Deoxygenation of dithiirane 1-oxides with Lawesson's reagent leading to the corresponding dithiiranes

Article abstract of DOI:10.1021/jo026367z

3,3-Disubstituted dithiirane 1-oxides were efficiently reduced with Lawesson's reagent (LR) to give the corresponding dithiiranes. X-ray diffraction analysis of 3,3-di(1-adamantyl)dithiirane is reported. Reaction of ³⁴S-labeled 3,3-di(1-adamant

Full text of DOI:10.1021/jo026367z

Deoxygen a tion of Dith iir a n e 1-Oxid es w ith
La w esson ’s Rea gen t Lea d in g to th e
Cor r esp on d in g Dith iir a n es
SCHEME 1
Akihiko Ishii,* Remi Yamashita, Masashi Saito, and
J uzo Nakayama*
Department of Chemistry, Faculty of Science, Saitama
University, Saitama, Saitama 338-8570, J apan
ishiiaki@chem.saitama-u.ac.jp
Received August 29, 2002
CHART 1
Abstr a ct: 3,3-Disubstituted dithiirane 1-oxides were ef-
ficiently reduced with Lawesson’s reagent (LR) to give the
corresponding dithiiranes. X-ray diffraction analysis of 3,3-
3
4
di(1-adamantyl)dithiirane is reported. Reaction of S-
labeled 3,3-di(1-adamantyl)dithiirane 1-oxide with LR pro-
3
4
duced the corresponding dithiirane in which the S atoms
were retained quantitatively.
1
,2,4
atures or under basic conditions.
Phosphorus sulfide
The chemistry of dithiiranes has been drawing much
attention in view of the fundamental interest in organo-
sulfur chemistry.1 Recent progress in the chemistry
includes the preparation of dithiirane derivatives by the
reagents, such as LR,7
8
8d,9
P
2
S
5
,
and SdPBr
3
,
were
reported to convert sulfoxides to sulfides under conditions
appropriate for the present study. Indeed, LR reportedly
converts thioketone S-oxides into dithiiranes as men-
tioned above. Thus, we examined deoxygenation of 1
with LR and succeeded in removal of the oxygen atom
from 1.
A typical procedure is as follows: equimolar amounts
of dithiirane 1-oxide 1 and LR were dissolved in dichlo-
romethane under argon, and the mixture was stirred at
room temperature for 11 h (eq 1). After the solvent was
-4
reaction of thioketone S-oxides with Lawesson’s reagent
2
2
(
LR), reported by Shimada and co-workers, and the
observation of the parent dithiirane under matrix condi-
3
tions at 10 K by Mloston and co-workers. In our study
on the synthesis of isolable dithiiranes,4 we recently
reported two methods to prepare dithiirane 1-oxides 1:
thermal decomposition of tetrathiolane 2,3-dioxides 25
and the reaction of diazoalkanes with an S
Scheme 1). As a variety of structurally diverse dithi-
O equivalent6
2
(
iranes 3 are necessary to study the intrinsic chemical and
physical properties of dithiiranes, we next investigated
deoxygenation of 1 to lead it to the corresponding
dithiiranes 3. A reducing reagent that serves under mild
conditions must be employed for this transformation
because of the expected instability of 3 at high temper-
removed under reduced pressure, the residue was washed
with hexane several times to leave a sparingly soluble
residue derived from LR. The washings were combined
and purified by column chromatography. The results are
summarized in Table 1 with relevant spectroscopic data.
(1-Adamantyl)-tert-butyldithiirane (3a ) was obtained in
high yields from stereoisomers, 1a and 1b (entries 1 and
(1) (a) Ishii, A.; Nakayama, J . Reviews on Heteroatom Chemistry;
Oae, S., Ed.; MYU: Tokyo, J apan, 1999; Vol. 19, pp 1-34. (b)
Nakayama, J .; Ishii, A. Adv. Heterocycl. Chem. 2000, 77, 221-284.
(2) Shimada, K.; Kodaki, K.; Aoyagi, S.; Takikawa, Y.; Kabuto, C.
Chem. Lett. 1999, 695-696.
3) Mloston, G.; Romanski, J .; Reisenauer, H. P.; Maier, G. Angew.
Chem., Int. Ed. 2001, 40, 393-396.
4) (a) Ishii, A.; Akazawa, T.; Ding, M.-X.; Honjo, T.; Nakayama, J .;
(
(
2
). The low yield of 3d is attributed to its instability
Hoshino, M.; Shiro, M. J . Am. Chem. Soc. 1993, 115, 4914-4915. (b)
Ishii, A.; Akazawa, T.; Maruta, T.; Nakayama, J .; Hoshino, M.; Shiro,
M. Angew. Chem., Int. Ed. Engl. 1994, 33, 777-779. (c) Ishii, A.;
Maruta, T.; Teramoto, K.; Nakayama, J . Sulfur Lett. 1995, 18, 237-
under the reaction conditions (entry 4). The reaction of
spirodithiirane 1-oxide 1e (Chart 1) with LR completed
in a shorter reaction time (entry 5) in comparison to other
cases. In all cases, the corresponding thioketone was
obtained as a byproduct. A control experiment showed
2
42. (d) Ishii, A.; J in, Y.-N.; Nagaya, H.; Hoshino, M.; Nakayama, J .
Tetrahedron Lett. 1995, 36, 1867-1870. (e) Ishii, A.; Akazawa, T.; Ding,
M.-X.; Honjo, T.; Maruta, T.; Nakamura, S.; Nagaya, H.; Ogura, M.;
Teramoto, K.; Shiro, M.; Hoshino, M.; Nakayama, J . Bull. Chem. Soc.
J pn. 1997, 70, 509-523. (f) Ishii, A. J . Synth. Org. Chem., J pn. 1997,
5
5, 897-906. (g) Ishii, A.; Umezawa, K.; Nakayama, J . Tetrahedron
(7) Rasmussen, J . B.; J ørgensen, K. A.; Lawesson, S.-O. Bull. Soc.
Chim. Belg. 1978, 87, 307-308.
Lett. 1997, 38, 1431-1434. (h) Ishii, A.; Saito, M.; Murata, M.;
Nakayama, J . Eur. J . Org. Chem. 2002, 979-982.
(8) (a) Still, I. W. J .; Hasan, S. K.; Turnbull, K. Synthesis 1977, 468-
469. (b) Still, I. W. J .; Hasan, S. K.; Turnbull, K. Can. J . Chem. 1978,
56, 1423-1428. (c) Baechler, R. D.; Daley, S. K. Tetrahedron Lett. 1978,
101-104. (d) Baechler, R. D.; Daley, S. K.; Daly, B.; McGlynn, K.
Tetrahedron Lett. 1978, 105-108. (e) Kuipers, J . A. M.; Lammerink,
B. H. M.; Still, I. W. J .; Zwanenburg, B. Synthesis 1981, 295-296.
(9) Still, I. W. J .; Reed, J . N.; Turnbull, K. Tetrahedron Lett. 1979,
1481-1484.
(5) (a) J in, Y.-N.; Ishii, A.; Sugihara, Y.; Nakayama, J . Tetrahedron
Lett. 1998, 39, 3525-3528. (b) Ishii, A.; Nakabayashi, M.; Nakayama,
J . J . Am. Chem. Soc. 1999, 121, 7959-7960. (c) Ishii, A.; Nakabayashi,
M.; J in, Y.-N.; Nakayama, J . J . Organomet. Chem. 2000, 611, 127-
1
35.
(6) Ishii, A.; Kawai, T.; Tekura, K.; Oshida, H.; Nakayama, J . Angew.
Chem., Int. Ed. 2001, 40, 1924-1926.
1
0.1021/jo026367z CCC: $25.00 © 2003 American Chemical Society
Published on Web 01/03/2003
J . Org. Chem. 2003, 68, 1555-1558
1555

TABLE 1. Deoxygen a tion of Dith iir a n e 1-Oxid es 1 to Dith iir a n e 3 w ith La w esson ’s Rea gen t (LR)a
dithiirane 1-oxide 1 dithiirane 3
R1
R2
compd no.
b
compd no.
yield (%)
δCb
λmax/nm, (ꢀ)c
entry
δC
1
2
3
4
5
1-Ad
t-Bu
1-Ad
Ph
t-Bu
1-Ad
1-Ad
t-Bu
1a
1b
1c
1d
1e
86.2
87.7
87.4
86.2
89.0
3a
3a
3c
3d
3e
59d (86)e
84.7
452 (78)
59 (63)e
d
d
57
20
86.2
79.0
88.4
454 (93)
451 (50)
455 (ca. 40)
f
75f
a
Conditions: CH2Cl2, rt, 11 h (entries 1-4) or 1.25 h (entry 5). b 13C NMR chemical shifts of dithiirane carbons. c In CH2Cl2. d Isolated
yields. Determined by UV-vis. f Determined by H NMR in CDCl3.
e
1
SCHEME 2
F IGURE 1. ORTEP drawing of 3,3-di(1-adamantyl)dithiirane
3c) (50% ellipsoid). Relevant bond lengths (Å) and angles (deg)
(
data: S1-S2, 2.047(2); S1-C1, 1.826(5); S2-C1, 1.843(5); C1-
C2, 1.575(6); C1-C3, 1.581(6); S1-S2-C1, 55.7(2); S2-S1-
C1, 56.5(2); S1-C1-S2, 67.8(2); C2-C1-C3, 123.2(4).
that ca. 40% of dithiirane 3c decomposed to the corre-
unknown species as far as we know;12 however, a stable
dioxaphosphirane was recently reported.13 Thiosulfoxides
(RR′SdS) have been proposed as intermediates in deoxy-
sponding thioketone after 7 h by treatment with LR at
4
a
room temperature. The reaction of dithiirane 1-oxide 1f
4
b
(Chart 1) did not yield the corresponding dithiirane 3f
genation of sulfoxides with phosphorus sulfide reag-
under these conditions.
Dithiiranes 3 exhibited an absorption maximum due
ents.8
a,9,11
Steudel reported ab initio calculations on
simple dialkyl thiosulfoxides that are less stable by 80
to the S-S bond in a range of 450-455 nm in UV-vis
-
1
14
spectroscopy. In 13C NMR spectroscopy, dithiirane car-
kJ mol than the corresponding disulfides. Flammang
and co-workers recently showed by mass spectrometry
methodology that thiosulfoxides are stable in the gas
phase.15 In a theoretical, mechanistic study on the
bons of 3,3-dialkyldithiiranes, 3a , 3c, and 3e, resonated
at around δ 86, and that of alkylaryldithiirane 3 at a little
4
b
higher field (3d , δ 79.0; 3f, δ 80.6 ), while the corre-
sponding carbon of dithiirane 1-oxides 1 appeared in a
relatively narrow range (δ 86-89) independent of the
type of substituents.
1
6
thermal desulfurization of thiirane 7, thiirane 1-sulfide
was considered as a likely intermediate that lost sulfur
atoms finally to yield ethylene with generation of S , S
or S (Scheme 3). Chew and Harpp proposed an alterna-
8
2
3
,
4
Figure 1 depicts an ORTEP drawing of 3c with the
relevant bond lengths and angles data. The S-S bond
length of 2.047(2) Å is shorter by 0.051 Å than that of
the corresponding dithiirane 1-oxide 1c [2.098(1) Å].5
Two reaction pathways are considered for this deoxy-
genation reaction (Scheme 2). One (path A) is a mecha-
nism analogous to that proposed for reduction of sulfox-
tive, plausible mechanism on the basis of their experi-
mental results that sterically hindered thiiranes lose of
the sulfur atom by a concatenation process through the
a
thiirane S-sulfide intermediate to give the corresponding
17
alkenes and S
6
or S
8
.
Taking this reactivity of thiirane
S-sulfides into consideration, the intervention of dithi-
irane 1-sulfides 5 may be unlikely in the present reaction
8
a,b
9
ides to sulfides with P
1
4
S
10
3
or SdPBr . Dithiirane
1
0
-oxide 1 would react with LR′ to form a sulfurane
(
12) (a) Ishiguro, K.; Sawaki, Y. Bull. Chem. Soc. J pn. 2000, 73,
535-552. (b) Schoeller, W. W.; Busch, T. Chem. Ber. 1992, 125, 1319-
323. (c) Yu, H.; Chi, Y.; Fu, H.; Huang, X.; Li, Z.; Sun, J . Sci. China,
Ser. B: Chem. 2002, 45, 282-288; Chem. Abstr. 137, 11224.
13) Nakamoto, M.; Akiba, K. J . Am. Chem. Soc. 1999, 121, 6958-
6959.
intermediate 4, which gives dithiirane 3 through dithi-
irane 1-sulfide 5, or directly by elimination of 6.
Oxathiaphosphirane P-sulfides 6 (X ) O, Y ) S) or
dithiaphosphirane P-oxides 6 (X ) S, Y ) O) are
1
(
(14) Steudel, R.; Drozdova, Y.; Miaskiewicz, K.; Hertwig, R. H.; Koch,
W. J . Am. Chem. Soc. 1997, 119, 1990-1996. See also references
therein.
(10) (a) Scheibye, S.; Shabana, R.; Lawesson, S.-O.; Romming, C.
Tetrahedron 1982, 38, 993-1001. (b) Cherkasov, R. A.; Kutyrev, G.
A.; Pudovik, A. N. Tetrahedron 1985, 41, 2567-2624. (c) Cava, M. P.;
Levinson, M. I. Tetrahedron 1985, 41, 5061-5087.
(15) Gerbaux, P.; Salpin, J .-Y.; Bouchoux, G.; Flammang, R. Int. J .
Mass Spectrom. 2000, 195/196, 239-249.
(16) Steudel, Y.; Steudel, R.; Wong, M. W. Chem. Eur. J . 2002, 8,
217-228.
(11) Kutney, G. W.; Turnbull, K. Chem. Rev. 1982, 82, 333-357.
1
556 J . Org. Chem., Vol. 68, No. 4, 2003

SCHEME 3
quencies of 3c and 12 were determined to be 541 and
-
1
19,20
5
27 cm , respectively.
Exp er im en ta l Section
1
Gen er a l Meth od s. Melting points are uncorrected. H and
C NMR spectra were recorded at 400 and 100.6 MHz in CDCl ,
3
1
3
respectively. Dithiirane 1-oxides 1 and 10 were prepared by the
reported method.6
3
-(1-Ad a m a n tyl)-3-ter t-bu tyld ith iir a n e (3a ): Dithiirane
1
-oxide 1a (10.0 mg, 0.0352 mmol) and LR (17.9 mg, 0.0443
mmol) were dissolved in dichloromethane (10 mL) and the
mixture was stirred for 11 h at room temperature under argon.
The solution was concentrated under reduced pressure until an
oily material appeared, and then hexane was added to precipi-
tate the decomposition products of LR. The precipitates were
removed by filtration, and the filtrate was evaporated to dryness.
Hexane was then added again to the residue and the above
filtration-evaporation process was repeated two times. The
resulting residue was subjected to column chromatography
SCHEME 4
(
SiO
mp 92-93 °C (hexane-CH
br s, 6H), 2.00 (br s, 9H); 13C NMR δ 29.6, 32.5, 36.7, 42.5, 42.8,
2
, hexane) to give dithiirane 3a (5.6 mg, 59%): orange plates,
1
2
2
Cl ). H NMR δ 1.31 (s, 9H), 1.63
(
-
3
3
4
(
6
3.5, 84.7; UV-vis (CH
78) nm. Anal. Calcd for C15
7.18; H, 9.10.
,3-Di(1-a d a m a n tyl)d ith iir a n e (3c): In a manner similar
2
Cl
2
, c 3.82 × 10 mol/dm ) λmax (ꢀ) 452
24 2
H S
: C, 67.10; H, 9.01. Found: C,
3
to the above, 3c was obtained in 57% isolated yield (7.1 mg)
together with di(1-adamantyl) thioketone (3.1 mg, 27%) from
because it is barely believed that 5 gives only dithiirane
1
3.2 mg (0.036 mol) of 1c and 14.7 mg (0.036 mmol) of LR in
3
without formation of the corresponding thioketone,
dichloromethane (11.5 mL). 3c: orange plates, mp 136-139 °C
which was not a primary product as mentioned above.
1
dec (pentane). H NMR δ 1.58-1.69 (m, 12H), 1.98 (br s, 6H),
2.04 (br s, 12H); 13C NMR δ 29.6, 36.7, 42.9, 44.1, 86.2; UV-vis
Interestingly, the reaction of the parent thiolane
-
3
3
(
CH
for C21
Cr ysta l d a ta for 3c: C21
2
Cl
H
2
, 4.15 × 10 mol/dm ) λ max (ꢀ) 454 nm (93). Anal. Calcd
1
-oxide with LR was reported to give not only thiolane
S
30 2
: C, 72.77; H, 8.72. Found: C, 72.67; H, 8.81.
, orthorhombic, Pna2 , a )
but also the parent 1,2-dithiane, a ring expansion prod-
H
30
S
2
1
7
uct. If this is true of the present reaction, the formation
3
2
1.887(1) Å, b ) 11.037(1) Å, c ) 7.1080(3) Å, V ) 1717.1(2) Å ,
of trithietanes would be expected. However, when the
reactions of 1a and 1b with LR were monitored by UV-
vis spectroscopy, no remarkable absorption due to other
species appeared except for the absorption maximum
-3
-1
Z ) 4, Fcalcd ) 1.341 g cm , µ(Mo KR) ) 0.308 mm . An orange
3
plate with dimensions 0.26 × 0.16 × 0.05 mm was mounted on
a Mac Science DIP3000 diffractometer with a graphite mono-
chromator. Oscillation and nonscreen Weissenberg photographs
were recorded on the imaging plates of the diffractometer by
using Mo KR radiation (λ ) 0.71073 Å) at 153 K, and the data
reduction was made by the MAC DENZO program system.
Intensity data of 1893 independent reflections were collected in
the range of -27 e h e 27, 0 e k e 13, 0 e l e 7. The structure
(λmax 450 nm) due to dithiirane 3a . The reaction of 1c
3
1
with LR was traced with P NMR spectroscopy to result
in the observation of several signals in a range of δ 40s
1
8
1
25 probably due to the decomposition products of LR.
2
1
was solved by direct methods using SIR and refined with full-
matrix least-squares (SHELXL-9722) using all independent
reflections (1893 reflections) for 208 parameters. Absorption
The other likely mechanism (Scheme 2, path B) is the
reaction of thioketone S-oxide 9, formed by decomposition
2
23
of 1 in the reaction medium, with LR. A control experi-
corrections were done by a multiscan method (SORTAV ). The
ment showed that, for example, the reaction of thioketone
non-hydrogen atoms were refined anisotropically, and hydrogen
atoms were placed at calculated positions. The final R1 ) 0.0517
1
2
S-oxide 9 (R ) Ph, R ) t-Bu) with LR gave dithiirane
d in a shorter reaction time (5 min) than that of 1d with
LR. To distinguish the two paths A and B, we prepared
(
I > 2σ(I), 1420 reflections), wR2 ) 0.1552 (for all), GOF ) 1.059;
3
-
3
max/min residual density ) 1.366/-0.431 e Å
.
3
-ter t-Bu tyl-3-p h en yld ith iir a n e (3d ): Dithiirane 1-oxide
3
4
dithiirane 1-oxide 10 labeled with two S atoms by
1d (13.6 mg, 0.060 mmol) and LR (24.3 mg, 0.060 mmol) were
dissolved in dichloromethane (17 mL), and the solution was
stirred for 11 h at room temperature under argon. Water was
added and the resulting mixture was extracted with dichlo-
reaction of diazoalkane 11 and 34
6
8
S O and subjected 10
to the reaction with LR. Mass spectra of the resulting
2 showed almost quantitative retention of the 3 S atoms
4
1
romethane. The extract was washed with water, dried, and
to clearly rule out path B (Scheme 4).
evaporated to dryness. The 1H NMR spectrum of the residue
Dithiirane 3c and its 34S-labeled dithiirane 12 in hand
provided us with an opportunity to determine frequencies
of the S-S stretching vibrations of the dithiirane rings
by comparison of their Raman spectra. Thus, taking the
results of DFT calculations into consideration, the fre-
was measured with dibenzyl (3.90 mg, 0.0214 mmol) as the
(19) (a) Sugeta, H.; Go, A.; Miyazawa, T. Bull. Chem. Soc. J pn. 1973,
4
6, 3407-3411. (b) Van Wart, H. E.; Cardinaux, F.; Scheraga, H. A.
J . Phys. Chem. 1976, 80, 625-630. (c) Van Wart, H. E.; Scheraga, H.
A. J . Phys. Chem. 1976, 80, 1823-1832.
(20) Sakamoto, A.; Yamashita, R.; Ishii, A. Unpublished results.
Details of Raman and IR spectra of 1c, 3c, 10, and 12 will be reported
elsewhere.
(
17) (a) Chew, W.; Harpp, D. N. Tetrahedron Lett. 1992, 33, 45-48.
b) Chew, W.; Hynes, R. C.; Harpp, D. N. J . Org. Chem. 1993, 58, 4398-
404. (c) Chew, W.; Harpp, D. N. J . Org. Chem. 1993, 58, 4405-4410.
d) Chew, W.; Harpp, D. N. Sulfur Lett. 1993, 15, 247-252.
(
4
(
(21) Altomare, A.; Cascarano, G.; Giacovazzo, C.; Guagliardi, A. J .
Appl. Crystallogr. 1993, 26, 343-350.
(22) Sheldrick, G. M. SHELXL-97, Program for Crystal Structure
Refinement; G o¨ ttingen University: G o¨ ttingen, Germany, 1997.
(23) Blessing, R. H. Acta Crystallogr. 1995, A51, 33-38.
(18) Rauchfuss, T. B.; Zank, G. A. Tetrahedron Lett. 1986, 27, 3445-
3
448.
J . Org. Chem, Vol. 68, No. 4, 2003 1557

1
internal standard to indicate the formation of 3d (0.0121 mmol,
0%), thiopivalophenone (0.00577 mmol, 10%), and cis-3,5-di-
tert-butyl-3,5-diphenyl-1,2,4-trithiolane (0.00024 mmol, 0.4%).
and the reaction was monitored by H NMR spectroscopy. The
2
starting dithiirane 1-oxide 1e was consumed completely after
75 min. The yields of dithiirane 3e and the corresponding
thioketone28 were estimated to be 75% and 9%, respectively.
In a larger scale experiment employing 10 mg (0.041 mmol)
of 1e and 16 mg (0.041 mmol) of LR in dichloromethane (6 mL)
for 4.5 h, a 10:1 mixture of 3e and the thioketone was obtained
after removal of the decomposition products of LR by filtration.
Despite much effort, pure 3e could not be obtained by chromato-
graphic methods or recrystallization because of the decomposi-
tion to the thioketone, which hampered elemental analysis. 3e:
2
4
An analytical sample of 3d was obtained as follows. A solution
of thiopivarophenone S-oxide (90 mg, 0.46 mmol) with LR (0.13
g, 0.32 mmol) in dichloromethane (15 mL) was stirred at room
2
temperature. Water was added and the resulting mixture was
extracted with dichloromethane. The extract was dried and
evaporated to dryness. Hexane was added to precipitate the
decomposition products of LR and the resulting insoluble
materials were removed by filtration. The filtrate was concen-
trated under reduced pressure to leave an orange oily residue.
As dithiirane 3d could not be purified by chromatography or
distillation because of the occurrence of decomposition, the
decomposition products of LR were removed as much as possible
1
13
H NMR δ 1.37 (s, 12H), 7.22-7.25 (m, 4H); C NMR δ 31.4,
48.5, 88.4, 122.6, 127.5, 148.2; UV-vis (CH
-3
2
Cl
2
, c ) ca. 6 × 10
3
mol/dm ) λmax (ꢀ) 455 nm (ca. 40).
3
4
2
3,3-Di(1-a d a m a n tyl)- S -d ith iir a n e 1-oxid e (10): To a
1
solution of 34S8 (99.8%, 96 mg, 0.35 mmol) in CH Cl (24 mL)
2 2
by repeating the above manipulations: orange oil; H NMR δ
.11 (s, 9H), 7.14-7.21 (m, 3H), 7.29-7.34 (m, 2H); 1 C NMR δ
3
was added an acetone solution of dimethyldioxirane25 (0.083 M,
1
2
6
8.7, 38.8, 79.0, 126.3, 127.6, 131.5, 141.2; UV-vis (CH
2
Cl
.75 × 10 mol/dm ) λmax (ꢀ) 451 nm (50). Anal. Calcd for
: C, 62.81; H, 6.71. Found: C, 63.32; H, 6.82.
,1,3,3-Tetr a m eth ylin d a n e-2-sp ir o-3′-d ith iir a n e 1′-oxid e
1e): To a solution of S (64 mg, 0.25 mmol) in dichloromethane
7.5 mL) was added an acetone solution of dimethyldioxirane
0.104 M, 2.4 mL, 0.25 mmol) at 0 °C, and the mixture was
2
, c )
4.0 mL, 0.33 mmol) at 0 °C, and the mixture was stirred for 1 h
at 0 °C. To the mixture was added a dichloromethane solution
(5 mL) of di(1-adamantyl)diazomethane (11), prepared by
treatment of di(1-adamantyl) ketone hydrazone (112 mg, 0.357
mmol) with nickel peroxide30 (112 mg) in ether (20 mL). After
the mixture was stirred for 1.5 h, the solvent was removed under
reduced pressure, and the residue was passed through a short
Cl 1:1). The fraction containing
2 2
10 was subjected to HPLC [a reverse-phase column, MeCN, for
removal of di(1-adamantyl) ketone and di(1-adamantyl) S-
thioketone] to give 33 mg of 10 (26%).
-
3
3
2
9
C
11
H
14
S
2
2
9
1
(
(
(
8
2
5
column of silica gel (hexane-CH
stirred for 1 h at 0 °C. To the mixture was added a solution of
,1,3,3-tetramethyl-2-diazoindane26 (10 mg, 0.050 mmol) in
1
3
4
dichloromethane (2.5 mL). After being stirred for 2 h at room
temperature, the mixture was evaporated to dryness. The
3
4
3
2
,3-Di(1-a d a m a n tyl)- S -d ith iir a n e (12): By a method
residue was subjected to HPLC (SiO
2
, hexane-CH
2 2
Cl 1:1) to
similar to the case of 3a , 12 was obtained in 65% isolated yield
(6.2 mg) together with di(1-adamantyl) 34S-thioketone (2.3 mg,
27%) from 10.0 mg (0.027 mol) of 10 and 11.0 mg (0.027 mmol)
of LR in dichloromethane (8.5 mL). 12: MS (EI, 70 eV) m/z 350
give 1e (5.8 mg, 0.023 mmol, 46%) and 1,2,3,3-tetramethyl-1H-
2
7
indene (4.0 mg, 0.023 mmol, 47%). 1e: colorless crystals, mp
1
1
(
(
03-104 °C dec (hexane-CH
2 2
Cl ). H NMR δ 0.96 (s, 3H), 1.48
s, 3H), 1.56 (s, 3H), 1.78 (s, 3H), 7.14-7.18 (m, 1H), 7.24-7.35
+
+
34
+
34
1
3
2
(M , 6.7%), 316 (M - S, 99.7), 282 (M - S , 23.5), 181 (58.5),
m, 3H); C NMR δ 26.6, 29.7, 29.8, 31.8, 48.6, 50.9, 89.0, 121.9,
135 (100). The 34S content in 12 was calculated to be 99% based
22.4, 127.8, 128.1, 146.8, 149.1; IR (KBr) 1098 cm- (SdO).
1
1
on the average value of 10 scans.
Anal. Calcd for C13
H
16OS : C, 61.87; H, 6.39. Found: C, 61.82;
2
H, 6.45. The structure of 1e was confirmed by X-ray crystal-
lography, the details of which are given in the Supporting
Information.
Ack n ow led gm en t. We thank Dr. Akira Sakamoto
Saitama University) for measuring Raman spectra.
This work was supported by a Grant-in-Aid for Scientific
Research (No. 12440174) from the Ministry of Educa-
tion, Culture, Sports, Science and Technology, J apan.
(
1
,1,3,3-Tetr am eth ylin dan e-2-spir o-3′-dith iir an e (3e): Dithi-
irane 1-oxide 1e (1.9 mg, 0.0077 mmol) and LR (3.0 mg, 0.0071
mmol) were dissolved in CDCl (0.4 mL) in an NMR sample tube.
3
Dibenzyl (1.5 mg, 0.0085 mmol) was added as an internal
standard. The NMR sample tube was stood at room temperature,
Su p p or tin g In for m a tion Ava ila ble: Details of X-ray
crystallographic analyses of 3c and 1e, H NMR spectra of 3d ,
1
3
e, 10, and 12, and mass spectra of 12. This material is
(
24) Ishii, A.; Oshida, H.; Nakayama, J . Bull. Chem. Soc. J pn. 2002,
5, 319-328.
25) (a) Adam, W.; Bialas, J .; Hadjiarapoglou, L. Chem. Ber. 1991,
available free of charge via the Internet at http://pubs.acs.org.
7
(
J O026367Z
1
1
24, 2377. (b) Adam, W.; Hadjiarapoglou, L.; Smerz, A. Chem. Ber.
991, 124, 227-232.
(
I.; M u¨ ller, R.; Sch u¨ tz, M.; Wietzke, M.; Wilke, M. Chem. Ber. 1984,
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(
(28) Klages, C.-P.; Voss, J . Chem. Ber. 1980, 113, 2255-2277.
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1
27) Buddrus, J . Chem. Ber. 1968, 101, 4152-4162.
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