Synthesis and reactions of a monosubstituted dithiirane 1-oxide, 3-(9-triptycyl)dithiirane 1-oxide

Article abstract of DOI:10.1016/j.tet.2005.05.017

A 3-monosubstituted dithiirane 1-oxide, 3-(9-triptycyl)dithiirane 1-oxide, was prepared for the first time, by the reaction of (9-triptycyl)diazomethane and S₈O. The dithiirane 1-oxide was obtained as cis- and trans-isomers, and the structure of the trans-isomer was verified by X-ray crystallography. The cis-isomer isomerized gradually to the trans-isomer in solution. The divalent sulfur atom of the cis- and trans-dithiirane 1-oxides were removed on treatment with triphenylphosphine to give the corresponding Z- and E-sulfines, respectively. The reaction of the trans-dithiirane 1-oxide with (Ph₃P)₂Pt(C₂H₄) provided the (sulfenato-thiolato)Pt^II complex, and that with Lawesson's reagent yielded the 1,3,4,2-trithiaphospholane and 1,2,4,5,3-tetrathiaphosphorinane derivatives.

Full text of DOI:10.1016/j.tet.2005.05.017

Tetrahedron 61 (2005) 6693–6699
Synthesis and reactions of a monosubstituted dithiirane 1-oxide,
3
-(9-triptycyl)dithiirane 1-oxide
Akihiko Ishii, Tetsuhiko Kawai, Mariko Noji and Juzo Nakayama
*
Department of Chemistry, Faculty of Science, Saitama University, Sakura-ku, Saitama 338-8570, Japan
Received 12 April 2005; revised 9 May 2005; accepted 10 May 2005
Abstract—A 3-monosubstituted dithiirane 1-oxide, 3-(9-triptycyl)dithiirane 1-oxide, was prepared for the first time, by the reaction of
(9-triptycyl)diazomethane and S O. The dithiirane 1-oxide was obtained as cis- and trans-isomers, and the structure of the trans-isomer was
8
verified by X-ray crystallography. The cis-isomer isomerized gradually to the trans-isomer in solution. The divalent sulfur atom of the cis-
and trans-dithiirane 1-oxides were removed on treatment with triphenylphosphine to give the corresponding Z- and E-sulfines, respectively.
II
) provided the (sulfenato-thiolato)Pt complex, and that with Lawesson’s
The reaction of the trans-dithiirane 1-oxide with (Ph
3
P)
2
Pt(C
reagent yielded the 1,3,4,2-trithiaphospholane and 1,2,4,5,3-tetrathiaphosphorinane derivatives.
2
H
4
q 2005 Elsevier Ltd. All rights reserved.
1. Introduction
We report here, the synthesis of 3-(9-triptycyl)dithiirane
1
-oxide 1, the first, isolable 3-monosubstituted dithiirane
1
dithiiranes had been recognized as elusive intermediates,
-oxide, and its physical and chemical properties. While
–7
1
we discovered the formation of isolable dithiiranes 2 and
dithiirane 1-oxides 3 by oxidative hydrolysis of bicyclic 1,3-
8
–14
dithietanes 4 and 5, respectively.
two routes for dithiirane oxides 6: one is the elimination of
We have also disclosed
1
5,16
S2O from tetrathiolane 2,3-dioxides and the other is the
reaction of diazoalkanes with S O. Dithiirane 1-oxides 6
can be led to the corresponding dithiiranes 7 by treatment
1
7
8
1
8
with Lawesson’s reagent (LR). On the other hand,
Shimada and co-workers succeeded in the synthesis of
dithiiranes 8 and 9 by the reaction of the corresponding
thioketone S-oxides (sulfines) with LR. Mloston and
Maier reported the isolation of the parent dithiirane in the
argon matrix at 10 K together with the parent thioformalde-
1
9
2
0
hyde S-sulfide (thiosulfine). Thus, dithiiranes isolated so
far at room temperature in air are limited to 3,3-dialkyl- and
3
-alkyl-3-aryldithiirane derivatives. 3-Monosubstituted
dithiiranes are of great interest not only for their physical
and chemical properties but also from the viewpoint of to
what extent the steric demand of the substituent can be
reduced for the intrinsically unstable dithiirane ring.
Previously, we reported that reactions of (2,4,6-trimethyl-
Keywords: Dithiirane oxide; Steric protection; 9-Triptycyl; Diazo com-
pound; Octasulfur monoxide.
*
Corresponding author. Tel.: C81 48 858 3394; fax: C81 48 858 3700;
e-mail: ishiiaki@chem.saitama-u.ac.jp
0040–4020/$ - see front matter q 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2005.05.017

6694
A. Ishii et al. / Tetrahedron 61 (2005) 6693–6699
phenyl)- and (2,4,6-tri-t-butylphenyl)diazomathanes with
S O failed to give the corresponding monosubstituted
8
1
dithiirane 1-oxides. Thus we next, employed 9-triptycyl
7
2
as the substituent, and the reaction of (9-triptycyl)diazo-
1
methane (10) with S O furnished the desired 3-mono-
8
substituted dithiirane 1-oxide. Hereafter, the 9-triptycyl
group is abbreviated to Trip for convenience.
2
. Results and discussion
(9-Triptycyl)diazomethane (10), prepared by oxidation of
the corresponding hydrazone (TripCHNNH ), was treated
2
with S O in dichloromethane at room temperature. After
8
chromatographic purification, we obtained the desired cis-1
[
(1R*,3S*)-1] (8%) and trans-1 [(1S*,3S*)-1] (10%)
together with 1,3,4-thiadiazoline 11 (16%), azine 12 (2%),
and sulfines Z-13 (7%) and E-13 (5%) (Eq. 1). The
formation of 11 is explained by the reaction of 10 with
1
7,22
TripCHS,
though TripCHS was not obtained in this
reaction or in reactions reported later in this paper. The
2
3
Figure 1. ORTEP drawing of trans-1 (30% ellipsoidal probability).
˚
Relevant bond lengths (A) and bond angles (deg) data: S1–O1 1.436(6),
S1–C1 1.787(5), S1–S2 2.119(3), S2–C1 1.798(5), C2–C16 1.521(5), C2–
C10 1.533(6), C2–C4 1.537(5), C2–C1 1.540(6), O1–S1–C1 113.2(3), O1–
S1–S2 115.8(4), C1–S1–S2 54.01(18), C1–S2–S1 53.53(18), C16–C2–C10
stereochemistry of 11 was determined as trans by X-ray
crystallography. Azine 12 may be formed by the reaction
of 10 with SO2. Sulfines 13 are the decomposition
products of 1 on silica gel.
2
4
1
7,25–27
1
1
1
05.7(3), C16–C2–C4 105.6(3), C10–C2–C4 105.9(3), C16–C2–C1
11.0(4), C10–C2–C1 119.7(4), C4–C2–C1 108.0(4), C2–C1–S1
23.4(4), C2–C1–S2 124.3(4), S1–C1–S2 72.5(2).
disappearance of cis-1 to leave trans-1 (71%) and Z-13
(29%) (Eq. 2). This isomerization apparently obeyed the
K7 K1
2
first-order kinetics (kZ4.0!10
s
, r Z0.966). The
presence of a small amount of a radical scavenger, 1,1-
(1)
diphenyl-2-picryl hydrazyl (DPPH), led to substantial
retardation of the isomerization (kZ0.81!10
0
K7 K1
2
s
.913); after 1 month, the isomerization proceeded up to
, r Z
5
7% without DPPH and down to 31% in the presence of
DPPH, suggesting the isomerization is caused by a radical
contaminant. We have observed a similar retardation of the
0
The structures of dithiirane 1-oxides, cis-1 and trans-1, were
elucidated by their spectroscopic data. In the H NMR
epimerization between dithiirane 1-oxides 2 (RZPh) and 2
(RZPh) by DPPH (Eq. 3).
1
32
spectra (400 MHz) measured at 298 K, dithiirane ring
protons of cis-1 and trans-1 appeared at d 4.98 and 5.49,
respectively. The low-field shift in trans-1 is due to the
anisotropic effect of the S]O group being cis to the
(
(
2)
3)
2
8,29
proton. At this temperature, three benzene rings of cis-1
are not equivalent to each other, indicating that free rotation
of the 9-triptycyl group in cis-1 is slowed by the steric
3
0
13
hindrance due to the cis oxygen atom. In the C NMR
spectra, dithiirane ring carbons of cis-1 and trans-1
resonated at d 66.7 and 66.9, respectively, and the
1
13
1
J ( C– H) coupling constants determined with gated
decoupling were 169 and 173 Hz, respectively. These J
1
1
3
1
C– H) values are comparable to those of other three-
(
membered cyclic compounds such as cyclopropane
The divalent sulfur atom in a dithiirane 1-oxide is readily
removed by treatment with tripheylphosphine to give the
corresponding sulfine with retention of stereochemistry.
Treatment of cis-1 and trans-1 with triphenylphosphine
gave Z-13 and E-13, respectively, in high yields (Eqs. 4 and
3
161 Hz) and thiirane (171 Hz). The stereochemistry of
1
16
(
trans-1 was verified by X-ray crystallography as depicted in
Figure 1.
5
). The reaction of trans-1 with (Ph P) Pt(C H ) yielded
3 2 2 4
II
33
cis-1 was not obtained in the pure form by chromatographic
purification or recrystallization because of its gradual
isomerization to trans-1 in solution. The reverse isomeriza-
tion from trans-1 to cis-1 was not observed under similar
conditions. Standing a CDCl solution of cis-1 at room
3
temperature in the dark for 3 months led to the complete
(sulfenato-thiolato)Pt complex 14 in 88% isolated yield.
When cis-1 was allowed to react with (Ph P) Pt(C H ), the
3
2
2 4
same complex was formed as the major product. A much
low-field shift of the four-membered ring proton of 14 [d
6.75 (d, JZ2.3 Hz)] compared with the corresponding
dithiirane protons of cis-1 (d 4.98) and trans-1 (d 5.49)

A. Ishii et al. / Tetrahedron 61 (2005) 6693–6699
6695
implies the cis configuration of the hydrogen to the S]O
oxygen.
3. Conclusion
-Monosubstituted dithiirane 1-oxides trans-1 and cis-1
3
were successfully synthesized, for the first time, by taking
advantage of a 9-triptycyl group as the steric-demanding
group. The dithiirane 1-oxides 1 presented reactivities
similar to those of 3,3-disubstituted dithiirane 1-oxides but
the reaction with LR gave sulfur–phosphorus-containing
heterocycles.
(
(
4)
5)
4. Experimental
4.1. General
(6)
The melting points were determined on a Mel-Temp
C
NMR spectra were determined on Bruker AM400 or
1
capillary tube apparatus and are uncorrected. H and
13
DRX400 (400 and 100.6 MHz, respectively), AC300P
(
In the hope of obtaining the corresponding unoxidized
dithiirane, trans-1 was treated with LR in benzene at room
temperature. However, we obtained not the desired
dithiirane but stereoisomers of 1,3,4,2-trithiaphospho-
lanes 15a,b and 1,2,4,5,3-tetrathiaphosphorinanes 16a,b.
The structures of 15a,b and 16a,b were elucidated by their
1
300 MHz for H), or AC200 (200 and 50 MHz, respect-
1
8
ively), spectrometers using CDCl as the solvent at 25 8C,
3
3
1
unless otherwise noted. P NMR spectra were determined
on Bruker AM400 or DRX400 (162 MHz) spectrometers
using 85% H PO as the external standard in CDCl at
3
4
3
1
13
31
25 8C. IR spectra were taken on a Hitachi 270-50
spectrometer. Mass spectra were determined on a JEOL
JMS-DX303 or a JEOL JMS-700AM spectrometers operat-
ing at 70 eV in the EI mode. FAB MS was measured with
m-nitrobenzyl alcohol as the matrix. Elemental analysis was
performed by the Chemical Analysis Center of Saitama
University. Column chromatography was performed with
silica gel (70–230 mesh), high-pressure liquid chromato-
H, C, and P NMR data and mass spectroscopic data,
though their stereochemistries were not determined. In the
1
H NMR of 15a, the 1,3,4,2- trithiaphospholane ring proton
appeared as a doublet with 2.7 Hz of the J ( H– P)
3
1
31
1
3
coupling constant, and in the C NMR, the ring carbon
2
13
31
appeared as a doublet with 4.5 Hz of the J ( C– P)
coupling constant. Similarly, the corresponding proton and
carbon of 15b resonated as a doublet. Such long-range
couplings were not observed for 16a,b, and their tetra-
thiaphosphorinane ring protons and the carbons appeared as
a broad singlet. These observations would rule out 1,2,3,5,4-
tetrathiaphosphorinane structures 17 for the six-membered
compounds. Compounds 15a,b formally correspond to
adducts of TripCHS with ArPS (ArZ4-MeOC H ), and
graphy (HPLC) with a packed SiO column (INERTSIL
2
PREP-SIL: 10 mm i.d. or 20 mm i.d., GL Science Inc.), and
gel permeation chromatography (GPC) on a Japan Analyti-
cal Industry LC-908; the eluent is shown in parentheses.
4
4
.2. Preparation of (9-triptycyl)diazomethane (10)
2
2
6 4
16a,b correspond to those of TripCHS3 with ArPS2.
Incidentally, we have recently, obtained adducts of
.2.1. Preparation of triptycene-9-carbaldehyde. Butyl-
lithium (1.56 M in hexane, 5.6 mL, 8.74 mmol) was added
thioketones with ArPS , which are 1,3,2-dithiaphosphetane
2
3
5
3
4
to a solution of 9-bromotriptycene (1.42 g, 4.25 mmol) in
benzene (60 mL) and ether (95 mL) at K15 8C under argon,
and the solution was stirred for 1 h at K15 8C. To the
solution was added ethyl formate (5.6 mL, 69 mmol), and
the mixture was warmed to room temperature. After stirring
for 15 min, aqueous ammonium chloride and then ether
were added to the mixture. The organic layer was washed
with water, dried over anhydrous magnesium sulfate, and
the solvent was removed under reduced pressure. The
residue was subjected to column chromatography (CH Cl /
derivatives. Noteworthy is the formation of trithia-
phospholanes 15a and 15b by the reaction of sulfine Z-13
with LR in 31 and 17% yields, respectively. It has been
reported that the reaction of a sulfine with LR gave the
1
9
dithiirane. At present, however, we do not have direct
evidence of intervention of TripCHS in these reactions.
2
2
2
hexane 1:1) to give the aldehyde (825 mg, 69%).
3
6
1
Triptycene-9-carbaldehyde. Colorless crystals. H NMR
300 MHz) d 5.40 (s, 1H), 6.98–7.05 (m, 6H), 7.40–7.44 (m,
(
3H), 7.59–7.63 (m, 3H), 11.22 (s, 1H).
(7)
4.2.2. Preparation of triptycene-9-carbaldehyde hydra-
zone. A solution of triptycene-9-carbaldehyde (1.40 g,
4
0
0
.96 mmol) and hydrazine monohydrate (22 mL,
.41 mol) in diethylene glycohol (50 mL) was refluxed for
.5 h. The mixture was cooled to room temperature, diluted
with water, and then extracted with dichloromethane. The

6696
A. Ishii et al. / Tetrahedron 61 (2005) 6693–6699
˚
˚
extract was washed with water and dried over anhydrous
magnesium sulfate, and the solvent was removed under
reduced pressure. The residue was subjected to column
chromatography (CH Cl ) to give the hydrazone (1.438 g,
monoclinic, P2 /c, aZ15.761(2) A, bZ8.1384(13) A, cZ
1
3
˚
˚
13.756(2) A, bZ112.596(12)8, VZ1629.0(5) A , rcalcdZ
1.413 g cm , ZZ4, m(Cu Ka)Z2.981 cm . Mac Science
MXC3KHF diffractometer with graphite-monochromated
K3
K1
2
2
˚
9
8%).
Cu Ka radiation (lZ1.54178 A), q/2q scans method in the
range 38!2q!1408 (K19!h!17, 0!k!9, 0!l!16),
2740 independent reflections. Absorption correction was
Triptycene-9-carbaldehyde hydrazone. Colorless powder,
1
41
done by the psi-can method. The structure was solved with
mp O352 8C decomp. (EtOH–water). H NMR (400 MHz)
d 5.39 (s, 1H), 5.93 (br s, 2H), 6.95–7.05 (m, 6H), 7.35–7.43
4
2
a direct method (SIR97 ) and refined with full-matrix least-
1
m, 3H), 7.56–7.65 (m, 3H), 8.44 (s, 1H); C NMR
3
43
squares (SHELXL-97 ) using all independent reflections,
(
(
(
(
100.6 MHz) d 54.3 (CH), 54.6 (C), 123.0 (CH), 123.6
CH), 124.9 (CH), 125.2 (CH), 141.1 (CH), 145.4 (C), 145.8
where nonhydrogen atoms were refined anisotropically and
hydrogen atoms isotropically without the AFIX code except
C(1)–H. R1Z0.0894 (IO2sI, 2485 reflections), wR2Z
0.2674 (for all), GOFZ1.070, 271 parameters; max/min
K1
C); IR (KBr) 3378 (NH ), 1455, 754, 729 cm . Anal.
2
Found: C, 84.09; H, 5.53; N, 9.23. Calcd for C H -
2
1 16
K3
˚
N $0.112C H O$0.213H O: C, 83.48; H, 5.64; N, 9.17 (the
2
residual electron densityZ1.021/K0.542 e A . CCDC-
2
6
2
1
H NMR spectrum of the sample subjected to the elemental
analysis showed that it contained 11.2 mol% of ethanol and
268216 contains the supplementary crystallographic data.
These data can be obtained free of charge at www.ccdc.cam.
ac.uk/conts/retrieving.html or from the Cambridge Crystal-
lographic Data Centre, 12, Union Road, Cambridge CB2
1EZ, UK [Fax: (internat.) C44-1223 336-033; E-mail:
deposit@ccdc.cam.ac.uk].
2
1.3 mol% of H O).
2
4
.2.3. Preparation of (9-triptycyl)diazomethane (10). To
a solution of triptycene-9-carbaldehyde hydrazone (221 mg,
.745 mmol) in benzene was added 378 mg (1.54 g-atom of
oxygen) of nickel peroxide (4.08!10 g-atom of oxygen/
0
K3
1
4
NMR (400 MHz) d 4.98 (s, 1H), 5.42 (s, 1H), 6.86 (td,
.3.2. c-3-(9-Triptycyl)dithiirane r-1-oxide (cis-1).
H
3
7,38
g).
The mixture was stirred for 1 h at room temperature.
After filtration, the solvent was removed under reduced
pressure to give (9-triptycyl)diazomethane (10). The
diazomethane was used without further purification.
JZ7.7, 1.3 Hz, 1H), 6.94 (td, JZ7.4, 0.9 Hz, 1H), 7.03–
7
3
.21 (m, 4H), 7.34 (dd, JZ7.2, 1.1 Hz, 1H), 7.43–7.48 (m,
13
H), 7.92 (d, JZ8.6 Hz, 1H), 7.94 (d, JZ8.5 Hz, 1H);
C
1
NMR (100.6 MHz) d 54.5 [two carbons: CH with
(
J
3
9
1
-Triptycyl)diazomethane (10). Orange oil. H NMR
9
13
1
1
13
1
C– H)Z141 Hz and C], 59.9 [CH, J ( C– H)Z
69 Hz], 121.6 (CH), 121.9 (CH), 123.2 (CH), 123.78
CH), 123.82 (CH), 124.0 (CH), 125.1 (CH), 125.3 (CH),
(
6
300 MHz) d 5.07 (s, 1H), 5.42 (s, 1H), 7.01–7.09 (m,
H), 7.38–7.43 (m, 6H); IR (neat) 2063, 1456, 748 cm
1
(
K1
.
1
1
25.5 (CH), 126.0 (CH), 126.1 (CH), 128.0 (CH), 141.4 (C),
43.3 (C), 145.4 (C), 146.1 (C), 146.2 (C), 146.8 (C); IR
4
.3. Reaction of (9-triptycyl)diazomethane (10) with S O
8
K1
(KBr) 1462, 1130, 1122 (S]O), 752 cm
.
4
A mixture of S O (415 mg, 1.53 mmol) and 10, prepared
0
8
above, in dichloromethane (45 mL) under argon was stirred
for 1.5 h at room temperature. The solvent was evaporated
to dryness, and the residue was passed through a short
column of silica gel (dichloromethane). The fraction
containing products was further subjected to HPLC
4.3.3. 2,5-Di-(9-triptycyl)-1,3,4-thiadiazoline (11). Color-
less crystals, mp 207–210 8C decomp. (hexane–CH Cl ). H
NMR (300 MHz) d 5.49 (s, 2H), 6.85 (d, JZ7.7 Hz, 2H),
1
2
2
6
7
.98–7.12 (m, 10H), 7.19 (td, JZ7.7, 1.4 Hz, 2H), 7.45–
.53 (m, 6H), 7.59 (d, JZ7.4 Hz, 2H), 8.10 (s, 2H), 8.54 (d,
(
dichloromethane/hexane 60:40 and then 80:20 for E-5) to
1
3
JZ7.7 Hz, 2H); C NMR (100.6 MHz) d 54.8 (CH), 59.0
give a mixture of thiadiazoline 11 and azine 12, cis-
dithiirane 1-oxide cis-1 (21.7 mg, 8%), trans-dithiirane
(C), 102.6 (CH), 121.8 (CH), 122.7 (CH), 123.5 (CH), 123.8
(CH), 124.2 (CH), 124.6 (CH), 124.8 (CH), 125.1 (CH),
1-oxide trans-1 (26.2 mg, 10%), Z-sulfine Z-5 (16 mg, 7%),
and E-sulfine E-5 (11.8 mg, 5%) in this order. The mixture
1
1
25.2 (CH), 125.5 (CH), 125.7 (CH), 126.0 (CH), 141.1 (C),
45.0 (C), 145.1 (C), 146.0 (C), 146.4 (C), 147.2 (C); IR
of 11 and 12 was subjected to GPC (CHCl ) and again
3
HPLC (dichloromethane/hexane 40:60) to give thiadiazo-
line 11 (36.5 mg, 16%) and azine 12 (4 mg, 2%).
K1
(KBr) 1458, 744 cm . Anal. Found: C, 81.31; H, 4.98; N,
4
8
.27. Calcd for C H N S$0.354CH Cl $0.261C H : C,
42 28 2 2 2 6 14
1
1.74; H, 5.06; N, 4.34 (the H NMR spectrum of the
sample subjected to the elemental analysis showed that it
contained 35.4 mol% of CH Cl and 26.1 mol% of hexane).
4
1
5
7
.3.1. t-3-(9-Triptycyl)dithiirane r-1-oxide (trans-1). Mp
1
86–187 8C (Et O–CH Cl ). H NMR (400 MHz): 300 K: d
2
2
2
2
2
.40 (s, 1H), 5.49 (s, 1H), 6.90 (br s, 1H), 7.09 (br s, 6H),
.43 (br s, 3H), 7.83 (br s, 2H); 323 K: d 5.36 (s, 1H), 5.47
3
4.3.4. Triptycene-9-carbaldehyde azine (12). Colorless
9
1
(
3
s, 1H), 6.80–8.06 (br s, 3H), 7.03 (br s, 6H), 7.38–7.41 (m,
J
crystals, mp O352 8C decomp. (CHCl3). H NMR
(400 MHz) d 5.50 (s, 2H), 7.06–7.14 (m, 12H), 7.47–7.49
1
H); C NMR (100.6 MHz, 323 K) d 54.5 [CH,
3
1
1
3
1
1
13
1
13
(m, 6H), 7.85–7.88 (m, 6H), 9.72 (s, 2H); C NMR
(
1
(
C– H)Z138 Hz], 55.0 (C), 66.9 [CH, J ( C– H)Z
73 Hz], 122.6 (br, CH), 124.0 (CH), 125.4 (CH), 126.0
CH), 143.9 (br, C), 146.2 (C); IR (KBr) 1460, 1128 (S]O),
(100.6 MHz) d 54.5 (CH), 55.4 (C), 123.1 (CH), 123.9
(CH), 125.2 (CH), 125.7 (CH), 144.5 (C), 145.9 (C), 164.4
K1
K1
(CH); IR (KBr) 1661, 1456, 758 cm . Anal. Found: C,
742 cm . Anal. Calcd for C H OS : C, 72.80; H, 4.07.
2
Found: C, 72.43; H, 3.93.
1
14
2
88.79; H, 4.87; N, 4.92. Calcd for C H N $0.0457CHCl :
28
4
2
2
3
1
C, 89.20; H, 4.99; N, 4.95 (the H NMR spectrum, measured
in CD Cl , of the sample subjected to the elemental analysis
showed that it contained at least 4.57 mol% of CHCl3).
Crystallographic data for trans-1. C H OS , M Z
3
2
1
14
2
w
2
2
3
46.470, colorless plate, 0.20!0.12!0.06 mm ,

A. Ishii et al. / Tetrahedron 61 (2005) 6693–6699
6697
4.3.5. (9-Triptycyl)methanethial (E)-S-oxide (E-13).
Colorless crystals, mp 239–241 8C (CH Cl –hexane). H
130.3 (C, L), 130.4 (p-CH, L), 134.2 (CH, L), 134.3 (CH,
L), 134.5 (CH, L), 134.6 (CH, L), 143.4 (C), 144.1 (C),
144.8 (C), 146.6 (C), 146.7 (C), 147.0 (C) [L in the
1
2
2
NMR (400 MHz) d 5.45 (s, 1H), 7.02–7.09 (m, 6H), 7.40–
7
1
.46 (m, 6H), 10.15 (s, 1H); C NMR (100.6 MHz) d 54.1
3
parentheses means that the signal is due to the Ph P
3
1
ligand. Their J ( C– P) coupling constants are not
3
31
(
(
1
CH), 58.2 (C), 122.1 (CH), 124.1 (CH), 125.3 (CH), 126.1
CH), 143.9 (C), 145.1 (C), 180.1 (CH); IR (KBr) 1457,
determined, and signals due to the Ph P ligands are listed
3
K1 C
103 (S]O), 743 cm . MS (EI) m/z 314 (M ). HRMS
31
2
31 31
as appeared]; P NMR (162 MHz) d 16.2 [d, J ( P– P)Z
1 31 195 2 31 31
(
EI): Calcd for C H OS: M 314.0765. Found: m/z
2
25 Hz, J ( P– Pt)Z2418 Hz], 17.7 [d, J ( P– P)Z
1 31 195
1 14
3
Found: C, 79.53; H, 4.40.
14.0792. Anal. Calcd for C H OS: C, 80.22; H, 4.49.
2
25 Hz, J ( P– Pt)Z3189 Hz]; IR (KBr) 1484, 1460,
1438, 1096 (S]O), 1000, 982, 746, 692 cm . Calcd for:
1 14
K1
C H OP PtS $CHCl : C, 58.76; H, 3.83. Found: C, 58.28;
5
7
44
2
2
3
4
.3.6. (9-Triptycyl)methanethial (Z)-S-oxide (Z-13).
Colorless crystals, mp 245–246 8C (CH Cl –hexane). H
H, 3.74.
1
2
2
NMR (400 MHz, CDCl ) d 5.45 (s, 1H), 7.03–7.08 (m, 6H),
3
4.6. Reaction of dithiirane 1-oxide trans-1 with
Lawesson’s reagent (LR)
1
3
7
.37–7.42 (m, 3H), 7.42–7.47 (m, 3H), 9.01 (s, 1H);
C
NMR (100.6 MHz, CDCl ) d 54.1 (CH), 60.5 (C), 121.8
3
(
(
CH), 124.2 (CH), 125.1 (CH), 126.0 (CH), 141.0 (C), 144.7
C), 165.5 (CH); IR (KBr) 1457, 1120 (S]O), 753 cm
A solution of dithiirane 1-oxide trans-1 (31.4 mg,
0.091 mmol) and LR (76.2 mg, 0.188 mmol, Sigma-Aldrich
Co.) in dichloromethane (15 mL) under argon was stirred
for 4 h at room temperature. The solvent was removed under
reduced pressure. Polar decomposition products of LR were
removed by passing the residue through a short column of
silica gel (dichloromethane), and a mixture containing the
products thus obtained was subjected to HPLC (dichloro-
methane/hexane 45:55) to give tetrathiaphosphorinane 16a
(the major isomer) (20.8 mg, 41%), a 37:63 mixture of
tetrathiaphosphorinane 16b (the minor isomer) (13%) and
trithiaphospholane 15a (the major isomer) (22%), and
trithiaphospholane 15b (the minor isomer) (3.1 mg, 6%) in
this order. A mixture of 16b and 15a could be separated with
HPLC (dichloromethane/hexane 40:60) to give pure 16a
and 15a in this order.
K1
;
C
MS (EI) m/z 314 (M ). HRMS (EI): Calcd for C H OS:
2
M 314.0765. Found: m/z 314.0774. Anal. Calcd for
C H OS: C, 80.22; H, 4.49. Found: C, 80.04; H, 4.41%.
1 14
2
1 14
4.4. Reaction of dithiirane 1-oxides cis-1 and trans-1 with
triphenylphosphine
Dithiirane 1-oxide cis-1 (7.0 mg, 0.02 mmol) and tri-
phenylphosphine (5.6 mg, 0.021 mmol) were dissolved in
dichloromethane (4 mL) under argon, and the solution was
stirred at 0 8C for 5 min. The solvent was removed under
reduced pressure, and the residue was subjected to HPLC
(
(
dichloromethane/hexane 65:35) to give sulfine Z-13
4.5 mg, 72%).
In a similar manner, trans-1 (11 mg, 0.032 mmol) was
treated with triphenylphosphine (8.6 mg, 0.033 mmol) in
dichloromethane (3 mL) to yield E-13 (8.9 mg, 88%).
4.6.1. 1,2,4,5,3-Tetrathiaphosphorinane (16a). White
powder, mp 219–221 8C decomp. (CH Cl –hexane).
1
H
2
2
NMR (400 MHz) d 3.94 (s, 3H), 5.34 (s, 1H), 6.19 (br s,
H), 6.97–7.10 (m, 4H), 7.10–7.21 (m, 4H), 7.21–7.45 (m,
3H), 7.47 (dd, JZ7.0, 1.0 Hz, 1H), 8.03 (br s, 1H), 8.31 (br
1
4
(
.5. Reaction of dithiirane 1-oxides trans-1 with
Ph P) Pt(C H )
1
3
s, 1H), 8.44 (dd, JZ13.1, 8.8 Hz, 2H); C NMR
100.6 MHz) d 54.6 (CH), 55.7 (CH ), 59.5 (br s, CH),
3
2
2
4
(
3
1
3
31
To a solution of trans-1 (15.8 mg, 0.456 mmol) in toluene
61.6 (br s, C), 114.4 [d, J ( C– P)Z15 Hz, CH), 122.0 (br
s, CH), 123.7 (br s, 2CH), 124.0 (br s, 2CH), 124.6 (2CH),
125.3 (CH), 125.6 (br s, 3CH), 126.3 (CH) 134.5 [d, J
(
(
5 mL) under argon at 0 8C was added a solution of
Ph P) Pt(C H ) (34.1 mg, 0.456 mmol) in toluene (4 mL).
3
2
2 4
1
3
31
The mixture was stirred for 1 h at 0 8C, and the solvent
was removed under reduced pressure. The residue was
subjected to column chromatography (dichloromethane/
( C– P)Z12 Hz, CH], 139.9 (C), 144.3 (2C), 145.0 (C),
13 31
146.4 (C), 147.3 (C), 164.4 [d, J ( C– P)Z3 Hz, C] (the
quaternary carbon bonded to the P atom was not observed
probably because of overlapping with signals due to CH
II
ether 3:1) to give (sulfenato-thiolato)Pt complex 14
(
3
1
42.5 mg, 88%).
.5.1. [(9-Triptycyl)methanedithiolato(2-)-kS,kS ]bis(tri-
phenylphosphine)platinum S-oxide (14). Yellow crystals,
carbons); P NMR (162 MHz) d 91.2; MS (FAB) m/z 565
C
M C1). Anal. Calcd for C H OPS : C; 59.55%, H;
(
3.75%. Found: C; 59.53%, H; 3.63%.
28 21 5
0
4
1
mp 192–193 8C decomp. (hexane–CHCl3). H NMR
(
4.6.2. 1,2,4,5,3-Tetrathiaphosphorinane (16b). Off-white
H
1
400 MHz) d 5.23 (s, 1H), 6.75 (d, JZ2.3 Hz, 1H), 6.81–
powder, mp 172–177 8C decomp. (MeOH–MeCN).
6
0
1
7
7
.89 (m, 3H), 6.92 (td, JZ7.5, 1.3 Hz, 1H), 7.05 (td, JZ7.4,
.7 Hz, 1H), 7.13 (td, JZ7.5, 1.2 Hz, 1H), 7.17–7.21 (m,
3H), 7.23–7.32 (m, 6H), 7.36 (dd, JZ7.3, 0.7 Hz, 1H),
.44–7.53 (m, 13H), 7.82 (d, JZ7.5 Hz, 1H), 8.14 (d, JZ
NMR (400 MHz) d 3.93 (s, 3H), 5.34 (s, 1H), 6.32 (br s,
1H), 6.98–7.15 (m, 8H), 7.34–7.37 (m, 2H), 7.46–7.65 (m,
2H), 7.96 (br s, 1H), 8.09 (br s, 1H), 8.29 (dd, JZ13.6,
1
3
8.8 Hz, 2H); C NMR (100.6 MHz) d 54.5 (CH), 55.7
1
3
13
31
.5 Hz, 1H), 8.55 (d, JZ7.6 Hz, 1H);
C NMR
(CH ), 61.3 (br s, CH and C), 114.5 [CH, J ( C– P)Z
3
(
(
100.6 MHz) d 54.9 (CH), 64.4 (C), 75.4 (CH), 122.7
CH), 123.0 (CH), 123.2 (CH), 123.3 (CH), 124.2 (CH),
15 Hz], 122.5 (br s, CH), 123.8 (br s, 3CH), 124.1 (CH),
124.8 (3CH), 125.2 (br s, CH), 125.6 (br s, 2CH), 126.2
(CH), 133.5 [d, J ( C– P)Z13 Hz, CH), 140.1 (br s, C),
144.2 (2C), 145.3 (C), 145.4–147.3 (2C), 164.1 (C) (the
quaternary carbon bonded to the P atom was not observed
1
3
31
1
(
24.36 (CH), 124.44 (CH), 124.5 (CH), 124.6 (2CH), 125.5
CH), 127.0 (CH), 127.9 (CH, L), 128.0 (CH, L), 128.1 (CH,
L), 128.2 (CH, L), 129.4 (C, L), 129.7 (C, L), 129.8 (C, L),

6698
A. Ishii et al. / Tetrahedron 61 (2005) 6693–6699
probably because of overlapping with signals due to CH
Supplementary data
3
carbons); P NMR (162 MHz) d 94.1; MS (EI) m/z (rel.
1
C
intensity) 564 (M , 3), 298 (100), 265 (74), 253 (67), 252
Supplementary data associated with this article can be found,
in the online version, at doi:10.1016/j.tet.2005.05.017
C
C
65). The intensity ratio of m/z 564 (M )/565 (M C1)/566
(
C
M C2) was 100/34.1/28.8, which is consistent with the
(
calculated value of 100/35.8/28.6 for C H OPS .
2
8
21
5
4
.6.3. 1,3,4,2-Trithiaphospholane (15a). White powder,
References and notes
1
mp 199–200 8C decomp. (MeOH–MeCN). H NMR
400 MHz) d 3.90 (s, 3H), 5.36 (s, 1H), 6.75 [d,
(
1
. Nakayama, J.; Ishii, A. Adv. Heterocycl. Chem. 2000, 77,
21–284.
1
31
J ( H- P)Z2.7 Hz, 1H], 6.95–7.13 (m, 7H), 7.19 (td, JZ
2
7
1
.5, 1.1 Hz, 1H), 7.33–7.40 (m, 2H), 7.46 (d, JZ7.0 Hz,
H), 7.52–7.56 (m, 1H), 8.02 (d, JZ7.5 Hz, 1H), 8.35 (dd,
2
. Fabian, J.; Senning, A. Sulfur Rep. 1998, 21, 1–42.
. Murray, R. W.; Singh, M. Comprehensive Heterocyclic
Chemistry II; Katritzky, A. R., Rees, C. W., Scrivan,
E. E. V., Eds.; Pergamon: UK, 1996, Vol. 1A, pp 429–456.
. Senning, A.; Hansen, H. C.; Abdel-Megeed, M. F.;
Mazurkiewicz, W.; Jensen, B. Tetrahedron 1986, 42, 739–746.
. Senning, A. Sulfur Lett. 1986, 4, 213–216.
3
1
3
JZ14.2, 8.8 Hz, 2H), 8.83 (d, JZ7.5 Hz, 1H); C NMR
(
(
100.6 MHz) d 54.5 (CH), 55.7 (CH ), 57.5 [d, J
31
3
1
3
31
13
C– P)Z5 Hz, C), 74.4 [d, J ( C– P)Z6 Hz, CH],
4
5
1
3
31
13
31
1
1
1
14.5 [d, J ( C– P)Z15 Hz, CH], 122.2 [d, J ( C– P)Z
1 Hz, CH], 122.7 [d, J ( C– P)Z85 Hz, C], 123.4 (CH),
23.6 (CH), 123.7 (CH), 123.8 (CH), 124.76 (CH), 124.80
13 31
6. Senning, A. Sulfur Lett. 1990, 11, 83–86.
(
1
1
CH), 125.0 (CH), 125.7 (CH), 125.8 (CH), 126.0 (CH),
31
7. Kutney, G. W.; Turnbull, K. Chem. Rev. 1982, 82, 333–357.
8. Ishii, A.; Akazawa, T.; Ding, M.-X.; Honjo, T.; Nakayama, J.;
Hoshino, M.; Shiro, M. J. Am. Chem. Soc. 1993, 115,
4914–4915.
1
3
26.9 (CH), 134.9 [d, J ( C– P)Z14 Hz, CH], 139.5 (C),
44.0 (C), 145.0 (C), 145.5 (C), 146.3 (C), 147.2 (C), 163.9
1
3
31
31
[
MS (EI) m/z (rel. intensity) 532 (M , 5), 298 (100), 265
(
(
consistent with the calculated value of 100/35.0/23.9 for
C H OPS .
d, J ( C– P)Z3 Hz, C); P NMR (162 MHz) d 101.8;
C
9. Ishii, A.; Akazawa, T.; Maruta, T.; Nakayama, J.; Hoshino,
M.; Shiro, M. Angew. Chem., Int. Ed. Engl. 1994, 33, 777–779.
10. Ishii, A.; Maruta, T.; Teramoto, K.; Nakayama, J. Sulfur Lett.
1995, 18, 237–242.
C
72), 252 (63). The intensity ratio of m/z 532 (M )/533
C
M C1)/534 (M C2) was 100/33.8/25.4, which is
C
11. Ishii, A.; Jin, Y.-N.; Nagaya, H.; Hoshino, M.; Nakayama, J.
Tetrahedron Lett. 1995, 36, 1867–1870.
2
8
21
4
1
2. 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. Jpn. 1997,
4
.6.4. 1,3,4,2-Trithiaphospholane (15b). Off-white
1
powder, mp 198–200 8C (MeOH–MeCN). H NMR
400 MHz) d 3.93 (s, 3H), 5.34 (s, 1H), 6.84–6.90 (m, 2H
(
7
3. Ishii, A. J. Synth. Org. Chem., Jpn. 1997, 55, 897–906.
0, 509–529.
1
31
d 6.86 [d, J ( H- P)Z5.9 Hz]), 6.98–7.10 (m, 7H), 7.34–
1
7
1
.38 (m, 2H), 7.46 (d, JZ7.5 Hz, 1H), 7.81 (d, JZ7.5 Hz,
H), 7.92 (d, JZ7.5 Hz, 1H), 8.06 (d, JZ8.0 Hz, 1H), 8.18
1
4. Ishii, A.; Umezawa, K.; Nakayama, J. Tetrahedron Lett. 1997,
3
8, 1431–1434.
5. Ishii, A.; Nakabayashi, M.; Nakayama, J. J. Am. Chem. Soc.
1999, 121, 7959–7960.
1
3
(
dd, JZ15.0, 8.6 Hz, 2H); C NMR (100.6 MHz) d 54.5
1
13 31
(
CH), 55.6 (CH ), 57.8 [d, J ( C– P)Z5 Hz, C], 73.9 [d,
3
1
3
31
13
31
J ( C– P)Z6 Hz, CH), 114.4 [d, J ( C– P)Z16 Hz,
CH], 123.2 (CH), 123.3 (CH), 123.6 (CH), 123.8 (CH),
16. Ishii, A.; Nakabayashi, M.; Jin, Y.-N.; Nakayama, J.
J. Organomet. Chem. 2000, 611, 127–135.
1
(
24.0 (CH), 124.3 (CH), 124.9 (CH), 125.1 (CH), 125.4
CH), 125.7 (CH), 125.8 (CH), 126.2 (CH), 129.0 [d,
17. Ishii, A.; Kawai, T.; Tekura, K.; Oshida, H.; Nakayama, J.
Angew. Chem., Int. Ed. 2001, 40, 1924–1926.
1
3
31
13
31
J ( C– P)Z83 Hz, C], 133.1 [d, J ( C– P)Z14 Hz, CH],
39.9 (C), 143.8 (C), 145.0 (C), 145.5 (C), 146.1 (C), 147.0
18. Ishii, A.; Yamashita, R.; Saito, M.; Nakayama, J. J. Org.
Chem. 2003, 68, 1555–1558.
1
1
3
31
31
(C), 163.3 [d, J ( C– P)Z4 Hz, C); P NMR (162 MHz)
d 108.0; MS (EI) m/z (rel. intensity) 532 (M , 4), 298 (100),
19. Shimada, K.; Kodaki, K.; Aoyagi, S.; Takikawa, Y.; Kabuto,
C. Chem. Lett. 1999, 695–696.
C
C
65 (73), 252 (62). The intensity ratio of m/z 532 (M )/533
2
(
20. Mloston, G.; Romanski, J.; Reisenauer, H. P.; Maier, G.
Angew. Chem., Int. Ed. 2001, 40, 393–396.
C
C
M C1)/534 (M C2) was 100/35.4/24.0, which is
2
1. Nakamura, N. J. Am. Chem. Soc. 1983, 105, 7172–7173.
2. Barton, D. H. R.; Guziec, F. S., Jr.; Shahak, I. J. Chem. Soc.,
Perkin Trans. 1 1974, 1794–1799 and references cited therein.
3. Okazaki, R.; Ishii, A.; Inamoto, N. Unpublished results:
Reaction of TripLi with HC(]S)OEt and that of
consistent with the calculated value of 100/35.0/23.9 for
C H OPS .
2
2
8
21
4
2
2
4
.7. Reaction of sulfine Z-13 with LR
2 2 2
TripCH]NNH with S Cl failed to give TripCHS.
A mixture of Z-13 (29 mg, 0.091 mmol) and LR (74.7 mg,
.185 mmol) in dichloromethane was stirred under argon at
4. The trans stereochemistry of 11 was unambiguously deter-
mined by X-ray crystallography, though the positions of the
sulfur atom and the –N]N– moiety in the thiadiazoline ring
could not be determined because of disorder.
0
room temperature for 7 h. The solvent was removed under
reduced pressure, and the residue was subjected to a short
column of silica gel (dichloromethane) to remove deriva-
tives of LR. A mixture of 15a and 15b thus obtained was
separated with HPLC (CH Cl /hexane 45:50) to give 15a
25. Opitz, G. Angew. Chem., Int. Ed. Engl. 1967, 6, 107–123.
26. v. Vargha, L.; Kov a´ cs, E. Ber. 1942, 75, 794–802.
27. Tokura, N.; Nagai, T.; Matsumura, S. J. Org. Chem. 1966, 31,
349–350.
2
2
(
15 mg, 31%) and 15b (8.0 mg, 17%).

A. Ishii et al. / Tetrahedron 61 (2005) 6693–6699
6699
2
8. Sollman, P. B.; Nagarajan, R.; Dodson, R. M. Chem. Commun.
967, 552–554.
9. Wr o´ bel, J. T.; Ruszkowska, J.; Bielawska, H. Polish J. Chem.
979, 53, 39–48.
37. Nakagawa, K.; Onoue, H.; Minami, K. Chem. Commun. 1966,
730–731.
1
2
38. Konaka, R. J. Synth. Org. Jpn. 1972, 30, 479–484.
39. Brunovlenskaya, I. I.; Gudasheva, T. A.; Skvarchenko, V. R.
Zh. Org. Khim. 1974, 10, 1495–1497.
1
3
0. Oki, M. Top. Stereochem. 1983, 14, 1–81.
3
1. Kalinowski, H.-O.; Berger, S.; Braun, S. Carbon-13 NMR
Spectroscopy; Wiley: Chichester, 1984; pp 495–501.
2. Ishii, A.; Nakamura, S.; Yamada, T.; Nakayama, J.
Tetrahedron 1997, 53, 12203–12214.
40. Steudel, R.; Latte, J. Angew. Chem., Int. Ed. Engl. 1974, 13,
603–604.
3
3
3
3
3
41. North, A. C. T.; Phillips, D. C.; Mathews, F. S. Acta
Crystallogr. Sect. A 1968, A24, 351–359.
3. Ishii, A.; Saito, M.; Murata, M.; Nakayama, J. Eur. J. Org.
Chem. 2002, 979–982.
4. Oshida, H.; Ishii, A.; Nakayama, J. Tetrahedron Lett. 2004, 45,
42. Sheldrick, G. M. SHELXL-97: Program for Crystal Structure
Refinement; G o¨ ttingen University, Germany, 1997.
43. Altomare, A.; Burla, M. C.; Camalli, M.; Cascarano, G. L.;
Giacovazzo, C.; Guagliardi, A.; Moliterni, A. G. G.; Spagna,
R. J. Appl. Crystallogr. 1999, 32, 115–119.
1
331–1334.
5. Dence, J. B.; Roberts, J. D. J. Org. Chem. 1968, 33,
251–1253.
1
6. Kornfeld, E. C.; Barney, P.; Blankley, J.; Faul, W. J. Med.
Chem. 1965, 8, 342–347.