Reactions of O
2
(1∆
g
) with Anancomeric 1,3-Dithianes
J . Org. Chem., Vol. 64, No. 15, 1999 5625
3
C
6
D
6
) δ 0.72 (d, 3J H-H ) 6.8 Hz, 3H, CH
3
CS), 1.17 (d, J H-H
)
cis-3,5-Dim eth yl-1,2-d ith iola n e 1-oxid es (13a a n d 13b)
2
3
6
.8 Hz, 3H, CH
3
CSO), 1.31 (dt, J H-H ) 14.8 Hz, J H-H ) 2.8
2
were formed as a mixture in the oxidation of 12 with SeO -
2
3
36
Hz, 1H, H(5)eq), 1.41 (dt, J H-H ) 14.8 Hz, J H-H ) 11.5 Hz,
H, H(5)ax), 1.48 (d, 3
H-H ) 7.0 Hz, 3H, CH C), 2.17 (dqd,
H-H ) 11.5, 6.8, 2.8 Hz, 1H, CHCH S), 2.34 (dqd, J H-H
1.5, 6.8, 2.8 Hz, 1H, CHCH SO), 3.37 (q, J H-H ) 7.0 Hz, 1H,
CHCH ); MS (70 eV) m/e (relative intensity) 178 (19, M ), 69
2 2 2
H O . The mixture was separated by chromatography on SiO
1
J
3
to give pure samples of each diastereomer. cis-3,5-d im eth yl-
3
3
1
J
3
)
1,2-d ith iola n e-cis-1-oxid e (13a ): slightly yellow liquid; H
3
3
1
3
NMR (400.13 MHz, CDCl ) δ 1.45 (d, J H-H ) 6.7 Hz, 3H,
3
+
3
2
3
CH C), 1.54 (d, J
3
H-H
) 6.7 Hz, 3H, CH C), 2.41 (td, J
3
H-H
)
+
3
2
(100, C
5
H
9
). Anal. Calcd for C
7
H
14
S
2
O: C, 47.15; H, 7.91; S,
13.7 Hz, 1H, J
Hz,
6.7, 4.1 Hz, 1H, CHCH S), 3.96 (dqd,
Hz, 1H, CHCH
CCH
) 11.4 Hz, H(4)ax), 2.63 (ddd, J
H-H
) 13.7
H-H
3
5.96. Found: C, 46.90; H, 7.87; S, 35.72.
3
J H-H ) 5.0, 4.2 Hz, 1H, H(4)eq), 3.26 (dqd,
J H-H ) 11.5, 6.7, 5.0
SO); C δ NMR (100.61 MHz, CDCl ) 68.88
SO), 50.83 (CCH ), 43.76 (CH ), 22.03 (CH ), 12.12 (CH
CHSO). Anal. Calcd for C : C, 39.97; H, 6.71; S, 42.68.
3
J H-H ) 13.7,
r -2,tr a n s-4,tr a n s-6-Tr im eth yl-1,3-d ith ia n e tr a n s-oxid e
3
3
1
(
4bSOa x): white crystals; mp 81-82 °C; H NMR (400.13 MHz,
13
3
3
3
3
CDCl
3
) δ 1.24 (d, J H-H ) 6.9 Hz, 3H, CH
3
CS), 1.33 (d, J H-H
(
3
3
2
3
3
-
2
3
)
6.9 Hz, 3H, CH
3
CSO), 1.55 (dt, J H-H ) 14.6 Hz, J H-H
)
5
H10OS
2
3
2
.6 Hz, 1H, H(5)eq), 1.63 (d, J H-H ) 7.5 Hz, 3H, CH
3
C), 1.99
Found: C, 39.75; H, 6.77; S, 42.87. cis-3,5-d im eth yl-1,2-
d ith iola n e-tr a n s-1-oxid e (13b). Slightly yellow liquid. 1H
dt, J H-H ) 14.6 Hz, 3J H-H ) 11.9 Hz, 1H, H(5)ax), 2.54 (dqd,
2
(
3
3
J
H-H ) 11.9, 6.9, 2.6 Hz, 1H, CHCH
1.9, 6.9, 2.6 Hz, 1H, CHCH
CHCH ); MS (70 eV) m/e (relative intensity) 178 (17, M ), 69
3
S), 3.04 (dqd, J H-H
)
) δ 1.45 (d, 3
J H-H ) 7.1 Hz, 3H,
2
NMR (400.13 MHz, CDCl
3
3
1
3
SO), 3.84 (q, J H-H ) 7.5 Hz, 1H,
3
CH
3
C), 1.48 (d, J H-H ) 7.1 Hz, 3H, CH
3
C), 1.88 (ddd, J H-H )
+
3
3
3
1
3.6 Hz, J H-H ) 8.0 Hz, J H-H ) 7.2 Hz, 1H, H(4)ax), 3.02
+
(100, C
5
H
9
). Anal. Calcd for C
7
H
14
S
2
O: C, 47.15; H, 7.91; S,
2
3
(
dt, J H-H ) 13.6 Hz, J H-H ) 5.8 Hz, 1H, H(4)eq), 3.65 (dqd,
3
5.96. Found: C, 47.08; H, 7.84; S, 36.01.
3
3
3
J
H-H ) 8.0 Hz, J H-H ) 7.2 Hz, J H-H ) 5.8 Hz, 1H, CHCH
3
S),
r -2,tr a n s-4,tr a n s-6-Tr im et h yl-1,3-d it h ia n e cis-oxid e
3
3
3
3
1
.96 (dqd, J H-H ) 7.2 Hz, J H-H ) 7.1 Hz, J H-H ) 5.8 Hz,
1
(
4bSOeq): white crystals; mp 92-93 °C; H NMR (400.13 MHz,
13
H, CHCH
3
SO). C NMR (100.61 MHz, CDCl
), 46.60 (CH ), 20.45 (CH
CHSO). Anal. Calcd for C
3
) δ 76.55 (CCH
3
3
3
-
-
3
3
CDCl
)
1
3
) δ 1.17 (d, J H-H ) 6.9 Hz, 3H, CH
3
CS), 1.38 (d, J H-H
C),
SO), 50.96 (CCH
3
2
), 16.20 (CH
3
6.9 Hz, 3H, CH
3
CSO), 1.75 (d, J H-H ) 7.1 Hz, 3H, CH
3
5
H
10OS
2
: C, 39.97; H, 6.71; S, 42.68.
2
3
.86 (dt, J H-H ) 14.7 Hz, J H-H ) 12.2 Hz, 1H, H(5)ax), 2.18
Found: C, 40.06; H, 6.68; S, 42.61.
2
3
(
dt, J H-H ) 14.7 Hz, J H-H ) 2.5 Hz, 1H, H(5)eq), 2.87 (dqd,
3
3
2, 2′-R,S-[(r -2-Ca r b om et h oxy-cis-4,cis-6-d im et h yl-1,3-
d ith ia n yl tr a n s-oxid e)-r -2′-ca r bom eth oxy-cis-4′, cis-6′-
d im eth yl-1′,3′-d ith ia n e tr a n s-oxid e] (11). Photooxidation
of 4c gave a mixture of dimeric diastereomers of which 11 was
J
H-H ) 12.2, 6.9, 2.5 Hz, 1H, CHCH
2.2, 6.9, 2.50 Hz, 1H, CHCH SO), 3.91 (q, J H-H ) 7.1 Hz, 1H,
CHCH ); MS (70 eV) m/e (relative intensity) 178 (18, M ), 69
3
S), 3.16 (dqd, J H-H )
3
1
3
+
3
+
(
100, C H ). Anal. Calcd for C H S O: C, 47.15; H, 7.91; S,
5 9 7 14 2
the major component. The diastereomers were inseparable by
3
5.96. Found: C, 46.95; H, 7.86; S, 35.69.
1
thin-layer chromatography: H NMR (400.13 MHz, C
6
D
6
) δ
r -4,cis-6-Dim eth yl-1,3-d ith ia n e tr a n s-oxid e (4eSOeq):
3
3
1
1.10 (d, J H-H ) 6.8 Hz, 6H, CH
3
C), 1.11 (d, J H-H ) 6.8 Hz,
colorless needles; mp 155-157 °C; H NMR (400.13 MHz,
2
3
3
3
6H, CH
3
CSO), 1.20 (dt, J H-H ) 14.2 Hz, J H-H ) 2.7 Hz, 2H,
CDCl
)
1
3
) δ 1.20 (d, J H-H ) 6.8 Hz, 3H, CH
3
CS), 1.43 (d, J H-H
2
3
2
3
H(5)eq), 1.40 (dt, J H-H ) 14.2 Hz, J H-H ) 12.1 Hz, 2H, H(5)-
6.8 Hz, 3H, CH
3
CSO), 1.91 (dt, J H-H ) 15.0 Hz, J H-H
)
2
3
ax), 2.70-2.85 (m, 4H, SCHCH , CHCH SO), 3.23 (s, 6H,
1.8 Hz, 1H, H(5)ax), 2.26 (dt, J H-H ) 15.0 Hz, J H-H ) 2.4
3
3
+
3
3
CH O); MS (70 eV) m/e (relative intesity) 442 (1, M ), 69 (100,
Hz, 1H, H(5)eq), 2.67 (dqd,
CHCH
J
H-H ) 11.8, 6.8, 2.4 Hz, 1H,
+
+
3
C H9 ); HREI/MS (M ) calcd 442.0612, obsd 442.0615.
S), 3.04 (dqd, J H-H ) 11.8, 6.82, 2.4 Hz, 1H, CHCH
3
-
5
3
2
2
SO), 3.76 (d, J H-H ) 12.7 Hz, 1H, H(2)eq), 3.96 (d, J H-H ) 12.7
Hz, 1H, H(2)ax); MS (70 eV) m/e (relative intensity) 164 (15,
Ack n ow led gm en t. We thank the National Science
Foundation and the donors of the Petroleum Research
Fund, administered by the American Chemical Society,
for their generous support of this research. We also
thank Professor Frank J ensen (Odense University
Denmark) for valuable discussions.
+
+
5 9 6 12 2
H ). Anal. Calcd for C H S O: C, 43.87; H,
M ), 69 (100, C
.36; S, 39.04. Found: C, 43.60; H, 7.30; S, 39.25. Anal. Calcd
for C O: C, 43.87; H, 7.36; S, 39.03. Found: C, 43.60; H,
.30; S, 39.25.
,5-cis- Dim eth yl-1,2-d ith iola n e (12) was synthesized by
7
6
12 2
H S
7
3
3
5
the method of Eliel from meso-2,4-pentanediol ditosylate and
sodium disulfide in DMF. It was purified by fractional distil-
1
lation to give a yellow liquid: bp 68-69 °C (20 mm Hg); H
Su p p or t in g In for m a t ion Ava ila b le: 3C NMR and MS
3
NMR (400.13 MHz, CDCl
3
) δ 1.44(d,
J
H-H ) 6.6 Hz, 6H,
data for 1,3-dithianes and oxides. Experimental data for k
r
2
3
CH
2
(
3
C), 1.47(dt, J H-H ) 12.8 Hz, J H-H ) 9.0 Hz, 1H, H(4)ax),
.67(dt, J H-H ) 12.8 Hz, J H-H ) 5.8 Hz, 1H, H(4)eq), 3.69-
measurements and error analysis for isotope effects. Kinetic
data for decomposition of 1,4-dimethylnaphthalene-1,4-endo-
peroxide. Proton NMR for dimer 11. This material is available
free of charge via the Internet at http://pubs.acs.org.
2
3
3
13
dqd, J H-H ) 9.0, 6.6, 5.8 Hz, 2H, CHCH
MHz, CDCl ) δ 51.64 (CCH ), 51.43 (CH ), 20.64 (CH
Calcd for C : C, 44.73; H, 7.51; S, 47.76. Found: C, 44.87;
H, 7.48; S, 47.57.
3
); C NMR (100.61
3
3
2
3
). Anal.
5
10 2
H S
J O990709S