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CH2); (12) 7.62 (2H, m, Ph), 7.27 (3H, m, Ph), 3.28 (2H, dt,
J¼4.2, 10.1 Hz, H1H3), 3.03 (2H, s, OH), 2.77 (1H, t,
J¼10.1 Hz, H2), 1.6–1.2 (6H, m, CH2); m/z 272 (M), 158
[M2(Phþ2OH)], 97 [M2(SePhþOH)].
(3H, s, Me); (19) 7.57 (2H, m, Ph), 7.26 (3H, m, Ph), 5.90
(1H, dd, J¼17.4, 10.7 Hz, Hx), 5.14 (1H, dd, J¼17.4,
1.2 Hz, Ha), 4.99 (1H, dd, J¼10.7, 1.2 Hz, Hb), 3.2 (2H, br s,
OH), 2.65 (1H, m, CHSe), 2.2–1.4 (4H, m, CH2), 1.37, 3H,
s, Me), 1.33 (3H, s, Me), 1.28 (3H, s, Me); m/s 328 (M), 171
[M2(SePhþOH)], 127 [M2(SePhþOHþCHvCH2)];
HRMS (EI): Mþ, found 328.0963. C16H24SeO2 requires
328.0942.
4.2.7. r-2-Phenylseleno-3,5,5-trimethylcyclohexane-cis-
1,trans-3-diol (13). From isophorol as a mixture (960 mg,)
from which white crystals of (13) formed on standing
(670 mg, 42%), mp 103–105 8C; [Found: C, 57.7; H, 7.1.
C15H22O2Se requires C, 57.51; H, 7.08%]; nmax (CCl4)
3500, 3460, 1475, 1365, 1040 cm21; dH 7.61 (2H, m, Ph),
7.25 (3H, m, Ph), 4.28 (1H, tt, J¼11.3, 3.8 Hz, H1), 4.27
(1H, dt, J¼11.3, 3.8, 11.3 Hz, one of the 11.3 couplings
disappears with a D2O shake, H1), 3.40 (1H, dt, J¼3.8,
1.8 Hz, H2), 2.49 (1H, d, J¼11.3 Hz, OH), 1.65 (1H, ddt,
J¼11.4, 3.8, 1.8 Hz, H6e), 1.52 (1H, d, J¼14.6 Hz, H4a),
1.48 (3H, s, Me), 1.38 (1H, dt, J¼14.6, 1.8 Hz, H4e), 1.32
(1H, s, OH), 1.14 (3H, s, Me), 1.13 (1H, dd, J¼11.4,
11.3 Hz, H6a), 0.95 (3H, s, Me); dC 143.8, 134.0, 129.3,
127.6 (Ar), 76.4 (C3), 68.1 (C1), 65.6 (C2), 46.8 (C4), 45.8
(C6), 33.6 (Me), 31.8 (Me), 28.2 (Me); m/z 314 (M), 297
(M2OH), 139 [M2(SePhþH2O)], 121 [M2(SePhþ2H2O)].
4.2.11. Reactions of crotyl acetate (20). Using the above
general procedure. 3-Hydroxy-2-phenylselenobutyl acetate
(23) and 2-hydroxy-3-phenylselenobutyl acetate (24) were
prepared from crotyl acetate, using the general procedure, as
a yellow oil (460 mg, 32%), bp 145 8C, 0.05 mm (block)
which was an inseparable mixture in the ratio 57:43 (23:24);
n
max (film) 3350, 1720, 1560, 1030 cm21; dH (24) 7.59 (2H,
m, Ph), 7.27 (3H, m, Ph), 4.19 (2H, m, CH2OAc), 3.87 (1H,
m, CHOH), 3.44 (1H, dq, J¼4.7, 7.0 Hz, CHSe), 2.60 (1H,
br d, J¼4.1 Hz, OH), 2.05 (3H, s, COMe), 1.43 (3H, d,
J¼7.0 Hz, Me); (23) 7.59 (2H, m, Ph), 7.27 (3H, m, Ph),
4.20 (2H, m, CH2OAc), 3.68 (1H, m, CHO), 3.55 (1H, m,
CHSe), 2.74 (1H, br s, OH), 2.06 (3H, s, COMe), 1.46
(3H, d, J¼6.8 Hz, Me); m/z 288 (M), 245 (M2Ac), 131
(M2SePh); HRMS (EI): Mþ, found 288.0253. C12H16O3Se
requires 288.0264.
4.2.8. 2-Hydroxymethyl-2-phenylseleno-3-hydroxy-6,6-
dimethyl-bicyclo[3.3.1]-heptane (15). From (1R)(2)
myrtenol, as a complex mixture from which it was possible
to isolate the selenide (15) by chromatography as an oil
(216 mg, 13%); nmax (film) 3360, 1580, 1480, 1375, 1160,
1020, 740 cm21; dH 7.61 (2H, m, Ph), 7.28 (3H, m, Ph), 4.36
(1H, d, J¼12.6 Hz, CHaOH), 4.10 (1H, m, CHOH), 4.19
(1H, d, J¼12.6 Hz, CHbOH), 2.2–1.6 (6H, m), 2.0 (2H, br s,
OH), 1.20 (3H, s, Me), 1.18 (3H, s, Me); m/z 326 (M), 309
(M2OH), 232 [M2(OHþPh)], 151 (M2(OHþSePh)], 42
(CMe2); HRMS (EI): Mþ, found 326.0796. C16H22O2Se
requires 326.0785.
Further elution gave a mixture of (3) and (4), in the ratio 4:1,
as a colourless oil (455 mg, 37%).
With phenylselanyl chloride in methanol. To crotyl acetate
(114 mg, 1 mmol) in dry methanol (10 ml) under nitrogen
was added phenylselanyl chloride (191 mg, 1 mmol) and the
reaction was stirred at room temperature for 18 h. The
solvent was removed under reduced pressure and the residue
chromatographed to give 3-methoxy-2-phenylselenobutyl
acetate (26) as a light yellow oil (260 mg, 86%); nmax (film)
1730, 1580, 1480, 1125, 1100, 700 cm21; dH 7.57 (2H, m,
Ph), 7.25 (3H, m, Ph), 4.43 (1H, dd, J¼11.7, 4.5 Hz, H1a),
4.36 (1H, dd, J¼11.7, 6.4 Hz, H1b), 3.62 (1H, qn, J¼6.1 Hz,
H3), 3.49 (1H, dt, J¼4.6, 6.1 Hz, H2), 3.35 (3H, s, OMe),
1.97 (3H, s, COMe), 1.34 (3H, d, J¼6.1 Hz, Me); m/z 302
(M), 242 (M2OAc), 184 (M2{OAcþ[CH3CH(OMe)]}),
157 (SePh), 85; HRMS (EI): Mþ, found 302.0423.
C13H18O3Se requires 302.0421.
4.2.9. 3(S p),7-Dimethyl-2(S p)-phenylselenooct-6-ene-
1,3-diol (17) and 3,7-dimethyl-6-phenylselenooct-2-ene-
1,7-diol (16). From geraniol (308 mg, 2 mmol) as a yellow
oil which was an inseparable mixture of (17) and (16) in
the ratio 7:5 (400 mg, 62%); nmax (film) 3350, 1580, 1480,
1040 cm21; dH (17) 7.60 (2H, m, Ph), 7.25 (3H, m, Ph), 5.20
(1H, t, J¼6.7 Hz, H6), 4.03 (1H, m, H1a), 4.02, (1H, m, H1b),
3.07 (1H, m, H2), 2.76 (2H, s, OH), 2.43 (1H, m, H5a), 2.20
(1H, m, H5b), 1.8–1.6 (2H, m, H4), 1.51 (3H, s, Me), 1.35
(3H, s, Me) 1.24 (3H, s, Me); (16) 7. 57 (2H, m, Ph), 7.24
(3H, m, Ph), 5.09 (1H, t, J¼6.8 Hz, H2), 4.10 (2H, dd,
J¼15.0, 6.8 Hz, H1aH1b), 3.60 (1H, m, H6), 2.47 (2H, br s,
OH), 2.1–1.9 (4H, m, CH2), 1.67 (3H, s, Me), 1.59 (3H, s,
Me), 1.27 (3H, s, Me); m/z 328 (M), 154 [M2(SePhþOH)];
HRMS (EI): Mþ, found 328.0938. C16H24O2Se requires
328.0941.
With phenylselanyl chloride and zinc chloride in methanol.
To a stirred mixture of crotyl acetate (114 mg, 1 mmol) and
zinc chloride (136 mg, 1 mmol) in dry methanol (10 ml)
under nitrogen was added phenylselanyl chloride (191 mg,
1 mmol). The mixture was stirred at room temperature for
18 h, the solvent removed under reduced pressure and the
residue chromatographed to give a mixture of 3-methoxy-2-
phenylselenobutyl acetate (26) and 2-methoxy-3-phenyl-
selenobutyl acetate (31) in the ratio 7:3 as a yellow oil
(83 mg, 27%); dH (31) 7.60 (2H, m, Ph), 7.26, (3H, m, Ph),
4.39 (2H, m, H1aH1b), 3.64, (1H, dt (J¼6.3, 6.1 Hz), H2),
3.47 (1H, m, H3), 3.33 (3H, s, OMe), 1.98 (3H, s, COMe),
1.37, (3H, d J¼6.1 Hz, Me).
4.2.10. 2,6(S p)-Dimethyl-3(R p)-phenylseleno-oct-7-ene-
2,6-diol (18) and 2,6(S p)-dimethyl-3(S p)-phenyl-
selenoct-7-ene-2,6-diol (19). From linalool (308 mg,
2 mmol) as a yellow oil which was an inseparable mixture
of 18 and 19 in the ratio 1:1 (140 mg, 42%); nmax (CCl4)
3360, 1580, 1480, 1370, 1040 cm21; dH (18) 7.57 (2H, m,
Ph), 7.26 (3H, m, Ph), 6.80 (1H, dd, J¼17.4, 10.7 Hz, Hx),
5.22 (1H, dd, J¼17.4, 1.2 Hz, Ha), 5.03 (1H, dd, J¼10.7,
1.2 Hz, Hb), 3.35, (1H, m, CHSe), 3.2 (2H, br s, OH), 2.2–
1.4 (4H, m, CH2), 1.39 (3H, s, Me), 1.31 (3H, s, Me), 1.27
With phenylselanyl bromide in acetic acid. A mixture of
crotyl acetate (114 mg, 1 mmol), phenylselanyl bromide
(236 mg, 1 mmol) and anyhdrous sodium acetate (330 mg,
4 mmol) in glacial acetic acid (10 ml) was stirred at room