2346
C. Schur et al. / Tetrahedron 67 (2011) 2338e2347
13C NMR (CDCl3, 50 MHz, 20 ꢂC)
d
13.8, 27.9, 55.4, 91.9, 114.5, 119.0,
methylprop-2-oxy)-bicyclo[2.2.1]heptane 2-endo-3-exo-(16a). 1H
NMR (CDCl3, 600 MHz) 1.16e1.22 (m, 1H),1.20 (s, 9H),1.31 (dq,1H,
122.8,127.1,128.5,129.8,134.2,134.3,143.5,159.9,182.5. MS (EI) m/
z 253 (67), 236 (35), 205 (25),177 (27),155 (86),152 (100),137 (68),
117 (85), 102 (56). Anal. Calcd. For C20H20ClNO2S2 (405.96): C,
59.17; H, 4.97; N, 3.45. Found: C, 59.22; H, 4.99; N, 3.29. Crystals
d
Jd¼10.4 Hz, Jq¼1.8 Hz), 1.41e1.46 (m, 1H), 1.50e1.58 (m, 1H),
1.71e1.76 (m, 1H), 1.85 (ddt, 1H, Jd¼12.4, 9.3 Hz, Jt¼2.9 Hz) 2.01 (d,
1H, J¼5.0 Hz), 2.35e2.40 (m, 1H), 3.43 (t, 1H, J¼2.3 Hz), 3.90e3.91
suitable for X-ray diffraction were grown from a saturated solution
(m, 1H). 13C NMR (CDCl3, 151 MHz)
d 23.8, 25.0, 28.8, 34.5, 42.8,
ꢀ
in pentane/Et2O¼1:1 (v/v). T¼293(2) K,
l
¼0.71073 A, monoclinic,
44.6, 63.6, 73.6, 83.4. MS (EI) m/z 248 (2), 246 (2), 233 (3), 191 (16),
175 (5), 110 (11), 93 (15), 57 (100). 2-exo-3-exo-3-Bromo-3-(2-
methylprop-2-yl)-bicyclo[2.2.1]-heptane 2-exo-3-exo-(16a). 1H NMR
C2/c, a¼17.561(4) A, b¼8.8759(18) A, c¼26.777(5) A,
¼106.73(3)ꢂ,
ꢀ
ꢀ
ꢀ
b
Z¼8,
m
¼0.414 mmꢁ1, completeness to 2
¼95.1%, goodness-of-fit on
q
F2¼0.747, final R indices [I>2
s
(I)]: R1¼0.0312, wR2¼0.0612. 2-[2-
(CDCl3, 600 MHz) d 1.10e1.19 (m, 3H),1.21 (s, 9H),1.43e1.51 (m,1H),
(4-Chlorophenyl)-propyl-2-sulfanyl]-5-(4-methoxyphenyl)-4-methyl-
thiazole N-oxide (4e). Yield: 658 mg (33%), colorless solid, mp 102 ꢂC.
Rf¼0.29 for acetone/pentane¼1:1 (v/v). 1H NMR (CDCl3, 400 MHz)
1.51e1.57 (m, 1H), 1.97 (dquint, 1H, Jd¼10.3 Hz, Jquint¼1.9 Hz),
2.05e2.06 (m, 1H), 2.48e2.49 (m, 1H), 3.37e3.39 (m, 1H), 4.00 (dd,
1H, J¼6.1, 2.0 Hz). 13C NMR (151 MHz, CDCl3)
d 25.4, 27.5, 28.1, 33.4,
44.8, 46.6, 62.0, 74.2, 74.9. MS (EI) m/z 248 (1) 246, 233 (3), 191 (17),
d
1.89 (s, 6H), 2.42 (s, 3H), 3.85 (s, 3H), 6.97 (d, 2H, J¼8.9 Hz),
7.25e7.31 (m, 4H), 7.50e7.52 (d, 2H, J¼8.5 Hz). 13C NMR (CDCl3,
175 (3), 110 (11), 93 (14), 57 (100).
101 MHz)
d 12.7, 30.3, 55.4, 56.3, 114.5, 122.8, 128.2, 128.4, 129.8,
132.0,133.2,134.1,141.0,143.4,160.4. Anal. Calcd. For C20H20ClNO2S2
(405.97): C, 59.17; H, 4.97; N, 3.45. Found: C, 58.83; H, 4.71; N, 3.44.
4.3.2. Conversion of 3-(2-methyl-5-phenylpent-2-oxy)-thiazolethione
1c. BrCCl3 310 mg (750 mmol) and 1.50 g (7.50 mmol, 0.75 mL) in
C6H6 (9.0 mL) according to procedure in Section 4.3.1. Eluent used
for chromatographic purification: pentane/tert-butyl methyl
ether¼10:1 (v/v)/pentane/tert-butyl methyl ether¼2:1 (v/v).
2,2-Dimethyl-5-phenyltetrahydrofuran (10):37 Yield: 76.6 mg (58%),
yellow liquid, Rf¼0.65 for tert-butyl methyl ether/pentane¼1:2 (v/
v). 5-(4-Methoxyphenyl)-4-methyl-2-(trichlormethylsufanyl)-thiazole
11.17 Yield: 71.9 mg (27%), yellowish crystals. Rf¼0.43 for tert-butyl
methyl ether/pentane¼1:2 (v/v). 1,2-Bis-[5-(4-methoxyphenyl)-4-
methylthiaz-2-yl]-disulfane (5).33 Yield: 59.0 mg (33%), yellowish oil.
Rf¼0.19 for tert-butyl methyl ether/pentane¼1:2 (v/v). 2-Methyl-5-
phenylpentan-2-ol (3c). Yield: 30.5 mg (23%), yellowish oil. Rf¼0.18
for tert-butyl methyl ether/pentane¼1:2 (v/v).
4.2.8. Esterification of 2-phenylhex-5-en-2-ol (3f). Alkenol 3f
(7.05 g, 40 mmol) and MAnTTOH (2) (5.06 g, 20 mmol) were
treated as described in general method 4.2.2. EG: pentane/Et2O/
CH2Cl2¼5:1:1 (v/v/v)/acetone/pentane¼1:2 (v/v). 3-(1-Methyl-
1-phenylpent-4-en-1-oxy)-5-(4-methoxyphenyl)-4-methylthiazole-
2(3H)-thione (1f). Yield 1.48 g (18%), colorless solid, mp 94ꢁ95 ꢂC.
Rf¼0.30 for pentane/Et2O/CH2Cl2¼5:1:1 (v/v/v). UV (EtOH) lmax
(log 3 d 1.55
/m2 molꢁ1) 338 nm (3.28). 1H NMR (CDCl3, 400 MHz)
(s, 3H), 1.72e1.80 (m, 1H), 1.88 (s, 3H), 1.91e2.00 (m, 1H), 2.62 (dt,
1H, Jd¼12.8 Hz, Jt¼4.6 Hz), 2.89 (dt, 1H, Jd¼12.6 Hz, Jt¼5.0 Hz), 3.79
(s, 3H), 4.91 (dd, 1H, J¼10.2, 1.5 Hz), 4.95 (dd, 1H, J¼17.2, 1.6 Hz),
5.75 (ddt, 1H, Jd¼16.8, 10.2 Hz, Jt¼6.4 Hz), 6.87 (d, 2H, J¼8.5 Hz),
7.10 (d, 2H, J¼8.2 Hz), 7.34e7.41 (m, 3H), 7.53 (d, 2H, J¼7.5 Hz). 13C
4.3.3. Conversion of 3-(1-methyl-1-phenylpent-4-enyloxy)-thiazole-
thione 1f. Alkenoxythiazolethione 1f (308 mg, 748 mmol) and
NMR (CDCl3, 151 MHz)
d
13.6, 20.2, 29.4, 42.4, 55.3, 95.1,114.3,114.7,
118.7,122.7,126.2,128.3,128.6,129.1,129.7,134.6,137.7,159.7,182.1.
Anal. Calcd. For C23H25NO2S2 (411.58): C, 67.12; H, 6.12; N, 3.40.
Found: C, 67.22; H, 6.05; N, 3.68. 2-(1-Methyl-1-phenylpent-4-enyl-
2-sulfanyl)-5-(4-methoxyphenyl)-4-methylthiazole N-oxide (4f).
Yield 2.19 g (27%), yellowish oil. Rf¼0.35 for acetone/pentane¼1:1
BrCCl3 (1.49 g, 7.50 mmol) in C6H6 (9 mL) are treated according to
procedure 4.3.1 (35 min reaction time). GC/MS analysis of the re-
action mixture using n-decane as internal standard: phenyl methyl
ketone (7) (3.3 mg, 4%). The reaction mixture was worked up as
described in procedure 4.3.1. 5-Bromomethyl-2-methyl-2-phenyl-
tetrahydrofuran (13).42 Yield: 120 mg (63%), yellowish oil, 74/26-
mixture of cis/trans-isomers. Rf¼0.42 (trans) and 0.36 (cis) for
pentane/Et2O¼10:1 (v/v). Anal. Calcd. For C12H15OBr (255.15): C,
56.49; H, 5.93. Found: C, 56.14; H, 6.03. trans-5-Bromomethyl-2-
methyl-2-phenyltetrahydrofuran trans-(13). 1H NMR (CDCl3,
(v/v). 1H NMR (CDCl3, 400 MHz)
d 1.82e1.92 (m, 1H),1.92 (s, 3H),
2.07e2.23 (m, 2H), 2.34e2.41 (m,1H), 2.39 (s, 3H), 3.83 (s, 3H), 4.93
(dd, 1H, J¼10.2, 1.5 Hz), 4.98 (dd, 1H, J¼16.2, 1.2 Hz), 5.75 (ddt, 1H,
J¼16.9, 10.4 , 6.3 Hz), 6.93 (d, 2H, J¼8.6 Hz), 7.22e7.24 (m, 3H),
7.31e7.34 (m, 2H), 7.53 (d, 2H, J¼7.4 Hz). 13C NMR (CDCl3, 151 MHz)
d
12.6, 26.2, 29.1, 42.1, 55.4, 60.2, 114.5, 114.9, 123.0, 127.3, 127.4,
600 MHz) d 1.56 (s, 3H), 1.87e1.97 (m, 2H), 2.09e2.16 (m, 1H),
128.4, 129.8, 131.6, 134.7, 137.7, 140.7, 142.9, 160.3.
2.22e2.29 (m, 1H), 3.45 (dd, 1H, J¼10.0, 6.6 Hz), 3.54 (dd, 1H,
J¼10.0, 4.5 Hz), 4.26e4.30 (m, 1H), 7.21e7.24 (m, 1H), 7.31e7.34 (m,
4.3. Alkoxyl radical reactions
2H), 7.37e7.38 (m, 2H). 13C NMR (CDCl3, 151 MHz)
d 30.1, 30.4, 36.2,
38.8, 77.8, 86.0, 124.5, 126.5, 128.2, 147.5. MS (EI) m/z 241 (56), 239
(56), 179 (1), 177 (1), 161 (6), 143 (7), 128 (7), 117 (13), 115 (13), 105
(100). cis-5-Bromomethyl-2-methyl-2-phenyltetrahydrofuran cis-
4.3.1. Reaction of 3-(tert-butoxy)-thiazolethione 1a with norbornene
14. An oxygen-free solution of norbornene (14) (4.80 g, 51.0 mmol),
tert-butoxythiazolethione 1a (158 mg, 510
m
mol), and BrCCl3
(13). 1H NMR (CDCl3, 600 MHz)
d 1.52 (s, 3H), 1.72e1.76 (m, 1H),
(1.01 g, 5.10 mmol) in dry C6H5CF3 (18.5 mL, c104¼2.76 M) was
2.09e2.16 (m, 1H), 2.21e2.29 (m, 2H), 3.29 (dd, 1H, J¼10.0, 7.5 Hz),
3.54 (dd, 1H, J¼10.0, 5.4 Hz), 4.41e4.45 (m, 1H), 7.21e7.24 (m, 1H),
7.31e7.34 (m, 2H), 7.43e7.45 (m, 2H). 13C NMR (CDCl3, 151 MHz)
photolyzed for 40 min at 25 ꢂC in a RayonetÒ chamber reactor
equipped with 12 light bulbs (l¼350 nm). The resulting mixture
was concentrated under reduced pressure (100/20 mbar, 40 ꢂC) to
furnish a residue, which was purified by column chromatography
(SiO2) using pentane/Et2O¼20:1 (v/v) as eluent. 2-endo-3-exo-2-
Bromo-3-trichloromethylbicyclo[2.2.1]heptane 2-endo-3-exo-(17).47
Yield: 1.24 g (84%), colorless oil. Rf¼0.68 for pentane/Et2O¼20:1
(v/v). 2-exo-3-exo-2-Bromo-3-trichloromethylbicyclo[2.2.1]heptane
2-exo-3-exo-(17).47 Yield: 93.1 mg (6%), colorless oil, Rf¼0.60 for
pentane/Et2O¼20:1 (v/v). 2-Bromo-3-(2-methylprop-2-oxy)-bicyclo
[2.2.1]heptane (16a). Yield: 25.3 mg (20%), colorless oil, 20/80-
mixture of 2-exo-3-exo/2-endo-3-exo-isomers. Rf¼0.40 for pentane/
Et2O¼20:1 (v/v). Anal. Calcd. For C11H19OBr (247.17): C, 53.45; H,
7.75. Found: C, 53.22; H, 7.69. 2-endo-3-exo-2-Bromo-3-(2-
d 29.8, 30.7, 35.7, 39.2, 78.6, 85.7,124.6,126.5,128.1,148.1. MS (EI) m/
z 241 (50), 239 (50), 161 (4), 143 (7), 128 (9), 117 (16), 115 (16), 105
(100). 5-(4-Methoxyphenyl)-4-methyl-2-(trichlormethylsufanyl)-thi-
azole 10.17 Yield: 119 mg (45%), yellowish crystals. Rf¼0.14 for
pentane/Et2O¼10:1 (v/v). 2-Phenyl-5-hexen-2-ol.17 Yield: 119 mg
(45%), yellowish crystals. Rf¼0.14 for pentane/Et2O¼10:1 (v/v). 2-
Phenyl-5-hexene-2-ol65 (3f). Yield: 7.9 mg (6%), yellowish oil.
Rf¼0.07 for pentane/Et2O¼10:1 (v/v).1,2-Bis-[5-(4-methoxyphenyl)-
4-methylthiaz-2-yl]-disulfane (5).33 Yield: 55.0 mg (15%), yellow oil.
Crystallographic data (excluding structure factors) for the
structure of 3-(4-chlorocumyloxy)-alkoxythiazolethione 1e in this
paper have been deposited with the Cambridge Crystallographic