May 2012
Stereoselective Synthesis of Polycyclic Thiopyrans
519
2
3
3
2
(
.81 (dd, J = ꢀ11.3 Hz, J = 5.3 Hz, 1H, 9-H ), 3.11 (m, J
Table 2
b
4
4a-H, 9a-H) = 7.5 Hz, | J| (4a-H, 11-H ) = 1.8 Hz, 1H, 4a-
H), 7.13–7.34 (m, 4H, 5-H, 6-H, 7-H, 8-H). C NMR (CDCl ,
3
anti
Details of the X‐ray crystal structure analysis of 14.
1
3
1
4
1
00 MHz): d = 29.2, 29.7 (C-2, C-3), 34.0, 36.2 (C-9, C-11),
3.3, 43.6 (C-1, C-4), 48.7, 50.7 (C-4a, C-9a), 126.2, 126.5,
Formular
15
C H16OS
244.3 g m−
Colorless block
1.00 × 0.87 × 0.62 mm
Monoclinic
1
M
r
27.6, 129.1 (C-5, C-6, C-7, C-8), 136.1, 140.3 (C-8a, C-10a).
+
Habit
Crystal size
Crystal system
Space group
EI MS (70 eV): m/z (%) = 216 (74) [M ], 149 (100), 148
3
(
36), 147 (67). Anal. Calcd. for C14H16S (216.3): C, 77.72; H,
7.45. Found: C, 77.63; H, 7.12.
1
P2 /c
Cell constants
a
b
c
ß
V
Z
D
Radiation
μ
F (000)
T
θ
max
No of reflections
Measured
Independent
Observed
rac-1,2,3,4,4a,9a–Hexahydro-1,4-methano-8H-thioxanthene-
,3-dicarbocxylic acid (8). The preparation of 8 was accomplished
8.7296 (3) Å
12.3248 (2) Å
11.2111 (2) Å
92.034 (3) °
2
according to the procedure described for 6. After the evaporation of
the solvent, the residue was treated with saturated aqueous NaHCO
5 mL). The obtained filtrate was acidified with diluted HCl until
as a colorless solid started to precipitate.
Yield: 430 mg (71%); mp 191–194°C (ethanol). H NMR
CDCl , 400 MHz): d = 1.53 (m, 1H, 11-Hanti), 2.39 (m, 1H,
3
(
3
1205.44 (5) Å
4
1.346 g cm
8
1
−3
(
Cu‐K
α
2.201 mm
520
3
−
1
2
3
1
2
3
1-Hsyn), 2.46 (dd, J = ꢀ12.1 Hz, J = 12.0 Hz, 1H, 9-H ),
a
.52 (m, 2H, 1-H, 4-H), 2.58 (m, 1H, 9a-H), 2.83 (m, 1-H, 9a-H),
3
298 K
70°
.20 (m, 2H, 2-Hexo, 3-Hexo), 3.74 (m, J (4a-H, 9a-H) = 8.9
Hz, | J| (4a-H, 11-H ) = 1.5 Hz, 1H, 4a-H), 7.12–7.29 (m, 4H,
-H, 6-H, 7-H, 8-H).
d x= 35.6, 36.2 (C-9, C-11), 42.8, 45.7, 47.2, 47.5, 47.8, 48.1
C-1, C-2, C-3, C-4, C-4a, C-9a), 127.2, 127.4, 128.6, 129.8 (C-5,
4
anti
1
3
5
C NMR (CDCl , 100 MHz):
3
2524
2280
2253
(
C-6, C-7, C-8), 136.6, 140.9 (C-8a, C-10a), 172.9, 173.1 (COOH).
EI MS (70 eV): m/z (%) = 304 (10) [M ], 286 (81), 186 (38),
[F /σ(F ) > 4.0]
o
o
+
R
int
0.06
166
0
0.1256
0.0481
1.076
0.340
−0.470
1
85 (71), 149 (34), 148 (39), 147 (100), 71 (57), 57 (88). Anal.
Calcd. for C16 S (304.4): C, 63.14; H, 5.30. Found: C,
2.89; H, 5.01.
Parameters
Restraints
16 4
H O
2
ωR (F , all refl.)
6
2
2
R [F , >2 σ (F )]
1
,2,3,4,4a,9a-Hexahydro-1,3-methano-2,2-dimethyl-9H-
thioxanthene-9a-carbaldehyde (10) and 1,2,3,4,4a,9a-hexahydro-
,4-methano-3,3-dimethyl-9H-thioxanthene-4a-carbaldehyde
S
Max Δδ
Min Δδ
2
(
(
11). A solution of benzothiete (1) (814 mg, 6.66 mmol) and
ꢀ)-myrtenal (9) (990 mg, 6.58 mmol) in 20 mL of toluene
was heated at reflux for 4 h. Column chromatography (2 × 30cm
6
1
2
6
6.9 (C-4a), 126.9, 127.3, 127.7, 130.3 (C-5, C-6, C-7, C-8),
2
SiO , toluene/ethyl acetate 20:1) yielded after a first fraction of 4 the
isomeric products 10 and 11 in a 1:1 mixture (270 mg, 15%),
which could be separated by another column chromatography with
31.3, 141.6 (C-10a), 189.8 (CHO). EI MS (70 eV): m/z (%) =
+
72 (18) [M ], 147 (21), 123 (48), 91 (34), 79 (29), 77 (27),
9 (100), 45 (35), 43 (69), 41 (97). Anal. Calcd. for C17H20OS
the same conditions.
1
(272.4): C, 74.96; H, 7.39. Found: C, 74.82; H, 7.25.
1
0. Colorless solid, mp 78–80°C. H NMR (CDCl
3
, 400
),
), 1.89 (m, 1H, 11-Hsyn), 2.01 (m, 1H, 3-H),
0
0
Spiro[1-benzothiopyran-2,3 -bicyclo[2.2.1]heptan-2 -one]
MHz): d = 0.69 (s, 3H, endoꢀCH
3
), 1.28 (s, 3H, exoꢀCH
3
0
1
2
2
4
.79 (m, 1H, 4-H
b
(13) and spiro[1-benzothiopyran-3,3 -bicyclo[2.2.1.]heptan-
2 -one] (14). A solution of benzothiete (1) (812 mg, 6.66
mmol) and 3-methylene-norbornan-2-one (12) (805 mg, 6.58
mmol) in 20 mL of dry toluene was heated at reflux for 4–5 h.
Column chromatography (2 × 75 cm SiO , toluene/ethyl acetate
0
.41 (m, 1H, 11-Hanti), 2.42 (m, 1H, 1-H), 2.50 (m, 1H, 4-H ),
a
2
.63, 9-H /2.99, 9-H (AB, J = ꢀ14.0 Hz, 2H), 3.94 (m, 1H,
b
a
a-H), 7.03–7.50 (m, 4H, 5-H, 6-H, 7-H, 8-H), 9.32 (s, 1H,
13
CHO). C NMR (CDCl
3
, 100 MHz): d = 23.5 (endoꢀCH
3
),
2
26.2 (C-11), 26.5 (exo-CH ), 33.4 (C-4), 34.8 (C-4a), 39.2 (C-9),
10:1) yielded 128 mg (8%) of a 1:1 mixture of the isomers 13
and 14. EI MS (70 eV): m/z (%) = 244 (56) [M ], 216 (29),
3
+
3
9.8 (C-3), 49.7 (C-1), 61.2 (C-9a), 126.9, 127.2, 128.2, 128.6
(
C-5, C-6, C-7, C-8), 136.8, 136.9 (C-9a, C-10a), 205.0 (CO).
176 (23), 175 (100), 147 (58). Anal. Calcd. for C15
244.4): C, 73.73; H, 6.60. Found: C, 73.68; H, 6.51.
Repeated column chromatography under the same conditions
H16OS
+
(
EI MS (70 eV): m/z (%) = 272 (71) [M ], 175 (65), 147 (66),
23 (99), 121 (50), 91 (70), 43 (44), 41 (100). Anal. Calcd. for
1
C H OS (272.4): C, 74.96; H, 7.39. Found: C, 75.15; H, 7.36.
permitted the separation of the isomers: 13 was obtained as a
highly viscous, colorless oil and 14 as colorless crystals, mp
158°C.
1
7
20
1
1
1.
Colorless solid, mp 72–74°C. H NMR (CDCl ): d =
3
0
1
4
.71 (s, 3H, endoꢀCH
1-Hsyn), 1.75 (m, 1H, 1-H
-H), 2.35 (m, 1H, 1-H ), 2.43 (m, 1H, 11-Hanti), 2.49 (dd,
3
), 1.28 (s, 3H, exoꢀCH
3
), 1.74 (m, 1H,
), 2.05 (m, 1H, 2-H), 2.19 (m, 1H,
1
0
3
H NMR (CDCl , 400 MHz): d = 1.55 (m, 1H, 6 -H),
b
13.
1.61 (d, J = ꢀ11.3 Hz, 1H, 7 -H), 1.69 (m, 1H, 5 -H), 1.81 (m,
2
0
0
a
2
3
0
0
J = ꢀ13.2 Hz, J = 13.1 Hz, 1H, 9-H ), 2.81 (m, 1H, 9a-H),
1H, 5 -H), 1.89 (m, 1H, 6 -H), 1.99 (m, 1H, 3-H), 2.15 (m, 1H,
b
2
3
2
0
0
2
5
.97 (dd, J = ꢀ13.2 Hz, J = 4.8 Hz, 7.13–7.25 (m, 4H,
3-H), 2.29 (d, J = ꢀ11.3 Hz, 1H, 7 -H), 2.65 (m, 1H, 4 -H),
1
3
0
-H, 6-H, 7-H, 8-H), 8.83 (s, 1H, CHO). C NMR (CDCl
), 26.7 (exo-CH ), 27.2 (C-11), 29.5 (C-
a), 34.3 (C-1), 40.4 (C-2), 40.7 (C-3), 44.3 (C-9), 46.1 (C-4),
3
,):
2.71 (m, 1H, 1 -H), 2.76 (m, 1H, 4-H), 3.10 (m, 1H, 4-H), 6.98–
13
d = 22.1 (endoꢀCH
3
3
7.12 (m, 4H, 5-H, 6-H, 7-H, 8-H). C NMR (CDCl
3
, 100 MHz):
0
0
0
9
d = 22.7, 25.3 (C-5 , C-6 ), 27.3, 27.7 (C-3, C-4), 35.6 (C-7 ),
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet