C O MMU N I C A T I O N S
Table 1. Selected Structural Parameters of Anions of 2a and 4
bond length, pm
bond
[(CF3)3SO2]- a
[(CF3)3SO2]- b
anion of 4c
S(1)-C(1)
S(1)-C(2)
S(1)-C(3)
S(1)-O(1)
S(1)-O(2)
191.3(5)
192.4(6)
190.8(6)
145.7(4)
144.6(3)
196.1
196.1
194.1
146.5
146.5
177.2(3)
141.7(2)
142.6(2)
Figure 2. Experimental 13C NMR spectrum of the anion of 2a recorded at
243 K as compared to the simulated one (lower trace).
a X-ray investigation data, this work. b Calculated data [B3PW91/6-
311+G(3d)], this work. c X-ray investigation data.13c
The reactivity of salts 2 as a trifluoromethyl anion source was
demonstrated by reactions of 2b with SO2Cl2 and Me3SnCl, and
2a with benzaldehyde to give CF3SO2Cl (19F NMR yield 91%,
based on the transfer of one CF3 group), Me3SnCF3 (58%), and
2,2,2-trifluoro-1-phenylethanol (48%), respectively.
determined by mass spectrometry in the reaction mixture. No
evidence was obtained for the formation of any other products, that
is, silylated derivative (CF3)3S(O)OSiMe3. In the case of (Me2N)3-
-
C+Me3SiF2 as the fluoride source, the formation of (Me2N)3C-
CF3 only (δF ) -63), along with Me3SiF and an impurity of CF3H,
In conclusion, the first noncyclic [10-S-5] sulfuranide dioxides
with three S-C bonds were synthesized and fully characterized.
The syntheses of these compounds starting from different sulfur
electrophiles, the preparation of similar [10-S-5] species bearing
other substituents, and the study of chemical properties of newly
obtained compounds are underway in our group.
was observed in accordance with previous results.9a,15
The new compounds 2a,c are colorless crystals, whereas 2b was
obtained as a grayish powder. 2a,b are stable in a dry nitrogen
atmosphere at ambient temperature for days and can be stored
without decomposition at -30 °C for months. 2c is stable up to 0
°C but decomposes above 10 °C to furnish a brownish oil.
The salts obtained were characterized by elemental analysis,
multinuclear NMR spectroscopy, vibrational spectroscopy, and
X-ray analysis. Dissolved in common solvents, especially in protic
ones, the CF3-containing sulfuranide dioxides decompose upon
proton or deuterium abstraction to afford CF3H(D) and sulfone 5;
for example, for the 0.03 M solutions of 2a in Py-d5 and CD3CN
at 20 °C, the decomposition half times were found to be ca. 13 h
and 10 min, respectively, monitored by 19F NMR spectroscopy.
The X-ray investigation of 2a revealed a slightly distorted
trigonal-bipyramidal structure of anion [C(1)-S(1)-C(2) 178.9-
(3)°, C(3)-S(1)-C(1) 89.1(3)°, O(2)-S(1)-O(1) 129.2(2)°, O(2)-
S(1)-C(3) 114.4(3)°] (Figure 1). The equatorial and axial S-C
bonds are almost equal (see Table 1) and considerably longer as
compared to the equatorial S(1)-C(3) bond of 4 determined by
X-ray analysis.13c The C-F bonds of the axial trifluoromethyl
groups are somewhat longer than the corresponding ones in
equatorial CF3 - ca. 133 versus 129 pm. The S-O bonds are longer
as compared to the respective bond lengths of 4 (Table 1) and are
similar to the S-O bonds of dimethyl sulfone.16 For the related
Supporting Information Available: Preparation, analytical data,
and spectral parameters of compounds 2, experimental details of their
reactions with electrophiles, and X-ray investigation data of 2a (PDF
and CIF). This material is available free of charge via the Internet at
References
(1) (a) Organofluorine Compounds in Medicinal Chemistry and Biomedical
Applications; Filler, R., Kobayashi, Y., Yagupolskii, L. M., Eds.;
Elsevier: Amsterdam, 1993. (b) Organofluorine Chemistry - Principles
and Commercial Applications; Banks, R. E., Smart, B. E., Tatlow, J. C.,
Eds.; Plenum Press: New York, 1994.
(2) (a) Burton, D. J.; Yang, Z.-Y. Tetrahedron 1992, 48, 189-275. (b)
McClinton, M. A.; McClinton, D. A. Tetrahedron 1992, 48, 6555-6666.
(3) Ruppert, I.; Schlich, K.; Volbach, W. Tetrahedron Lett. 1984, 25, 2195-
2198.
(4) (a) Prakash, G. K. S.; Yudin, A. K. Chem. ReV. 1997, 97, 757-786. (b)
Singh, R. P.; Shreeve, J. M. Tetrahedron 2000, 56, 7613-7632. (c)
Prakash, G. K. S.; Mandal, M. J. Fluorine Chem. 2001, 112, 123-131.
(5) (a) Russel, J.; Roques, N. Tetrahedron 1998, 54, 13771-13782. (b) Large,
S.; Roques, N.; Langlois, B. R. J. Org. Chem. 2000, 65, 8848-8856. (c)
Blond, G.; Billard, T.; Langlois, B. R. Tetrahedron Lett. 2001, 42, 2473-
2475 and references therein.
(6) Chemistry of HyperValent Compounds; Akiba, K., Ed.; Viley-VCH: New
York, 1999.
- 9a
7a
(7) (a) Kolomeitsev, A.; Go¨rg, M.; Dieckbreder, U.; Lork, E.; Ro¨schenthaler,
G.-V. Phosphorus, Sulfur Silicon Relat. Elem. 1996, 109, 597-600. (b)
Kolomeitsev, A. A.; Dieckbreder, U.; Pavlenko, N. V.; Rozhenko, A. B.;
Lork, E.; Go¨rg, M.; Ro¨schenthaler, G.-V. 15th International Symposium
on Fluorine Chemistry; Vancouver, Canada, 2-7.08.1997, Abstract In(2)
C-6.
(CF3)2SiMe3
and (CF3)2PMe3 species with the same TBP
structure type, longer axial E-CF3 distances [Si-CF3 205.6(4),
P-CF3 197.4(4) vs S-C(1)F3 191.3(5) pm in 2a] were found.
The calculated [B3PW91/6-311+G(3d)] structural parameters
and vibrational frequencies of the [(CF3)3SO2]- ion are in good
agreement with the X-ray analysis data (see Table 1), as well as
with the experimental IR and Raman frequencies (cf., Supporting
Information).
(8) Tyrra, W.; Naumann, D.; Kirij, N. V.; Kolomeitsev, A. A.; Yagupolskii,
Yu. L. J. Chem. Soc., Dalton Trans. 1999, 657-658.
(9) (a) Kolomeitsev, A.; Bissky, G.; Lork, E.; Movchun, V.; Rusanov, E.;
Kirsch, P.; Ro¨schenthaler, G.-V. Chem. Commun. 1999, 1017-1018. (b)
Maggiarosa, N.; Tyrra, W.; Naumann, D.; Kirij, N. V.; Yagupolskii, Yu.
L. Angew. Chem., Int. Ed. 1999, 38, 2252-2253.
The structures of compounds 2 in Py-d5, CD3CN, and THF-d8
solutions were investigated by 19F NMR spectroscopy for the
temperature interval between -30 and 20 °C. Noteworthy, signals
of two different types of CF3 groups with an integral intensities
(10) (a) Patel, N. R.; Kirchmeier, R. L. Inorg. Chem. 1992, 31, 2537-2540.
(b) Sandhu, A.; Gard, G. L.; Patel, N. R.; Kirchmeier, R. L.; Shreeve, J.
M. Inorg. Chem. 1993, 32, 3205-3208.
(11) Kirij, N. V.; Yagupolskii, Yu. L.; Maggiarosa, N.; Tyrra, W.; Naumann,
D. J. Fluorine Chem. 2001, 112, 213-218.
(12) Sevenard, D. V.; Kirsch, P.; Ro¨schenthaler, G.-V.; Movchun, V. N.;
4
ratio of 2:1, split by a J (F,F) coupling constant of 16 Hz, were
Kolomeitsev, A. A. Synlett 2001, 379-381.
detected even at ambient temperature. This fact indicates the absence
of an exchange of axial and equatorial trifluoromethyl substituents
at the NMR time scale in the temperature interval investigated. The
13C NMR spectrum of 2a measured at -30 °C for a THF-d8 solution
also showed resonances of two different types of CF3 groups, the
signal of the equatorial CF3 group is a first-order quartet of septets,
while the resonance of the axial CF3 groups exhibits a complex
(13) (a) Garber, K.; Ault, B. S. Inorg. Chem. 1983, 22, 2509-2513. (b) Perkins,
C. W.; Martin, J. C. J. Am. Chem. Soc. 1983, 105, 1377-1379. (c) Perkins,
C. W.; Wilson, S. R.; Martin, J. C. J. Am. Chem. Soc. 1985, 107, 3209-
3218 and references therein. (d) Lee, I.; Kim, C. K.; Li, H. G.; Sohn, C.
K.; Kim, C. K.; Lee, H. W.; Lee, B.-S. J. Am. Chem. Soc. 2000, 122,
11162-11172. (e) Barrera, M. D.; Cheburkov, Yu.; Lamanna, W. M. J.
Fluorine Chem. 2002, 117, 13-16.
(14) Oberhammer, H.; Knerr, G. D.; Shreeve, J. M. J. Mol. Struct. 1982, 82,
143-146.
(15) Kolomeitsev, A. A.; Bissky, G.; Kirsch, P.; Ro¨schenthaler, G.-V. J.
Fluorine Chem. 2000, 103, 159-161.
(16) Langs, D. A.; Silverton, J. V.; Bright, W. M. J. Chem. Soc. D 1970, 1653.
12
13
12
A3B3M3X spin system with A ) F3 Cax, B ) F3 Cax, M ) F3 Ceq,
13
X ) Cax. The experimental spectrum is in excellent agreement
with the simulated spectrum (Figure 2).
JA030155H
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