H. P. Reisenauer, G. Mloston, J. Romanski, P. R. Schreiner
FULL PAPER
fur (S2) elimination. The proposed reaction pathway is well
supported by DFT computations that show that the desul-
furization of an oxathiirane is a highly exothermic two-step
process with nearly 0 kcalmol–1 activation enthalpy. This is
a prototypical sulfur transfer reaction involving oxathiirane
intermediates as sulfur donors.[20]
The desulfurization of putative oxathiirane intermediates
appears also important in some biological transformations,
e.g., in the context of oxidative stress damage of tRNA mo-
lecules containing 2-thiouridine nucleosides, which can be
converted, inter alia to their uridine analogues.[21]
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Experimental Section
General: A series of S-oxides 9 and sulfines 5 was prepared accord-
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trithiolanes and thioketones with m-chloroperbenzoic acid (m-
CPBA): 2,2,5,5-tetramethyl-1,2,4-trithiolane 4-oxide (9),[12b] thio-
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tor system fitted with CsI windows for IR and BaF2 windows for
UV/Vis measurements. Matrix temperatures were measured and
controlled by a Scientific Instruments 9600-1 silicon diode tempera-
ture controller. For irradiations, a mercury high-pressure lamp
(HBO 200, Osram) with a monochromator (Bausch & Lomb) was
used (band width ca. 10 nm). IR spectra were recorded with a
Bruker IFS 55 FTIR spectrometer (4500–300 cm–1, resolution
0.7 cm–1). UV/Vis spectra were recorded with a JASCO V-670 spec-
trophotometer. For the combination of high-vacuum flash pyrolysis
with matrix isolation, we employed a home-built, water-cooled
oven directly connected to the vacuum shroud of the cryostat. The
pyrolysis zone consisted of an empty quartz tube (inner diameter
8 mm, length of heating zone 50 mm) resistively heated by a
thermo-coax wire. The temperature was controlled by an Ni/CrNi
thermocouple. In order to produce matrix-isolated thioacetone S-
oxide (dimethylsulfine, 5d), 1,2,4-trithiolane 4-oxide 9 was evapo-
rated from a pre-cooled (0 °C) storage vessel and pyrolysed at ca.
600 °C. Thioketone S-oxides 5a,e–f were evaporated under high
vacuum (5a at 35 °C, 5e at 25 °C, 5f at –10 °C) and condensed with
a large excess of argon on a cold spectroscopic window. The ob-
tained matrices were photolyzed, and the products formed were
analyzed by means of FT-IR and UV/Vis spectroscopy.
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Supporting Information (see footnote on the first page of this arti-
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Acknowledgments
This study was supported by the Deutscher Akademischer Aus-
tauschdienst (DAAD) within the partnership between the Univer-
sity of Lodz and the Justus Liebig University. G. M. acknowledges
financial support from the Alexander-von-Humboldt Foundation
(Bonn).
[24]
M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria,
M. A. Robb, J. R. Cheeseman, J. Montgomery, J. A., T. Vreven,
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