1-Adamantyl-tert-butyltetrathiolane 2,3-dioxide: First isolable vic- disulfoxide and efficient precursor of S2O [15]

Full text of DOI:10.1021/ja9915955

J. Am. Chem. Soc. 1999, 121, 7959-7960
7959
putational chemistry,8 and space science9 but not in organic
chemistry.10,11 We report here the structure determination of the
tetrathiolane 2,3-dioxide 3 and satisfactory trapping experiments
of SO2 and S3.
1-Adamantyl-tert-butyltetrathiolane 2,3-Dioxide:
First Isolable Wic-Disulfoxide and Efficient Precursor
of S2O
A solution of 1a12 in dichloromethane was treated with an
acetone solution of dimethyldioxirane (DMD)13 (4 molar amounts)
at -20 °C and then the solvent was removed in vacuo at -20
°C.14 Recrystallization of the pale-yellow residue from a mixed
solvent of dichloromethane and hexane at -20 °C led to the two
polymorphic crystals; pale-yellow plates (major, mp 74-76 °C
dec) and yellow prisms (minor, mp 67-68 °C dec), which are
separable mechanically and gave the same 1H NMR spectrum at
-10 °C.15 The infrared spectrum of the crystals, which showed
two strong absorptions due to the SdO stretching vibrations (1109
and 1135 cm-1), and elemental analysis results are indicative of
the compound being a disulfoxide derivative of 1a. Finally, its
structure was determined to be the (2RS,3RS)-2,3-dioxide 3 by
Akihiko Ishii,* Masaaki Nakabayashi, and Juzo Nakayama*
Department of Chemistry, Faculty of Science
Saitama UniVersity, Urawa, Saitama 338-8570, Japan
ReceiVed May 13, 1999
Vic-Disulfoxides (R-disulfoxides) are one of the important
intermediates in the oxidation of oligosulfides and have been
drawing considerable attention.1-3 Nevertheless, most of them are
still elusive and only a few were detected by NMR spectroscopy.3
We recently reported that the oxidation of tetrathiolanes (1)
yielded the corresponding dithiirane 1-oxides (2),4 and have now
discovered that the intermediate, giving 2a, is the corresponding
tetrathiolane 2,3-dioxide (3), a Vic-disulfoxide, which can be
isolated as crystals at room temperature. In addition, we also
disclosed that the decomposition of 3 provides 2a and S2O, which
disproportionates to SO2 and S3. S2O and S3 are sulfur analogues
of O3 and have been drawing much attention in inorganic
chemistry,5 coordination chemistry,6 physical chemistry,7 com-
X-ray crystallographic analysis.16,17 Figure 1 depicts an ORTEP
drawing of 3 obtained from a yellow prism (minor) with the
relevant bond lengths and bond angles. Both oxygen atoms in 3
occupy axial orientations and are trans to each other with respect
to the S(2)-S(3) bond. The length of the bond S(2)-S(3) (2.301
Å) is approximately 12% longer than that of the corresponding
S-S bond of 1a (2.052 Å)12 and the value is comparable to that
of a calculated S-S bond length of meso-MeS(O)S(O)Me (2.303
Å) reported recently.18 The pale-yellow plates (major) were
disordered in the crystals and X-ray crystallographic analysis of
the mixture, which consisted of 86% of one enantiomer (2R,3R
or 2S,3S) and 14% of the other, led to unsatisfactory results.16
The 2,3-dioxide 3 was stable in the crystalline state even at
room temperature for several hours but in solution decomposed
above -10 °C cleanly to the corresponding diastereomeric
dithiirane 1-oxides, (1RS,3SR)- and (1RS,3RS)-2a (53 and 39%,
respectively), the tetrathiolane 1a (8%) (1H NMR), and elemental
(1) For reviews, see: (a) Freeman, F. Chem. ReV. 1984, 84, 117-135. (b)
Clennan, E.; Stensaas, K. L. Org. Prep. Proced. Int. 1998, 30, 551-600. (c)
Oae, S. Kagaku 1979, 33, 240-243. (d) Oae, S.; Takata, T. Kagaku 1978,
34, 891-899.
(2) For recent papers on Vic-disulfoxides: (a) Freeman, F.; Lee, C. J. Org.
Chem. 1988, 53, 1263-1266. (b) Block, E.; Bayer, T. J. Am. Chem. Soc.
1990, 112, 4584-4585. (c) Gu, D.; Harpp, D. N. Tetrahedron Lett. 1993, 34,
67-70. (d) Clennan, E. L.; Zhang, H. J. Org. Chem. 1994, 59, 7952-7954.
(e) Nakayama, J.; Mizumura, A.; Yokomori, Y.; Krebs, A.; Schu¨tz, K.
Tetrahedron Lett. 1995, 36, 8583-8586. (f) Clennan, E. D.; Stensaas, K. L.
J. Org. Chem. 1996, 61, 7911-7917 and references therein.
(3) (a) Freeman, F.; Angeletakis, C. N. J. Am. Chem. Soc. 1981, 103, 6232-
6235. (b) Freeman, F.; Angeletakis, C. N. J. Am. Chem. Soc. 1982, 104, 5766-
5774. (c) Freeman, F.; Angeletakis, C. N. J. Am. Chem. Soc. 1983, 105, 4039-
4049. (d) Fokins, P. L.; Harpp, D. N. J. Am. Chem Soc. 1991, 113, 8998-
9000.
(9) For examples, see: Na, C. Y.; Esposito, L. W. Icarus 1997, 125, 364-
368. Spencer, J. R.; McEwen, A. S.; McGrath, M. A.; Sartretti, P. Icarus
1997, 127, 221-237.
(4) Jin, Y.-N.; Ishii, A.; Sugihara, Y.; Nakayama, J. Tetrahedron Lett. 1998,
39, 3525-3528.
(5) For reviews on S2O, see: Murthy, A. R. V.; Kutty, T. R. N.; Sharma,
D. K. Int. J. Sulf. Chem. 1971, 6, 161-175. Fluck, E. Chem.-Ztg. 1980, 104,
252.
(10) Dodson, R. M.; Srinivasan, V.; Sharma, K. S.; Sauers, R. F. J. Org.
Chem. 1972, 37, 2367-2372.
(11) Ghosh, T.; Bartlett, P. D. J. Am. Chem. Soc. 1988, 110, 7499-7506.
(12) Ishii, A.; Jin, Y.; Sugihara, Y.; Nakayama, J. J. Chem. Soc., Chem.
Commun. 1996, 2681-2682.
(6) Urove, G. A.; Welker, M. E. Organometallics 1988, 7, 1013-1014.
Raseta, M. E.; Cawood, S. A.; Welker, M. E. J. Am. Chem. Soc. 1989, 111,
8268-8270. Brown, D. S.; Owens, C. F.; Wilson, B. G.; Welker, M. E.;
Rheingold, A. L. Organometallics 1991, 10, 871-875 and references therein.
For reviews, see: Schenk, W. A. Angew. Chem., Int. Ed. Engl. 1987, 26,
98-109. Pandey, K. K. Prog. Inorg. Chem. 1992, 40, 445-502. Hill, A. F.
AdV. Organomet. Chem. 1994, 36, 159-227.
(7) S2O: Blukis, U.; Myers, R. J. J. Phys. Chem. 1965, 69, 1154-1156.
Phillips, L. F.; Smith, J. J.; Meyer, B. J. Mol. Spectrosc. 1969, 29, 230-243.
Hapke, B.; Graham, F. Icarus 1989, 79, 47-55. Zhang, Q.; Dupre´, P.;
Grzybowski, B.; Vaccaro, P. H. J. Chem. Phys. 1995, 103, 67-79. S3: Meyer,
B.; Stroyer-Hansen, T.; Oommen, T. V. J. Mol. Spectrosc. 1972, 42, 335-
343. Lenain, P.; Picquenard, E.; Lesne, J. L.; Corset, J. J. Mol. Struct. 1986,
142, 355-358.
(8) S2O: Davy, R. D.; Skoumbourdis, E. Mol. Phys. 1998, 94, 539-546.
Mu¨ller, T.; Dupre´, P.; Vaccaro, P. H.; Pe´rez-Bernal, F.; Ibrahim, M.; Iachello,
F. Chem. Phys. Lett. 1998, 292, 243-253. S3: Salahub, D. R.; Foti, A. E.;
Smith, V. H., Jr. J. Am. Chem. Soc. 1978, 100, 7847-7859. Toscano, M.;
Russo, N.; Rubio, J. J. Chem. Soc., Faraday Trans. 1996, 92, 2681-2684.
Baeck, K. K.; Watts, J. D.; Bartlett, R. J. J. Chem. Phys. 1997, 107, 3853-
3863. S2O and S3: Patterson, C. H.; Messmer, R. P. J. Am. Chem. Soc. 1990,
112, 4138-4150. Ivanic, J.; Atchity, G. J.; Ruedenberg, K. J. Chem. Phys.
1997, 107, 4307-4317.
(13) Adam, W.; Bialas, J.; Hadjiarapoglou, L. Chem. Ber. 1991, 124, 2377.
Adam, W.; Hadjiarapoglou, L.; Smerz, A. Chem. Ber. 1991, 124, 227-232.
(14) Repeated recrystallization (3 times) of the residue at -20 °C from
CH2Cl2-EtOH gave pure 3 in 25-30% yield as pale-yellow, fine plates.
(15) 3: 1H NMR (400 MHz, CDCl3, 263 K) δ 1.45 (br s, 9H, t-Bu), 1.65
(br s, 6H), 2.09 (br s, 9H); 13C NMR (100.6 MHz, CDCl3, 263 K) δ 29.2
(CH), 33.4 (br s, CH3), 35.9 (CH2), 42.2 (CH2), 44.5 (C), 46.9 (C), 153.9 (C).
(16) X-ray data for 3: For yellow prisms: monoclinic, space group P21/n,
a ) 6.4150(3) Å, b ) 18.878(1) Å, c ) 13.7410(9) Å, â ) 97.349(4)°, V )
1650.4(2) Å3, Z ) 4, µ(Mo KR) ) 5.54 mm-1, temperature of data collection
153 K. R (Rw) ) 0.077 (0.086) and GOF ) 3.761; max/min residual electron
density ) 2.06/-1.97 e Å-3 for 3683 reflections [I g 2σ(I)] (286 parameters).
For pale-yellow plates: orthorhombic, space group P2nn, a ) 6.5200(6) Å,
b ) 13.970(1) Å, c ) 18.386(2) Å, V ) 1665.6(3) Å3, Z ) 4, µ(Mo KR) )
5.49 mm-1, temperature of data collection 153 K. R (Rw) ) 0.090 (0.094)
and GOF ) 3.422; max/min residual electron density ) 2.37/-0.83 e Å-3
for 1992 reflections [I g 2σ(I)] (210 parameters). For more details of the
X-ray single-crystal analyses, see Supporting Information.
(17) The structure of the precursor for 2 was previously4 assumed to be
the tetrathiolane 1-oxide and now should read the Vic-disulfoxide 3.
(18) Lacombe, S.; Loudet, M.; Dargelos, A.; Robert-Banchereau, E. J. Org.
Chem. 1998, 63, 2281-2291.
10.1021/ja9915955 CCC: $18.00 © 1999 American Chemical Society
Published on Web 08/12/1999

7960 J. Am. Chem. Soc., Vol. 121, No. 34, 1999
Communications to the Editor
Scheme 1
yield (85%) along with (1RS,3SR)- and (1RS,3RS)-2a (50 and
38%, respectively), 5 (10%), and 1a (2%). The formation of 4
and 6 can be explained as the results of the reaction of
2,3-dimethyl-1,3-butadiene with S2O and that of norbornene with
S3, respectively.11 The decomposition of 3 in the presence of both
2,3-dimethyl-1,3-butadiene and norbornene furnished 4 over-
whelmingly (72%) as the trapping product. In addition, the
decomposition rate of 3 and yields of 2a were independent of
the presence of the trapping reagents. Therefore, we conclude
that 3 splits into 2a and S2O (and 5 as the byproduct) initially
and S2O reacts quickly with 2,3-dimethyl-1,3-butadiene in a [4+2]
manner10 to give 4, whereas the reaction of S2O with norbornene
does not take place or is sluggish allowing S2O to disproportionate
to S3 and SO2; the S3 thus formed reacts with norbornene
effectively to give 6. Such a disproportionation was observed in
an argon matrix by Raman spectroscopy.21 The reaction of S3
with the thioketone 5 also explains the formation of 1a in the
absence of the trapping reagents.
Figure 1. ORTEP drawing (50% ellipsoids) of 1-adamantyl-tert-
butyltetrathiolane 2,3-dioxide (3). Relevant bond lengths (Å) and bond
angles (deg): C1-S1 1.868(2); S1-S2 2.054; S2-S3 2.301(1); S3-S4
2.052(1); S4-C1 1.861(2); C1-C2 1.606(3); C1-C3 1.599(3); S2-O1
1.461(2); S3-O2 1.409(2); C1-S1-S2 109.3(1); S1-S2-S3 94.4(1);
S2-S3-S4 93.0(1); C1-S4-S3 109.6(1); S1-C1-S4 107.8(1); C1-
S1-S2-S3 39.6(1); S1-S2-S3-S4 45.5(1); S2-S3-S4-C1 42.6(1).
sulfur (detected by TLC); vide infra, for the formation mechanism
of 1a. The decomposition of 3 obeyed the first-order kinetics with
a half-life of approximately 15 min at 25 °C in CDCl3 (k ) 6.8
× 10-4 s-1, c ) 2.75 × 10-2 M). The thermal stability of 3 in
solution is much larger than that of acyclic Vic-disulfoxides,
RS(O)S(O)R,3a-c which could be observed below -40 °C, and a
little larger than or comparable to that of bridged bicyclic Vic-
disulfoxides, 8-substituted 6,7-dithiabicyclo[3.2.1]octane 6,7-
dioxides.3d The dioxide 3 showed no tendency to rearrange to
the OS-sulfenyl sulfinate [R-S(O)OS-R] in contrast to the
behavior of other Vic-disulfoxides.1a,d,2a,3 Rearrangement-ring
expansion would widen the S(1)-C(1)-S(4) angle increasing the
unfavorable steric interaction between the two bulky substituents
and the neighboring sulfur atoms S(1) and S(4).
Formation of the trithiolane 6 at elevated temperatures11,20,22
was reported previously in reactions of norbornene with reactive
sulfur species, which were unspecified or proposed to be S3 or
S2. In the above trapping experiments no adducts23 between S2
and 2,3-dimethyl-1,3-butadiene were observed.
In summary, we have succeeded in the unambiguous structure
determination of the tetrathiolane 2,3-dioxide 3, the first isolable
Vic-disulfoxide. In addition, we revealed that 3 releases S2O, which
disproportionates to S3 and SO2, almost stoichiometrically at
ambient temperature.
Acknowledgment. This work was supported by Grants-in-Aid for
Scientific Research (Nos. 09239206, 10133206, and 09440213) from the
Ministry of Education, Science, Sports and Culture of Japan.
Supporting Information Available: Characterization data (1H and
13C NMR, IR, MS, and elemental analyses) for 3, 4, and 5, and structure
determination summaries and tables of X-ray structure data for 3 (PDF).
This material is available free of charge via the Internet at http://pubs.acs.org.
JA9915955
(20) Bartlett, P. D.; Ghosh, T. J. Org. Chem. 1987, 52, 4937-4943.
(21) Tang, S.-Y.; Brown, C. W. Inorg. Chem. 1975, 14, 2856-2858.
Hopkins, A. G.; Tang, S.-Y.; Brown, C. W. J. Am. Chem. Soc. 1973, 95,
3486-3490.
(22) Shields, T. C.; Kurtz, A. N. J. Am. Chem. Soc. 1969, 91, 5415-5416.
Steliou, K.; Salama, P.; Brodeur, D.; Gareau, Y. J. Am. Chem. Soc. 1987,
109, 926-927. Steliou, K.; Gareau, Y.; Milot, G.; Salama, P. Phosphorus,
Sulfur, Silica 1989, 43, 209-241. Sato, R.; Satoh, S.; Saito, M. Chem. Lett.
1990, 139-142. Steliou, K.; Gareau, Y.; Milot, G.; Salama, P. J. Am. Chem.
Soc. 1990, 112, 7819-7820. Gilchrist, T. L.; Wood, J. E. J. Chem. Soc., Chem.
Commun. 1992, 1460-1461. Micallef, A. S.; Bottle, S. E. Tetrahedron Lett.
1997, 38, 2303-2306. English, R. F.; Rakitin, O. A.; Rees, C. W.; Vlasova,
O. G. J. Chem. Soc., Perkin Trans. 1 1997, 201-205.
Trapping experiments were done to verify the formation of
S2O and S3 during the decomposition of 3. The results are
summarized in Scheme 1. Thus, 2,3-dioxide 3 was allowed to
decompose in the presence of 2,3-dimethyl-1,3-butadiene (8 molar
amounts) at room temperature to give the 3H,6H-1,2-dithiin
1-oxide 419 in 87% yield along with (1RS,3SR)- and (1RS,3RS)-
2a (53 and 33%, respectively), 1-adamantyl tert-butyl thioketone
(5)19 (11%), and 1a (3%), whereas in the presence of norbornene
(10 molar amounts), the trithiolane 619,20 was obtained in high
(23) For reviews on chemical reactivities of S2, see: Harpp, D. N.
Phosphorus, Sulfur, Silicon 1997, 120 & 121, 41-59. Tardif, S. L.; Rys, A.
Z.; Abrams, C. B.; Abu-Yousef, I. A.; Leste´-Lasserre, P. B. F.; Schultz, E. K.
V.; Harpp, D. N. Tetrahedron 1997, 53, 12225-12236. Steliou, K. Acc. Chem.
Res. 1991, 24, 341-350.
(19) The yields of 4 and 6 were determined by 1H NMR with dibenzyl as
the internal standard. See Supporting Information for 4 and 5.