´
J. SCIANOWSKI ET AL.
2
66
Table . Results of synthesis of epoxy stilbene.
Entry
Telluride
Yield [%]
Ratio Cis/trans [%]a
Ratio trans (S/S/R/R)b
<
4
5
/
/
/
/
/
/
9/91
:
84:16
:
:
:
:
:
6
7
8
9
10
a
Determined on the basis of H NMR spectroscopy.
b
Determined on the basis of HPLC analysis using a Chiralcel Daicel ODH column.
2
8.9 (CH3), 29.6 (CH), 30.1 (CH3), 31.3, 31.8 (CH2), 35.7 (CH) 2945, 2868, 1686, 1574, 1473, 1442, 1384, 1275, 1260, 1222, 1167,
(
CH) ppm. Mix of two epimers, (1S,3R,4S,6R)-(+)-4-Caranyl 1062,1018, 853, 732, 692. Elemental Anal. Calcd for C16H24Te
methyl telluride : (1S,3R,4R,6R)-(+)-4-Izocaranyl methyl tel- (343.96): C, 55.87; H, 7.03. Found: C, 56.01; H, 7.00.
luride (40:60).
General procedure for the synthesis of phenyl terpenyl
tellurides
(
1S,2R,5S)-(−)-Myrtanyl phenyl telluride 10
Yield: 94%), [α]23D = −40.2 (c 1.28, CHCl3); 1H NMR
To the solution of diphenyl ditelluride (1.02 g, 2.5 mmol) in
methanol (50 mL) NaBH4 (0.38 g, 10.0 mmol) was added. Tosy-
late (5.4 mmol) in methanol (20 mL) was added and the mix-
ture was stirred for 24 h at 80°C. Methanol was evaporated,
the solution was poured on water (100 mL), and extracted with
petroleum ether (3 × 100 mL). The combined organic layers
were dried, evaporated, and the obtained crude product was
purified by column chromatography (petroleum ether). The
reaction and column chromatography was performed under
argon atmosphere.
(
400 MHz, CDCl3): δ = 0.89 (d, J = 9.6 Hz, 1H), 1.02 (s,
3
3
3
2
2
H, CH3), 1.18 (s, 3H, CH3), 1.48–1.60 (m, 1H), 1.82–2.01 (m,
H), 2.03–2.17 (m, 2H), 2.33–2.46 (m, 2H), 3.08 (dd, J = 11.2,
0.0 Hz, 1H), 3.11 (dd, J = 11.6, 29.2 Hz, 1H), 7.19–7.24 (m,
H, 2x CHarom.), 7.26–7.32 (m, 1H, CHarom.), 7.72–7.77 (m,
H, 2x CHarom.) ppm; 13C NMR (100.6 Hz, CDCl3): δ = 18.6
(
(
CH2), 23.2 (CH3), 24.7 (CH2), 26.3 (CH2), 28.0 (CH3), 33.6
CH2), 38.7 (C), 41.3 (CH), 43.0 (CH), 47.8 (CH), 112.1 (Carom.),
1
27.4 (CHarom.), 129.1 (2x CHarom.), 138.3 (2x CHarom.) ppm; IR
−1
(
cm , film): 3066, 2912, 1574, 1474, 1433, 1365, 1165, 1062,
018, 908, 758, 729, 691. Elemental Anal. Calcd for C16H22Te
(341.95): C, 56.20; H, 6.48. Found: C, 56.29; H, 6.45.
1
(
1S,2S,5R)-(+)-Neomenthyl phenyl telluride 8
Yield: 40%, [α]23D = +85.9 (c 1.36, CHCl3); H NMR (400 MHz,
1
CDCl3): δ = 0.61–0.69 (m, 1H), 0.84 (d, J = 6.4 Hz, 3H, CH3),
0
0
1
2
1
.93 (d, J = 6.8 Hz, 3H, CH3), 0.97 (d, J = 6.8 Hz, 3H, CH3),
.89–1.03 (m, 2H), 1.51–1.64 (m, 2H), 1.73–1.80 (m, 1H), 1.84– (1S,3R,4S,6R)-(+)-4-Caranyl phenyl telluride 13,
.93 (m, 2H), 2.17 (ddd, J = 2.4, 4.8, 13.6 Hz, 1H), 3.50 (dt, J = (1S,3R,4R,6R)-(+)-4-izocaranyl phenyl telluride 14
.8, 5.6 Hz, 1H), 7.18–7.23 (m, 2H, 2x CHarom.), 7.28–7.33 (m,
1
Yield: 38%, H NMR (400 MHz, CDCl3): δ = 0.40–0.50 (m,
H, CHarom.), 7.83 (dd, J = 1.2, 8.0 Hz, 2H, 2x CHarom.) ppm;
1
3
2
1
(
4
H), 0.51–0.60 (m, 1H), 0.62–0.90 (m, 4H), 0.96 (d, J = 6.4 Hz,
H; CH3), 0.97 (s, 3H, CH3), 0.98 (s, 3H, CH3), 0.98 (s, 6H,
xCH3), 1.04 (d, J = 6.8 Hz, 3H; CH3), 1.45–1.50 (m, 1H) 1.60–
.70 (m, 1H), 1.80–1.95 (m, 2H), 1.95–2.05 (m, 1H), 2.10–2.38
1
3
C NMR (100.6 Hz, CDCl3): δ = 20.7 (CH3), 20.8 (CH3), 22.1
(
4
CH3), 29.1 (CH2), 30.2 (CH), 33.8 (CH), 35.3 (CH2), 41.5 (CH),
3.9 (CH2), 50.3 (CH), 112.0 (Carom.), 127.6 (CHarom.), 129.0 (2x
−1
CHarom.), 139.7 (2x CHarom.) ppm; IR (cm , film): 3400, 3065,
m, 3H), 2.89–2.99 (m, 1H), 3.75–3.85 (m, 1H), 7.13–7.25 (m,
H), 7.28–7.35 (m, 2H), 7.75–7.83 (m, 4H) ppm; 13C NMR
Table . Results of epoxidation with the use dicaranyl chalcogenides.
(
(
100.6 Hz, CDCl3): δ = 15.6 (CH3), 16.0 (CH3), 17.5 (C), 17.7
Dicaranyl
chalcogenide
Yield
[%]
Ratio
Ratio trans
(S/S/R/R)
C), 20.8 (CH), 21.2 (CH), 21.5 (CH), 22.9 (CH), 26.7 (CH2),
Cis/trans [%]a
b
Entry
2
7.9 (CH2), 28.4 (CH), 28.9 (CH), 29.2 (CH2), 31.25 (CH),
31.69 (CH2), 34.69 (CH), 34.78 (CH), 35.947 (CH), 111.85
C), 112.84 (C), 127.56 (CH), 127.80 (CH), 129.00 (2xCH),
29.04 (2xCH), 139.44 (2xCH), 140.37 (2xCH) ppm. Mix of
two epimers, (1S,3R,4S,6R)-(+)-4-Caranyl phenyl telluride :
1S,3R,4R,6R)-(+)-4-Izocaranyl phenyl telluride (57:43).
Sulfide
Selenide
Telluride 5
:
:
:
:
:
:
(
1
a
Determined on the basis of H NMR spectroscopy.
b
Determined on the basis of HPLC analysis using a Chiralcel Daicel ODH column.
(