Efficient synthesis of unsymmetrical disulfides through sulfenic acids

Article abstract of DOI:10.1002/ejoc.200900986

Unsymmetrical disulfides, some of which are biologically interesting, were prepared by the in situ generation of sulfenic acids from suitable sulfinyl precursors and their coupling with various thiols. This methodology represents an efficient and mild procedure to obtain disulfides in excellent yields. It allows the presence of base/acid and/or thermolabile functional groups in both the sulfenic acid and the thiol on the basis of the choice of suitable sulfenic acid precursors and offers wide chances of modulating the construction of the disulfide bridge between different structural skeletons such as homo- and heteroaromatic, amino acidic and sugar residues. Wiley-VCH Verlag GmbH & Co. KGaA.

Full text of DOI:10.1002/ejoc.200900986

FULL PAPER
DOI: 10.1002/ejoc.200900986
Efficient Synthesis of Unsymmetrical Disulfides through Sulfenic Acids
Maria Chiara Aversa,[a] Anna Barattucci,*[a] and Paola Bonaccorsi[a]
Keywords: Sulfenic acids / Synthetic methods / Cross-coupling / Sulfur
Unsymmetrical disulfides, some of which are biologically
interesting, were prepared by the in situ generation of sulf-
enic acids from suitable sulfinyl precursors and their cou-
pling with various thiols. This methodology represents an ef-
ficient and mild procedure to obtain disulfides in excellent
yields. It allows the presence of base/acid and/or thermola-
bile functional groups in both the sulfenic acid and the thiol
on the basis of the choice of suitable sulfenic acid precursors
and offers wide chances of modulating the construction of
the disulfide bridge between different structural skeletons
such as homo- and heteroaromatic, amino acidic and sugar
residues.
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2009)
rected cysteine mutagenesis with the reaction between its
thiol residue and glycosyl methane- or benzenethiosulfonate
reagents. A new synthetic route to ω-functionalized alkane
asymmetric disulfides, involving dialkoxylthiophosphorane-
sulfenyl halide precursors, has been described.[5] This pro-
cedure has been demonstrated to be efficient even in the
presence of more nucleophilic groups than the mercaptan
function: disulfides bearing acidic and basic terminal moie-
ties as well as groups used in biospecific self-assembly
monolayers have been prepared. Few examples of one-pot
formations of the disulfide bond are reported. Very recently,
the one-pot synthesis of unsymmetrical disulfides by using
1-chlorobenzotriazole was described.[6] 1-Chlorobenzotri-
azole was used as an environmentally friendly oxidizing
source to convert a thiol into a N-sulfenyl derivative that
could react in situ with a different thiol. Mild conditions
were adopted in a one-pot procedure that makes use of di-
ethyl azodicarboxylate to obtain a series of glycosyl disulf-
ides in good to excellent yields.[7]
It is well accepted that oxidation of the cysteine side
chain involving disulfide bond formation is initiated by the
generation of cysteine sulfenic acid.[8] Sulfenic acids are
generally too unstable to be isolated and self-condense to
give thiosulfinates.[9] However, Okazaki and Goto[10] syn-
thesized a stable arenesulfenic acid bearing a bowl-shaped
macrobicyclic cyclophane skeleton and treated it with a
large excess of 1-butanethiol, affording the corresponding
disulfide almost quantitatively. The bivalence of this result
is very well expressed by the authors who described the
event as “reminiscent of the formation of stable sulfenic
acid intermediates from cysteine in the active sites of some
enzymes, where the structural features of the environment
around the SOH group are believed to prevent its self-con-
densation” and “the first conclusive demonstration of disul-
fide formation from the reaction of a sulfenic acid with a
Introduction
The disulfide bridge plays a pivotal role in the structure
and stability of many proteins. The covalent bond between
the sulfur atoms of cysteine residues has been studied by
biologists to understand how it is formed, how it can be
cleaved and how it participates in protein folding.[1] Syn-
thetic chemists have developed different and efficient routes
to build the disulfide bond between glycose and peptide res-
idues with the idea of developing straightforward syntheses
of hydrolysis-resistant carbohydrate mimics for applications
in glycobiology and medicinal research.[2] Replacement of
the anomeric oxygen atom by a sulfur atom in glycopep-
tides leads to modifications that are tolerated by most bio-
logical systems and are less susceptible to acid/base or en-
zyme-mediated hydrolysis. In both cases, the deepened in-
vestigation on the disulfide bond has represented a useful
tool for the progress of scientific knowledge into secrets of
biology.
The synthesis of unsymmetrical disulfides, in particular,
has attracted the attention of several research groups, and
several methodologies have been developed for the prepara-
tion of various types of disulfides.[3] Few of these methods
employ mild and efficient conditions that do not require the
use of toxic reagents. The most popular approach involves
substitution of a sulfenyl derivative with a thiol or its deriv-
ative. Herein two recent examples are reported that illus-
trate this approach. An efficient synthesis of glycopeptides
and glycoproteins showing the disulfide linker was con-
ducted by Davis and co-workers[4] by combining site-di-
[a] Dipartimento di Chimica organica e biologica, Università degli
Studi di Messina,
Salita Sperone 31 (vill. S. Agata), 98166 Messina, Italy
Fax: +39-090-393895
E-mail: anna.barattucci@unime.it
Eur. J. Org. Chem. 2009, 6355–6359
© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
6355

M. C. Aversa, A. Barattucci, P. Bonaccorsi
FULL PAPER
thiol”. This reaction has been used several times for trap-
ping transient sulfenic acids, owing to the stability of the
produced unsymmetrical disulfides,[11] but, to the best of
our knowledge, it has never been regarded as a general
methodology for the synthesis of disulfides, including un-
symmetrical ones bearing bioresidues.
In accordance with our research interests devoted to the
development of synthetic procedures that involve sulfenic
acids as intermediates,[12] we describe in this paper their in
situ generation, from suitable sulfinyl precursors, and their
coupling with various thiols in an efficient and mild process
to obtain unsymmetrical disulfides in excellent yields, some
of which are of biological interest.
Results and Discussion
The synthetic strategy is illustrated in Scheme 1 and the
results are shown in Table 1. Two steps were required to
convert thiols 1a,b into sulfinyl precursors 6–9 of the corre-
sponding sulfenic acids 10a,b, through sulfides 2–
5.[12a,12b,12e,12h] Thermolysis of sulfoxides 6–9 that generate
transient sulfenic acids 10a,b was performed in the presence
of thiols 11b–h and 1,3-benzenedithiol (21) with an almost
2:1 sulfoxide/thiol group ratio (Table 1). The in situ cou-
pling between intermediates 10a,b and thiols 11b–h or 1,3-
benzenedithiol (21) led to the formation of unsymmetrical
disulfides 12–20, together with minor byproducts coming
from sulfenic acid autocondensation, which were easily re-
moved by flash chromatography (see Experimental Sec-
tion). This last reaction occurs without base or acid pro-
moters at reaction temperatures below 100 °C, allowing the
presence of base/acid-sensitive functional groups in both
the sulfenic acid and the thiol.
Scheme 1. Synthesis of unsymmetrical disulfides 12–20.
During the last decade, we have gained expertise in the
choice and preparation of sulfenic acid precursors.[12b,12h,13]
Entries 2–4 in Table 1 show how the use of sulfoxides 6–8,
as precursors of sulfenic acid 10a, in the presence of thiol
11c, allows the formation of disulfide 12 under different tected cysteine methyl ester 11c is reported in Entry 5
reaction conditions but always in excellent yields. This re- (Table 1). The formation of disulfide 14[14] can be regarded
sult can be regarded as indicative of the possible selection of as an alternative to the glycosylation of proteins by the use
the sulfenic acid precursor, in dependence of the structural of glycosyl methane- or benzenethiosulfonates.[4]
demands of the desired disulfide. For example, sulfoxide 8
The disulfide bridge has recently been introduced into
(Table 1, Entry 4) affords sulfenic acid 10a at room tem- carbohydrate chemistry as a new interglycosidic linker that
perature,[13] as required when temperature-sensitive residues offers some advantages in terms of flexibility, increased dis-
should be included in the disulfide skeleton. Furthermore, tance between the two glycosidic components, and opportu-
the use of 1-thio-β--glucopyranose 2,3,4,6-tetraacetate (1b nity to vary the monosaccharide units.[15] Sulfenic acid/thiol
= 11b) either as starting compound 1b in the synthesis of coupling allows the formation of disaccharide mimics such
sulfenic acid precursor 9 (Table 1, Entries 5–11) or as sulf- as compound 19 in excellent yield under mild conditions
enic acid acceptor 11b (Table 1, Entry 1) evidences the wide (Table 1, Entry 10).
chances that this route offers of modulating the synthesis
Benzene-spaced bis-β--glucopyranosyl disulfide 20
of unsymmetrical disulfides from thiols.
(Table 1, Entry 11) was obtained as part of our research
Most unsymmetrical disulfides obtained with this meth- programme centred on the study of the relationship be-
odology possess a glucosyl residue and were prepared by tween molecular structure and biological activity of tailored
thermolysis of sulfoxide 9 in the presence of various thiols, small molecules containing two glucopyranosyl units sepa-
always with the maintenance of the anomeric β-stereochem- rated by thioarene spacers.[16] The biopotentialities of bisdi-
istry. In particular, the reaction between glucosulfenic acid sulfide 20 are under study. Biologically significant hetero-
10b, generated from sulfinyl precursor 9, and N-Boc-pro- aromatic scaffolds have been also linked to the glucosyl resi-
6356
www.eurjoc.org
© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2009, 6355–6359

Efficient Synthesis of Unsymmetrical Disulfides through Sulfenic Acids
Table 1. Synthesis of unsymmetrical disulfides 12–20.
[a] All the reactions were conducted with a 2:1 molar ratio of sulfenic acid precursor/thiol except for entry 6 (9/21 molar ratio 5:1).
due by the disulfide bridge in compounds 17 and 18
(Table 1, Entries 8 and 9). In particular, disulfide 18, ob-
Conclusions
tained in excellent yield from the condensation of 2-thiocy-
Although the overall synthetic procedure described in
tosine (11g) with sulfenic acid 10b in acetone at 45 °C, rep- this paper is well known,[9b] to the best of our knowledge,
resents a promising candidate to the discovery of new anti- it has never been used before as a general methodology for
viral and anticancer agents.[17]
the preparation of unsymmetrical disulfides. It is a three-
Eur. J. Org. Chem. 2009, 6355–6359
© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
6357

M. C. Aversa, A. Barattucci, P. Bonaccorsi
FULL PAPER
(C-6), 53.2 (C-1Ј), 48.0 (C-7Ј), 45.1 (C-4Ј), 40.0 and 39.2 (C-3Ј,10Ј),
30.3 and 27.0 (C-5Ј,6Ј), 20.7, 20.58, 20.55, 20.51, 19.8 [C-8Ј,9Ј and
4ϫC(O)Me] ppm. C24H36O10S2 (548.67): calcd. C 52.54, H 6.61;
found C 52.51, H 6.60.
step procedure that offers the possibility of reacting struc-
turally complex thiols. The possible choice among different
sulfenic acid precursors, obtained from the same thiol, al-
lows the involvement of starting compounds carrying base/
acid-sensitive and thermolabile functional groups. Disul- 1-(2-Benzoxazolyldithio)-1-deoxy-β-
D-glucopyranose 2,3,4,6-Tetra-
acetate (16): White crystals, m.p. 157–159 °C (621.4 mg, 1.21 mmol,
92% yield, from 200.0 mg, 1.32 mmol, of 11e). Rf = 0.54. 1H NMR:
δ = 7.6–7.3 (m, 4 H, Harom), 5.26 (m, 2 H, 2-H and 3-H), 5.07 (m,
fides 13, 15–18 and 20 have not been described previously
in the literature.
1 H, 4-H), 4.75 (d, J1,2 = 9.6 Hz, 1-H), 4.01 (AB dd, J6A,6B
=
12.3 Hz, J5,6A = 4.7 Hz, 1 H, 6-HA), 3.96 (AB dd, J5,6B = 2.3 Hz,
1 H, 6-HB), 3.72 (m, 1 H, 5-H), 2.04, 1.99 and 1.81 (3 s, 12 H,
4ϫMe) ppm. 13C NMR: δ = 170.4, 170.1, 169.24 and 169.21
(4ϫC=O), 161.8 (C-2Ј), 152.2 (C-7aЈ), 141.8 (C-3aЈ), 125.1 and
124.7 (C-5Ј,6Ј), 119.5 (C-4Ј), 110.2 (C-7Ј), 86.4 (C-1), 76.0, 73.5,
69.2 and 67.7 (C-2–5), 61.6 (C-6), 20.6, 20.53, 20.48 and 20.3
(4ϫMe) ppm. C21H23NO10S2 (513.54): calcd. C 49.12, H 4.51, N
2.73; found C 49.08, H 4.49, N 2.74.
Experimental Section
General: Solvents were purified according to standard procedures.
Petroleum ether used refers to the fraction boiling at 40–60 °C. All
reactions were monitored by TLC on commercially available pre-
coated plates (Aldrich silica gel 60 F254) eluted with light petro-
leum/ethyl acetate (1:1), and the products were visualized with va-
nillin [1 g dissolved in MeOH (60 mL) and conc. H2SO4 (0.6 mL)].
Silica gel used for column chromatography was Aldrich 60. 1H and
13C NMR spectra were recorded with a Varian Mercury 300 spec-
trometer at 300 and 75 MHz, respectively, in CDCl3 solutions with
SiMe4 as internal standard; the attributions are supported by At-
tached Proton Test (APT) and homodecoupling experiments; pro-
ton and carbon nuclei identified by apex pertain to phenyl group
in compound 13, to isoborneol residue in 15 and to heteroaromatic
substituents in 16–18, whereas single and double apex identify pro-
ton and carbon nuclei of the two glucose residues in the bisdisulfide
20.
1-[2-(1-Methyl)imidazolyldithio]-1-deoxy-β-D-glucopyranose 2,3,4,6-
Tetraacetate (17): Colourless oil (776.7 mg, 1.63 mmol, 93% yield,
from 200.0 mg, 1.75 mmol, of 11f). Rf = 0.20. 1NMR: δ = 7.09 and
7.03 (2 d, J4Ј,5Ј = 1.5 Hz, 2 H, 4Ј-H and 5Ј-H), 5.24 (t, J2,3 = J3,4
= 9.2 Hz, 1 H, 3-H), 5.08 (m, 2 H, 2-H and 4-H), 4.89 (d, J1,2
=
9.9 Hz, 1-H), 4.26 (AB dd, J6A,6B = 12.5 Hz, J5,6A = 4.4 Hz, 1 H,
6-HA), 4.05 (AB dd, J5,6B = 2.6 Hz, 1 H, 6-HB), 3.81 (m, 1 H, 5-
H), 3.77 (s, 3 H, NMe), 2.07, 2.01, 1.99 and 1.94 [4 s, 12 H,
4ϫC(O)Me] ppm. 13C NMR: δ = 170.4, 169.9, 169.25 and 169.21
(4ϫC=O), 139.9 (C-2Ј), 130.0 and 124.2 (C-4Ј,5Ј), 88.8 (C-1), 75.9,
73.6, 69.7 and 67.8 (C-2–5), 61.7 (C-6), 34.1 (NMe), 20.6–20.4
[4ϫC(O)Me] ppm. C18H24N2O9S2 (476.52): calcd. C 45.37, H 5.08,
N 5.88; found C 45.43, H 5.06, N 5.87.
General Procedure for the Preparation of Disulfides 12–20: Solvents,
molar ratios, reaction times, temperatures and yields are indicated
in Table 1. A 0.2  solution of the sulfenic acid precursor was
added to a 0.2  solution of the thiol. The reaction, monitored by
TLC, was conducted until the sulfenic acid precursor disappeared.
All the obtained disulfides were purified by flash chromatography.
The undesired byproducts were always first eluted from the col-
umn, and not characterized. Spectral and analytical data were con-
sistent to those reported in the literature for disulfides 12 [241.0 mg,
0.51 mmol, 93% yield, from 200.0 mg, 0.55 mmol, of 1b (= 11b),],
14 (406.4 mg, 0.68 mmol, 80% yield, from 200.0 mg, 0.85 mmol,
of 11c) and 19 (327.0 mg, 0.45 mmol, 82% yield, from 200.0 mg,
0.55 mmol, of 11h).[7,17]
1-[2-(4-Amino)pyrimidyldithio]-1-deoxy-β-D-glucopyranose 2,3,4,6-
Tetraacetate (18): White crystals, m.p. 69–71 °C (704.9 mg,
1.44 mmol, 92% yield, from 200.0 mg, 1.57 mmol, of 11g). Rf =
1
0.22. H NMR: δ = 8.05 (d, J5Ј,6Ј = 5.6 Hz, 1 H, 6Ј-H), 6.20 (d, 1
H, 5Ј-H), 5.32 (br. s, 2 H, NH2), 5.20 (m, 2 H, 2-H and 3-H), 5.06
(m, 1 H, 4-H), 4.64 (d, J1,2 = 9.6 Hz, 1-H), 4.08 (m, 2 H, 6-H2),
3.68 (m, 1 H, 5-H), 2.05, 1.98 and 1.96 (3 s, 12 H, 4ϫMe) ppm.
13C NMR: δ = 170.6, 170.2, 169.33, 169.30 and 169.2 (C-2Ј and
4ϫC=O), 162.8 (C-4Ј), 156.1 (C-6Ј), 102.5 (C-5Ј), 86.4 (C-1), 75.8,
73.8, 69.7 and 61.8 (C-2–5), 60.3 (C-6), 20.7–20.5 (4ϫMe) ppm.
C18H23N3O9S2 (489.52): calcd. C 44.16, H 4.74, N 8.58; found C
44.20, H 4.73, N 8.56.
N-[(1,1-Dimethylethoxy)carbonyl]-S-(phenylthio)-L-cysteine Methyl
Ester (13): Colourless oil [from 200.0 mg, 0.85 mmol, of 11c,
233.6 mg, 0.68 mmol, 80% yield (Entry 2, Table 1) or 248.1 mg,
0.72 mmol, 85% yield (Entries 3 and 4) of 13 were obtained]. Rf =
0.75. 1H NMR: δ = 7.5–7.2 (m, 5 H, Harom), 5.29 (br. d, 1 H, NH),
4.60 (br. q, 1 H, 2-H), 3.72 (s, 3 H, OMe), 3.18 (m, 2 H, 3-H2),
1.42 (s, 9 H, CMe3) ppm. 13C NMR: δ = 171.1 (C-1), 154.6
(NHC=O), 136.6 (C-1Ј), 129.1, 128.3 and 127.4 (C-2Ј-6Ј), 80.2
(CMe3), 52.8 (C-2), 52.6 (OMe), 40.9 (C-3), 28.3 (CMe3) ppm.
C15H21NO4S2 (343.46): calcd. C 52.45, H 6.16, N 4.08; found C
52.49, H 6.15, N 4.10.
1,3-Bis-[(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl)dithio]benzene
(20): White crystals, m.p. 169–171 °C (606.9 mg, 0.70 mmol, 50%
1
yield, from 200.0 mg, 1.41 mmol, of 21). Rf = 0.48. H NMR: δ =
7.80 (t, Jmeta = 1.8 Hz, 1 H, 2-H), 7.45 (dd, Jortho = 7.7 Hz, 2 H, 4-
H and 6-H), 7.19 (t, 1 H, 5-H), 5.24 (m, 4 H, 2Ј-H, 2ЈЈ-H, 3Ј-H
and 3ЈЈ-H), 5.08 (m, 2 H, 4Ј-H and 4ЈЈ-H), 4.60 (m, 2 H, 1Ј-H and
1ЈЈ-H), 4.15 (AB dd, J5A,5B = 12.5 Hz, J5A,6 = 4.4 Hz, 2 H, 6Ј-HA
and 6ЈЈ-HA), 4.08 (AB dd, J5B,6 = 2.5 Hz, 2 H, 6Ј-HB and 6ЈЈ-HB),
3.74 (m, 2 H, 5Ј-H and 5ЈЈ-H), 2.03, 2.00, 2.02 and 2.01 (4 s, 24 H,
8 ϫ Me) ppm. 13C NMR: δ = 170.5, 170.1, 169.3 and 169.1
(8ϫC=O), 137.8 (C-1,3), 129.0, 127.6 and 127.1 (C-2,4–6), 87.7
(C-1Ј,1ЈЈ), 76.1, 73.7, 69.3 and 67.9 (C-2Ј-5Ј and C-2ЈЈ-5ЈЈ), 61.9 (C-
6Ј,6ЈЈ), 20.64, 20.61, 20.55 and 20.51 (8ϫMe) ppm. C34H42O18S4
(866.95): calcd. C 47.10, H 4.88; found C 47.04, H 4.89.
1-[(1S)-Isoborneol-10-dithio]-1-deoxy-β-
D-glucopyranose
2,3,4,6-
Tetraacetate (15): White crystals, m.p. 128–130 °C (559.6 mg,
1.02 mmol, 95% yield, from 200.0 mg, 1.07 mmol, of 11d). Rf =
1
0.61. H NMR: δ = 5.21 (m, 2 H, 2-H and 3-H), 5.08 (m, 1 H, 4-
H), 4.57 (d, J1,2 = 9.2 Hz, 1-H), 4.17 (m, 2 H, 6-H2), 3.96 (m, 1 H,
2Ј-H), 3.77 (m, 1 H, 5-H), 3.26 (AB d, J10ЈA,10ЈB = 12.0 Hz, 1 H,
10Ј-HA), 2.76 (AB d, 1 H, 10Ј-HB), 2.60 (br. s, 1 H, OH), 2.15,
2.02, 2.01 and 1.99 [4 s, 12 H, 4ϫ C(O)Me], 1.8–1.1 (m, 7 H, 3Ј-
H2, 4Ј-H, 5Ј-H2, and 6Ј-H2), 0.98 and 0.78 (2 s, 6 H, 8Ј-H3 and 9Ј-
H3) ppm. 13C NMR: δ = 170.6, 170.2, 169.3 and 169.2 [4ϫC(O)
Acknowledgments
The authors thank the Università degli Studi di Messina for finan-
Me], 88.1 (C-1), 76.2, 75.9, 73.7, 69.1 and 68.0 (C-2,2Ј,3,4,5), 62.0 cial support (PRA).
6358
www.eurjoc.org
© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2009, 6355–6359

Efficient Synthesis of Unsymmetrical Disulfides through Sulfenic Acids
Sammes, M. V. Taylor, J. Chem. Soc. Perkin Trans. 1 1973,
1182–1187; T. Kamiya, T. Teraji, Y. Saito, M. Hashimoto, O.
Nakaguchi, T. Oku, Tetrahedron Lett. 1973, 14, 3001–3004.
[12] a) M. C. Aversa, A. Barattucci, P. Bonaccorsi, C. Faggi, T. Pap-
alia, J. Org. Chem. 2007, 72, 4486–4496; b) M. C. Aversa, A.
Barattucci, M. C. Bilardo, P. Bonaccorsi, P. Giannetto, P. Rol-
lin, A. Tatibouët, J. Org. Chem. 2005, 70, 7389–7396; c) M. C.
Aversa, A. Barattucci, P. Bonaccorsi, P. Giannetto, J. Org.
Chem. 2005, 70, 1986–1992; d) M. C. Aversa, A. Barattucci,
M. C. Bilardo, P. Bonaccorsi, P. Giannetto, Synthesis 2003,
2241–2248; e) V. Aucagne, M. C. Aversa, A. Barattucci, P. Bon-
accorsi, P. Giannetto, P. Rollin, A. Tatibouët, J. Org. Chem.
2002, 67, 6925–6930; f) M. C. Aversa, A. Barattucci, P. Bonac-
corsi, P. Giannetto, M. Policicchio, J. Org. Chem. 2001, 66,
4845–4851; g) M. C. Aversa, A. Barattucci, P. Bonaccorsi, P.
Giannetto, F. Nicolò, J. Org. Chem. 1999, 64, 2114–2118; h)
M. C. Aversa, A. Barattucci, P. Bonaccorsi, P. Giannetto, D. N.
Jones, J. Org. Chem. 1997, 62, 4376–4384.
[1]
[2]
M. Hozoji, Y. Kimura, N. Kioka, K. Ueda, J. Biol. Chem.
2009, 284, 11293–11300; J. Beckwith, Genetics 2007, 176, 733–
740; T. E. Creighton, Biol. Chem. 1997, 378, 731–744.
K. Pachamuthu, R. R. Schmidt, Chem. Rev. 2006, 106, 160–
187.
[3]
[4]
D. Witt, Synthesis 2008, 2491–2509.
D. P. Gamblin, P. Garnier, S. J. Ward, N. J. Oldham, A. J. Fair-
banks, B. G. Davis, Org. Biomol. Chem. 2003, 1, 3642–3644;
B. G. Davis, M. A. T. Maughan, M. P. Green, A. Ullman, J. B.
Jones, Tetrahedron: Asymmetry 2000, 11, 245–262.
J. Kowalczyk, P. Barski, D. Witt, B. A. Grzybowski, Langmuir
2007, 23, 2318–2321.
[5]
[6] R. Hunter, M. Caira, N. Stellenboom, J. Org. Chem. 2006, 71,
8268–8271.
[7] G. Ribeiro Morais, R. A. Falconer, Tetrahedron Lett. 2007, 48,
7637–7641, and references therein.
[8] J. J. Mieyal, M. M. Gallogly, S. Qanungo, E. A. Sabens, M. D. [13] M. C. Aversa, A. Barattucci, P. Bonaccorsi, P. Rollin, A. Tati-
Shelton, Antioxid. Redox Signaling 2008, 10, 1941–1988; S. bouët, ARKIVOC 2009, 8, 187–198.
Carballal, R. Radi, M. C. Kirk, S. Barnes, B. A. Freeman, B. [14] See the Supporting Information of: G. J. L. Bernardes, E. J.
Alvarez, Biochemistry 2003, 42, 9906–9914; M. D. Percival, M.
Ouellet, C. Campagnolo, D. Claveau, C. Li, Biochemistry 1999,
38, 13574–13583.
Grayson, S. Thompson, J. M. Chalker, J. C. Errey, F. El Oualid,
T. D. W. Claridge, B. G. Davies, Angew. Chem. Int. Ed. 2008,
47, 2244–2247.
[9] a) M. C. Aversa, A. Barattucci, P. Bonaccorsi, P. Giannetto, [15] O. Ramström, J.-M. Lehn, ChemBioChem 2000, 1, 41–48.
Curr. Org. Chem. 2007, 11, 1034–1052; b) D. R. Hogg in The
Chemistry of Sulphenic Acids and Their Derivatives (Ed.: S. Pa-
tai), Wiley & Sons, Chichester, 1990, pp. 361–402.
[16] M. C. Aversa, A. Barattucci, P. Bonaccorsi, F. Marino-Merlo,
A. Mastino, M. T. Sciortino, Bioorg. Med. Chem. 2009, 17,
1456–1463.
[17] C. L. Bair, L. W. Black, J. Mol. Biol. 2007, 366, 768–778; L.
Lariviere, N. Sommer, S. Morera, J. Mol. Biol. 2005, 352, 139–
150; K. A. Watanabe, M. P. Kotick, J. J. Fox, J. Org. Chem.
1970, 35, 231–236.
[10] K. Goto, N. Tokitoh, R. Okazaki, Angew. Chem. Int. Ed. Engl.
1995, 34, 1124–1126.
[11] F. A. Davis, R. L. Billmers, J. Am. Chem. Soc. 1981, 103, 7016–
7018; H. Adams, R. Bell, Y.-Y. Cheung, D. N. Jones, N. C. O.
Tomkinson, Tetrahedron: Asymmetry 1999, 10, 4129–4142;
R. D. Allan, D. H. R. Barton, M. Girijavallabhan, P. G.
Received: August 31, 2009
Published Online: November 9, 2009
Eur. J. Org. Chem. 2009, 6355–6359
© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
6359