF (5 mL) at room
temperature was added 30% hydrogen peroxide (10 mmol). After
stirring for 3 h at 50 °C, the solvent was distilled, water (10
mL) was added to the residue, and the resulting mixture was
extracted with CH2Cl2 (3 × 10 mL). The combined extracts were
washed with brine and dried. Removal of the solvent and
chromatography of the residue (CH2Cl2-CH3OH 98:2) gave the
olefins as oils.
In summary we have demonstrated that both the
enantiomers of 1-methyl-2-cyclohexen-1-ol (1) were syn-
thetized in the diastereoselective manner from (R)-(+)-
limonene. The present work proved the utility of the
hydroxyselenenylation process for the construction of a
chiral allylic and tertiary hydroxy group. The ability of
the homo-allylic acetate to govern the diastereofacial
selectivity of olefin selenation bodes well for further
stereospecific applications.
(1S,4R)-4-Acetoxy-1-m eth yl-2-cycloh exen -1-ol (7): 81%;
1H NMR δ 1.21 (s, 3 H), 2.0 (s, 3 H), 5.11 (m, 1 H), 5.58 (dd, 1 H,
J ) 10.0, 3.0 Hz), 5.73 (d, 1 H, J ) 10.0 Hz); 13C NMR δ 170.4,
137.5, 126.7, 68.2, 67.3, 34.3, 28.3, 25.2, 21.0. Anal. Calcd for
C9H14O3: C, 63.49; H, 8.30. Found: C, 63.35; H, 8.35.
(1R,4R)-4-Acetoxy-1-m eth yl-2-cycloh exen -1-ol (9): 80%;
1H NMR δ 1.35 (s, 3 H), 2.05 (s, 3 H), 5.25 (m, 1 H), 5.71 (dd, 1
H, J ) 10.0, 3.0 Hz), 5.85 (d, 1 H, J ) 10.0 Hz); 13C NMR δ
170.7, 138.1, 125.9, 67.6, 67.4, 34.4, 28.4, 25.8, 21.1. Anal. Calcd
for C9H14O3: C, 63.49; H, 8.30. Found: C, 63.54; H, 8.26.
(1S,4R)-4-Acetyl-1-m eth yl-2-cycloh exen -1-ol (12): 90%; 1H
NMR δ 1.31 (s, 3 H), 2.21 (s, 3 H), 3.02 (m, 1 H), 5.82 (bs, 2 H);
13C NMR δ 209.3, 135.4, 125.2, 66.9, 49.3, 35.8, 28.7, 21.4. Anal.
Calcd for C9H14O2: C, 70.08; H, 9.16. Found: C, 70.14; H, 9.11.
Red u ctive Elim in a tion of Allylic Aceta tes w ith Li/NH3.
A solution of the acetate (1 mmol) in THF (5 mL) was added
during 20 min to a solution of Li (10 mmol) in liquid ammonia
(20 mL), and the reaction mixture was stirred at -40 °C for 10
min. A few drops of bromobenzene were added to the mixture,
the ammonia was evaporated in a stream of nitrogen, and a 0.5
N sulfuric acid solution (3 mL) was added to the residue. The
resulting mixture was extracted with CH2Cl2 (3 × 10 mL), and
the combined organic layers were washed with water, dried, and
evaporated. Column chromatography of the residue on a silica
gel/AgNO3 (10%) (CH2Cl2-CH3OH 98:2) gave olefins as colorless
oils.
Exp er im en ta l Section
Gen er a l. The same general procedures were followed as
described previously.11 (R)-(+)-limonene was purchased from
Fluka.
P r ep a r a tion of â-Hyd r oxy Selen id es. Benzeneselenenyl
chloride (1.1 mmol) was added to a stirring solution of the olefin
(1 mmol) in 10 mL of a 5:1 mixture of CH3CN-H2O. The
solution was stirred at room temperature for 30 min and then
neutralized with a saturated solution of NaHCO3 and extracted
with CH2Cl2 (3 × 5 mL). The combined organic layers were
washed with water, dried, and evaporated. Column chroma-
tography (CH2Cl2-CH3OH 98:2) gave â-hydroxy selenides as
pale yellow compounds.
(1S,2S,4R)-1-Meth yl-2-(p h en ylselen yl)cycloh exa n e-1,4-
d iol (5a ): 35%; 1H NMR δ 1.35 (s, 3 H), 3.61 (dd, 1 H, J ) 12.0,
5.0 Hz), 4.01 (m, 1 H), 7.18-7.71 (m, 5 H); 13C NMR δ 134.0,
(S)-1-Met h yl-2-cycloh exen -1-ol (1): 65%; [R]20 -75.6°
D
(Et2O), with the same spectral data as those reported;1 13C NMR
δ 133.7, 129.0, 67.2, 37.8, 29.3, 25.0, 19.4.
(S)-1-Met h yl-3-cycloh exen -1-ol (8): 28%; [R]20 -66.4°
(9) Ceccherelli, P.; Curini, M.; Epifano, F.; Marcotullio, M. C.; Rosati,
O. Tetrahedron Lett. 1995, 5079.
(10) Kametani, T.; Kurobe, H.; Nemoto, H. J . Chem. Soc., Perkin
Trans. I 1981, 756.
D
(Et2O); 1H NMR δ;12 13C NMR δ 125.6, 123.7, 68.3, 39.5, 34.7,
28.6, 23.0.
(11) Ceccherelli, P.; Curini, M.; Marcotullio, M. C.; Rosati, O.;
Wenkert, E. J . Org. Chem. 1991, 56. 7065.
(12) Staroscik, J . A.; Rickborn, B. J . Org. Chem. 1992, 37, 738.