Evidence for a nonradical pathway in the photoracemization of aryl sulfoxides

Article abstract of DOI:10.1021/ja017228m

Photolysis of (R_s,S_c)-1-deuterio-2,2-dimethylpropyl p-tolyl sulfoxide provides mainly (S_s,S_c)-1-deuterio-2,2-dimethylpropyl p-tolyl sulfoxide at low conversion, though the other two stereoisomers are formed to s

Full text of DOI:10.1021/ja017228m

Published on Web 02/20/2002
Evidence for a Nonradical Pathway in the Photoracemization
of Aryl Sulfoxides1
Brian W. Vos and William S. Jenks*
Contribution from the Department of Chemistry, Iowa State UniVersity, Ames, Iowa 50011-3111
Received October 4, 2001
Abstract: Photolysis of (RS,SC)-1-deuterio-2,2-dimethylpropyl p-tolyl sulfoxide provides mainly (SS,SC)-1-
deuterio-2,2-dimethylpropyl p-tolyl sulfoxide at low conversion, though the other two stereoisomers are
formed to smaller extents. Thus, the predominant process leading to sulfur inversion yields only sulfur
inversion, without inversion of the adjacent CHD stereogenic center. This is taken as evidence for a
mechanism for photochemical epimerization of sulfoxides that does not involve homolytic R-cleavage
chemistry.
Introduction
inversion mechanism is required to establish it as one of the
primary photoprocesses of sulfoxides, even if it has been
Sulfoxides undergo photochemically induced epimerization
at sulfur2-7 despite the ground-state barrier of approximately
40 kcal mol-1. It is well established that carbon-sulfur bond
homolysis (R-cleavage) is an extremely common photochemical
reaction of sulfoxides,8-12 and recombination of radical pairs
or biradicals so-generated necessarily provides a mechanism for
racemization. Nonetheless, it has been asserted that photochemi-
cal stereomutation occurs through a direct inversion of the sulfur
center,2,13-16 even though some results3,4,7,17 demand that
carbon-sulfur bond rupture occurs in the process of epimer-
ization of the sulfur. Since R-cleavage is required in some
instances of photochemical sulfoxide epimerization, and is
known to occur from product and laser flash photolysis
studies,8,11,12,18,19 it is clear that positive evidence for a direct
supposed by a series of authors. In this paper, we present such
evidence for a nonhomolytic pathway.
Circumstantial evidence in favor of the existence of a
nonhomolytic pathway for racemization has accumulated over
the last several years. Sulfoxides with substituents that would
form poorly stabilized radicals on R-cleavage have relatively
high quantum yields for racemization despite low quantum
yields for product formation.12,15,16 Higher product yields are
observed when the nascent radical is, for instance, benzyl.12,14
Formation of sulfinyl radicals on the ns-µs time scale follows
the same trend in that more stabilized alkyl radicals lead to
higher yields of PhSO• from phenyl sulfoxides.11
A second line of evidence is observed from the simple
sulfoxide derivatives of several fluorescent chromophores.15,16,20
In these compounds, the sulfoxide derivatives have decidedly
lower fluorescence yields than the parent arenes. This is not
accompanied by a rise in triplet yield or product formation and
is unique to the sulfoxide, among sulfide, sulfoxide, and sulfone
derivatives.20 It was hypothesized that the racemization event
was the source of the nonradiative decay. Finally, multireference
ab initio methods have been used to demonstrate that, for
DMSO, stationary points exist on excited-state energy surfaces
that have C2V symmetry and are lower in energy than any
geometry with Cs symmetry.21
* Address correspondence to this author: E-mail: wsjenks@iastate.edu.
(1) Photochemistry and Photophysics of Aromatic Sulfoxides. 11. For Part 10
in the series, see ref 20.
(2) Mislow, K.; Axelrod, M.; Rayner, D. R.; Gottardt, H.; Coyne, L. M.;
Hammond, G. S. J. Am. Chem. Soc. 1965, 87, 4958-9.
(3) Archer, R. A.; Kitchell, B. S. J. Am. Chem. Soc. 1966, 88, 3462-3.
(4) Archer, R. A.; De Marck, P. V. J. Am. Chem. Soc. 1969, 91, 1530-2.
(5) Spry, D. O. J. Am. Chem. Soc. 1970, 92, 5006-8.
(6) Kishi, M.; Komeno, T. Tetrahedron Lett. 1971, 28, 2641-4.
(7) Ganter, C.; Moser, J.-F. HelV. Chim. Acta 1971, 54, 2228-51.
(8) Still, I. W. J. In The Chemistry of Sulfones and Sulfoxides; Patai, S.,
Rappaport, Z., Stirling, C. J. M., Eds.; John Wiley & Sons Ltd.: New
York, 1988; pp 873-87.
(9) Jenks, W. S.; Gregory, D. D.; Guo, Y.; Lee, W.; Tetzlaff, T. In Organic
Photochemistry; Ramamurthy, V., Schanze, K. S., Eds.; Marcel Dekker:
New York, 1997; Vol. 1, pp 1-56.
The underlying assumption in these works is that excitation
of the sulfoxide is followed by geometric relaxation in the
excited state. The excited state geometry is presumed to be one
in which the sulfur is either no longer stereogenic or in which
the potential for inversion is considerably lower than in the
ground state. In this paper, we report evidence for just this sort
of process, based on photolysis of a substrate with two adjacent
(10) Guo, Y.; Darmanyan, A. P.; Jenks, W. S. Tetrahedron Lett. 1997, 38, 8619-
22.
(11) Darmanyan, A. P.; Gregory, D. D.; Guo, Y.; Jenks, W. S. J. Phys. Chem.
A 1997, 101, 6855-63.
(12) Guo, Y.; Jenks, W. S. J. Org. Chem. 1997, 62, 857-64.
(13) Schultz, A. G.; Schlessinger, R. H. J. Chem. Soc., Chem. Commun. 1970,
1294-5.
(14) Guo, Y.; Jenks, W. S. J. Org. Chem. 1995, 60, 5480-6.
(15) Tsurutani, Y.; Machida, S.; Horie, K.; Kawashima, Y.; Nakano, H.; Hirao,
K. J. Photochem. Photobiol., A 1999, 122, 161-8.
(16) Tsurutani, Y.; Yamashita, T.; Horie, K. Polym. J. 1998, 30, 11-6.
(17) Kropp, P. J.; Fryxell, G. E.; Tubergen, M. W.; Hager, M. W.; Harris, G.
D., Jr.; McDermott, T. P., Jr.; Tornero-Velez, R. J. Am. Chem. Soc. 1991,
113, 7300-10.
(19) Darmanyan, A. P.; Gregory, D. D.; Guo, Y.; Jenks, W. S.; Burel, L.; Eloy,
D.; Jardon, P. J. Am. Chem. Soc. 1998, 120, 396-403.
(20) Lee, W.; Jenks, W. S. J. Org. Chem. 2001, 66, 474-80.
(21) Cubbage, J. W.; Jenks, W. S. J. Phys. Chem. A 2001, 105, 10588-95.
(18) Guo, Y.; Darmayan, A.; Jenks, W. S. Tetrahedron Lett. 1997, 38, 8619-
22.
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10.1021/ja017228m CCC: $22.00 © 2002 American Chemical Society

Nonradical Pathway in the Photoracemization of Aryl Sulfoxides
A R T I C L E S
Scheme 1
stereogenic centers. Inversion of the sulfur center alone is the
predominant process.
Figure 1. C1-proton resonances of (RS,RC)-1 and (SS,SC)-1 as a function
of photolysis time. The spectra are normalized so that the height of the
(RS,RC)-1 peak is approximately constant. The ratios of (SS,SC)-1 to
(RS,RC)-1 were determined by line shape fitting of the spectra. The % 2.8
ppm was determined by integration of the overall 2.8 and 2.5 regions of
the spectra and represents the fraction of the total sulfoxide concentration
that is (RS,RC)-1 or (SS,SC)-1. The % SS was determined by chiral HPLC
and represents the fraction of the total sulfoxide concentration that is
(SS,RC)-1 or (SS,SC)-1.
Results and Discussion
Photolysis of (RS,SC)-1-deuterio-2,2-dimethylpropyl p-tolyl
sulfoxide [(RS,SC)-1] was used to probe for a noncleavage
pathway to sulfur inversion, as illustrated in Scheme 1. Because
there is only a trivial diastereomeric preference on recombination
of the radical pair produced by R-cleavage and because both
radicals are inherently achiral, R-cleavage will provide all three
new stereoisomers essentially without preference. In contrast,
direct sulfur inversion of (RS,SC)-1 provides (SS,SC)-1 exclu-
sively. The structure of 1 as an aryl primary-alkyl sulfoxide is
known to reduce the quantum yield for R-cleavage chemistry.12
The expected major product, a sulfenic ester, would be
recognized easily.
Photolysis of (RS,SC)-1 at 360 µM concentration in acetoni-
trile was followed by removal of samples as a function of time.
The solvent was evaporated from each sample, and the residual
material dissolved in CDCl3. The two RS stereoisomers are
separable by chiral chromatography from the two SS isomers
and were quantified relative to one another. However, the
stereogenic center at C1 does not lend itself to chromatographic
resolution. The C1-proton of the (RS,SC) and (SS,RC) enantiomeric
pair appears at 2.52 ppm and that of the (RS,RC) and (SS,SC)
enantiomers appears at 2.81. Thus each pair of enantiomers was
quantified in relation to the other. Use of a chiral shift reagent
provides modest resolution within each enantiomeric pair, based
again on the sulfur center. This allowed for direct quantification
of the ratio of the (SS,SC) and (RS,RC) isomers (Figure 1), but
the separation between enantiomers was not sufficient to allow
quantification of the minor (SS,RC) isomer in the presence of
the large quantity of (RS,SC)-1. However, estimates of the
concentrations of all four isomers were obtained by using a
combination of the three measurements. While very small
quantities of products other than stereoisomers of 1 were
undoubtedly formed, none was above the detection limit by
HPLC or NMR.
Figure 2. Concentrations of the minor isomers as a function of photolysis
time, along with the kinetic simulation.
isomers of 1 (<10-4 M) in the presence of ca. 0.1 M shift
reagent. The absolute concentration data are given in Figure 2.
The initial product of photolysis of (RS,SC)-1 is largely
(SS,SC)-1, though a smaller amount of (SS,RC)-1 is also formed.
Over the course of about 17% total conversion to the SS isomers,
the initial quantity of (RS,RC)-1 does not change significantly.
We believe this is because while it is being drained largely to
(SS,RC)-1, it is also being created by R-cleavage chemistry of
the major isomer (RS,SC)-1. The kinetic data were simulated22
by using two sets of rate constants that were each constrained
to be internally identical. The first, kS, connects (RS,RC)-1 and
(SS,RC)-1 as one pair and (SS,SC)-1 and (RS,SC)-1 as the other.
Figure 1 shows the region of the NMR spectrum where the
C1-protons of the (SS,SC) and (RS,RC) isomers are observed as
a function of photolysis time. The initial solution contained
approximately 94% (RS,SC)-1, 5% (RS,RC)-1, and 1% (SS,RC)-
1. As can be seen, (SS,SC)-1 grows in preferentially. The signal-
to-noise ratio was limited by the absolute concentrations of the
(22) Barshop, B. A.; Wrenn, R. F.; Frieden, C. Anal. Biochem. 1983, 130,
134-45.
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J. AM. CHEM. SOC. VOL. 124, NO. 11, 2002 2545

A R T I C L E S
Vos and Jenks
The second, kR, connects all isomers. Figure 2 illustrates the
best fit to the data. The rate constants are functionally equivalent
to the product of the photon flux and the quantum yield for
each isomerization. Since the photon flux is the same for both
processes, the rate constants are proportional to the quantum
yields. While the fit is not perfect, we believe it captures the
essence of the data.23 The ratio of kS/kR is 6.2, and is then
corrected by a factor of 1/2 to account for the fact that any given
stereoisomer can produce two products by the sulfur inversion
(kS) pathway, while the R-cleavage chemistry can produce any
of four isomers, assuming both pathways have random out-
comes. The resulting ratio of 3.1 thus represents at least a
qualitative estimate of the ratio of quantum yields for the sulfur-
only and R-cleavage stereochemical events.
The overall quantum yield of sulfur-center inversion [i.e., (RS)
to (SS)], independently measured by HPLC analysis against
azoxybenzene actinometry,24 was 0.45. This approaches the
expected maximum of 0.5, regardless of the mechanism.
The current results are the strongest evidence yet for a
nonhomolytic photochemical stereomutation process in sulfox-
ides. Taken in combination with previous work, we believe that
the scenario most consistent with all of the evidence is that the
noncleavage mechanism of stereomutation is a geometrical
relaxation of the electronically excited sulfoxide from its highly
pyramidalized ground-state structure to one that is at least
approximately trigonal at sulfur, followed by nonradiative decay
to the ground state at or near a geometry that is planar at the
sulfur center. This notion is analogous to the cis-trans isomer-
ization of olefins.
The issue of the state multiplicity from which this occurs is
slightly ambiguous, but we suggest the predominance of
evidence favors stereomutation from the singlet, with possible
involvement of the triplet. Previous product and flash photolysis
studies with phenyl-based sulfoxides produced no evidence for
long-lived triplet states at room temperature, and the product
study data were most consistent with R-cleavage occurring at
least largely from a singlet state.10-12,14,25 To be competitive
with R-cleavage, it is at least reasonable to speculate that the
geometrical relaxation would also occur from the singlet state,
though short triplet lifetimes are also compatible with nonra-
diative relaxation and decay.
With larger aromatic chromophores such as pyrene and
naphthalene, two groups have shown that the usual fluorescence
is quenched by sulfinyl substitution.10,15,16,20 This was not
accompanied by any systematic increase in triplet yield, as
determined by flash photolysis experiments.20 These results are
consistent with geometric relaxation providing a nonradiative
deactivation pathway from the singlet. Furthermore, fluorescence
yields of the larger aromatic systems went up when samples
were constrained in glassy matrices at 77 K, again suggestive
that fairly large geometry changes might be associated with the
nonradiative decay.20 If intersystem crossing were to occur
simultaneously with or after geometric relaxation, triplets would
be formed that would also end up giving racemized starting
material upon decay to ground state. However, triplet sensitiza-
tion and isoprene-quenching experiments on the larger aromatics
suggested that nearly all the isomerization occurred from a
singlet state.20
In very early experiments on methyl tolyl sulfoxide, Ham-
mond and co-workers used extremely high concentrations of
piperylene and lowered the yield of racemization of methyl tolyl
sulfoxide.26 However, subsequent careful experiments involving
inter- and intramolecular sensitization by naphthalene showed
that piperylene quenched naphthalene fluorescence with a rate
constant (7 × 107 M-1 s-1) consistent with interference with
the singlet chemistry rather than triplet.27 It is not straightforward
to show that piperylene quenches short-lived nonfluorescent
singlets, but it must be seen as at least plausible that these early
experiments do not demonstrate triplet involvement as surely
as once thought.
Further supporting the argument for geometric relaxation are
calculations carried out for DMSO.21 Using full valence28
CASSCF methodology, with energy corrected with MCQDPT
second-order perturbation theory,29,30 energies were obtained for
DMSO in multiple singlet and triplet states at the ground-state
equilibrium geometry and at the inversion transition state.
Additional stationary points in excited 1A′ and 1A′′ states were
found in both Cs and C2V symmetry. In the ground state, of
course, the lowest energy C2V structure is the transition state
for inversion. However, in the two lowest singlet excited states
(1A′ and 1A′′ symmetry), the stationary points with C2V
1
symmetry (1B1 and B2, respectively) are the lowest energy
structures found. The 1B1 stationary point is only 6 kcal mol-1
above the ground electronic state at its own optimized geometry,
which suggests that transitions to the ground electronic state
would be facile. Because the entry point onto the ground-state
surface is at a geometry where the sulfur center is planar, random
stereomutation is expected. It must be noted that these calcula-
tions do not include the type of conjugated aromatic chro-
mophore used here, but there is ample evidence from absorption,
emission, and chiroptical spectroscopy that the sulfinyl group
is a strong perturber of the aromatic chromophore.20,25,31-33
Conclusions
By showing that sulfur-only inversion predominates over
stereomutation of the adjacent stereogenic sites in 1, we have
provided the strongest evidence yet for a noncleavage mecha-
nism for photochemical stereomutation in sulfoxides. Given the
low quantum yield of product formation, the only remaining
argument against a noncleavage mechanism relies on the
confluence of (a) a nearly unity quantum yield for R-cleavage
regardless of the alkyl substituent structure, (b) a fraction of
recombination of the geminate sulfinyl-alkyl radical pairs that
is near unity for the neopentyl radical but much smaller for the
benzyl14 radical, (c) a pathologically high selectivity of the
neopentyl radical for reaction at the sulfur center of the sulfinyl
(26) Hammond, G. S.; Gottardt, H.; Coyne, L. M.; Axelrod, M.; Rayner, D. R.;
Mislow, K. J. Am. Chem. Soc. 1965, 87, 4959-60.
(27) Cooke, R. S.; Hammond, G. S. J. Am. Chem. Soc. 1970, 92, 2739-45.
(28) The CH bonds were neglected in the DMSO calculations, but a truly full
valence calculation that yielded analogous results was run on H2SO.
(29) Nakano, H. J. Chem. Phys. 1993, 99, 7983-92.
(23) The curvature of the data relative to the kinetic plots is probably reflective
of the fact that the sample size was depleted during the measurement, which
increases the effective photon flux to some degree. Any unaccounted for
systematic error due to product formation would decrease the amount of
(SS,RC)-1 from its apparent values and increase the value of kS/kR.
(24) Bunce, N. J.; LaMarre, J.; Vaish, S. P. Photochem. Photobiol. 1984, 39,
531-3.
(30) Nakano, H. Chem. Phys. Lett. 1993, 207, 372-8.
(31) Mislow, K.; Green, M. M.; Laur, P.; Melillo, J. T.; Simmons, T.; Ternay,
A. L. J. J. Am. Chem. Soc. 1965, 87, 1958-76.
(32) Leandri, G.; Mangini, A.; Passerini, R. J. Chem. Soc. 1957, 1386-95.
(33) Baliah, V.; Varadachari, R. Indian J. Chem. 1989, 28A.
(25) Jenks, W. S.; Lee, W.; Shutters, D. J. Phys. Chem. 1994, 98, 2282-9.
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Nonradical Pathway in the Photoracemization of Aryl Sulfoxides
A R T I C L E S
mixture was cooled to 0 °C, n-BuLi (1.78 M in hexane, 0.42 mL, 0.76
mmol) was added with stirring over 20 min. The mixture was then
cooled to -78 °C. (R)-Neopentyl p-tolyl sulfoxide (0.10 g, 0.48 mmol)
in 1 mL of THF was then added to the cold reaction mixture over 5
min. After an additional 5 min, the reaction was quenched with excess
D2O (2 mL). Ether (20 mL) and water (20 mL) were added and the
organic layer was separated. The ether layer was washed with brine
and dried (MgSO4) and solvent was removed. The crude product was
recrystallized three times from ethanol to obtain 30 mg (30%) of highly
purified material, which was a mixture of 94% (RS,SC), 5% (RS,RC),
and 1% (SS,SC) isomers. No sulfoxide containing two R-protons was
observed by NMR. The peaks at 2.81 and 2.52 ppm changed from
13.5 Hz doublets to 2 Hz triplets (deuterium coupling).
radical to form sulfoxides over sulfenic esters despite a much
lower selectivity for the benzyl radical, and (d) the selective
rotation of the p-Tol-SO• bond over the Me3C-CHD• bond in
the geminate radical pair. We do not find this combination of
requirements credible and conclude that photochemical stereo-
mutation of sulfoxides is accomplished both by R-cleavage and
by a noncleavage pathway, which we believe derives from
geometric relaxation in an electronically excited state.
Experimental Section
General Methods. Commercially available compounds were used
without purification except as noted. THF was distilled under Ar from
the sodium benzophenone ketyl and diisopropylamine was distilled from
CaH2. NMR spectra were obtained on either a Varian VXR-300 or a
Bruker Avance DXR 400. HPLC data were collected using a HP 1050
instrument equipped with a diode array UV/vis detector and an Astec
Chirobiotic V (Vancomycin stationary phase) column. Mass spectra
were collected on a VG Magnum ion trap GC-MS operating in EI mode.
The NMR chiral shift reagent of choice was (R)-(-)-N-(3,5-
dinitrobenzoyl) R-phenylethylamine34 in CDCl3. Best results were
obtained when the shift reagent was near 100 mM, given a sulfoxide
concentration of ca. 1 mM. Several other conditions were evaluated
and found inferior, including use of other solvents and use of
R-methoxyphenylacetic acid35 as a shift reagent. Spectra for analysis
were obtained at 400 MHz with deuterium decoupling.
The relative chemical shifts of the C1-protons of the RS and SS
isomers in the presence of the shift reagent were determined from a
sample of nondeuterated neopentyl tolyl sulfoxide that was of a known
RS:SS ratio of about 90:10. The resonance is slightly downfield for the
RS isomers. The absolute stereochemistry at the sulfur center was
determined from the sense of the CD spectrum.31
Photolyses for NMR Analysis. A solution of 1 (340 µM) in CH3CN
(100 mL) was prepared in a septum-sealed quartz tube equipped with
a stir bar. The solution was purged with Ar to remove O2. It was
irradiated at 254 nm using a low-pressure Hg lamp in a Rayonet
minireactor equipped with a magnetic stirrer and a fan. Only a 15 mm
gap of a single 4 W bulb was not covered with foil in order to slow
the reaction. At 2 min intervals, about 25 mL of the solution was
removed by syringe. No photoproducts aside from stereoisomers of
1 were observed by HPLC or NMR. The solvent was evaporated, and
the residue was dissolved in CDCl3 such that the concentration was
about 1 mM. The samples were split into two NMR tubes and then
analyzed. Spectra were obtained after adding successive 200 µL aliquots
of saturated (e200 mM) shift reagent in CDCl3. Typically, 256 scans
were obtained. The S/N ratio in Figure 1 is limited by the low
concentration of the (RS,RC) and (SS,SC) isomers (ca. 10-4 M) in
the presence of approximately 10-1 M shift reagent. The ratio of
[(RS,RC)-1 + (SS,SC)-1] to [(RS,SC)-1 + (SS,RC)-1] was determined by
ordinary integration of the 2.81 and 2.52 ppm peaks, and the ratios of
(RS,RC)-1 to (SS,SC)-1 were obtained using the line shape analysis
feature of WinNMR. The error bars in Figure 2 are best-estimate error
limits, based on estimates of systematic error and reproducibility of
the three measurements. The HPLC measurements do not contribute
significantly to the error.
(R)-Neopentyl p-Tolyl Sulfoxide.36 The procedure of Rieke37 was
used to generate the organometallic reagent. MgCl2 (2.75 g, 29.1 mmol),
KI (2.07 g, 53.0 mmol), and K (2.23 g, 13.2 mmol) were placed in a
flame-dried 250 mL round-bottom flask equipped with a condenser
and stir bar under argon. THF (70 mL) was added and the mixture
was held at reflux for 2 h, then at room temperature for 30 min.
Neopentyl bromide (1.67 mL, 13.2 mmol) was added and the system
was brought to reflux again for 20 min with vigorous stirring.
(1R,2S,5R)-(-)-Menthyl (S)-p-toluenesulfinate38 (3.18 g, 10.8 mmol)
in THF (10 mL) was added at room temperature and the system was
brought to reflux. After 4 h, the system was cooled, quenched with
saturated NH4Cl(aq), and extracted with ether. The organic layer was
washed with brine, dried (MgSO4), and concentrated. Purification by
flash chromatography (silica, 5% EtOAc in CH2Cl2) gave 0.50 g of
sulfoxide (22%). Typical enantiomeric ratios after initial workup were
95:5. Multiple recrystallizations from hexane gave samples with >99%
1
of the (R)-sulfoxide. H NMR (CDCl3) δ 1.20 (s, 9H); 2.42 (s, 3H);
Quantum Yields. Duplicate 4.0 mL solutions of (R)-neopentyl
p-tolyl sulfoxide (5 mM) in acetonitrile contained in 1 cm square
fluorescence cells were degassed by purging with Ar. Excitation was
provided by a 75 W Xe lamp filtered through a monochromator set to
254 nm with (12 nm linear dispersion. The stirred sample was held
in a fixed sample holder mounted at the monochromator exit, which
ensures complete absorption of the exiting light. Samples of a few
microliters each were periodically removed and analyzed by chiral
HPLC. Conversion from the RS isomers to SS isomers was linear with
time up to at least 10% conversion. The photon flux was determined
by azoxybenzene actinometry.
2.52 (d, J ) 13.5 Hz, 1H); 2.81 (d, J ) 13.5 Hz, 1H); 7.33 (d, J ) 8
Hz, 2H); 7.52 (d, J ) 8 Hz, 2H). 13C NMR (CDCl3) δ 142.6, 141.3,
130.1, 124.0, 74.1, 32.1, 30.0, 21.6. UV-vis (λmax 248.2 nm). Ion trap
MS m/e (relative abundance) 211 (M + 1, 100), 194 (10), 140 (38),
92 (14). HPLC (90:10, MTBE:acetonitrile, 1 mL/min) retention times
were 18.4 and 19.7 min for (S) and (R) sulfoxides, respectively. Racemic
sulfoxide was obtained by m-CPBA oxidation (1 equiv, -78 °C,
CH2Cl2) of the neopentyl tolyl sulfide, obtained from sodium p-toluene-
thiolate and neopentyl tosylate.39
(RS,SC)-1-Deuterio-2,2-dimethylpropyl p-Tolyl Sulfoxide (1). Di-
isopropylamine (0.11 mL, 0.81 mmol) and THF (10 mL) were charged
to a flame-dried 25 mL flask equipped with an argon inlet. After the
Acknowledgment. This work is dedicated to Professor
Ronald Breslow, on the occasion of whose 70th birthday
celebration its essential results were first discussed. We grate-
fully acknowledge financial support from the Research Corpora-
tion and the National Science Foundation and thank Professor
James Espenson for help with the kinetic simulations.
(34) Deshmukh, M.; Dun˜ach, E.; Juge, S.; Kagan, H. B. Tetrahedron Lett. 1984,
25, 3467-70.
(35) Buist, P. H.; Marecak, D.; Lolland, H. L.; Brown, F. M. Tetrahedron:
Asymmetry 1995, 6, 7-10.
(36) Rayner, D. R.; Gordon, A. J.; Mislow, K. J. Am. Chem. Soc. 1968, 90,
4854-60.
(37) Rieke, R. D.; Bales, S. E. J. Am. Chem. Soc. 1974, 96, 1775-81.
(38) Klunder, J. M.; Sharpless, K. B. J. Org. Chem. 1987, 52, 2598-602.
(39) Parham, W. E.; Edwards, L. D. J. Org. Chem. 1968, 33, 4150-4.
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