Chemical oxidation studies of β-hydroxysulfides with tris(4-bromophenyl)aminium hexachloroantimonate: Diastereoselective sulfoxide obtaining and pinacol-type rearrangement

Article abstract of DOI:10.1081/SCC-120018767

The chemical oxidation of some β-hydroxy-sulfides in the presence of tris(4-bromo-phenyl)aminium hexachloroantimonate (TBPA) is reported. The oxidation of 2-ethylsulfanyl-cyclohexan-1-ol (cis- and trans-) resulted the corresponding sulfoxides with good diastereoselectivity (d.e. 50%) and for 2-methyl-2-ethylsulfanyl-cyclohexan-1-ol and 2-ethylsulfanyl-1,2-diphenyl-ethanol, the corresponding nonsulfanylated ketones (61-75%) and ethyl ethanethiolsulfonate (51-65%) were obtained via oxidative cleavage and pinacol-type rearrangement.

Full text of DOI:10.1081/SCC-120018767

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Chemical Oxidation Studies of β-Hydroxy-sulfides with
tris(4-Bromophenyl)aminium Hexachloroantimonate:
Diastereoselective Sulfoxide Obtaining and Pinacol-
Type Rearrangement
Claudio Luis Donnici a , Sibele Guimarães a & Angelita Cristine de Melo a
a Departmento de Química , Universidade Federal de Minas Gerais , Brazil
Published online: 16 Aug 2006.
To cite this article: Claudio Luis Donnici , Sibele Guimarães & Angelita Cristine de Melo (2003) Chemical Oxidation Studies
of β-Hydroxy-sulfides with tris(4-Bromophenyl)aminium Hexachloroantimonate: Diastereoselective Sulfoxide Obtaining and
Pinacol-Type Rearrangement, Synthetic Communications: An International Journal for Rapid Communication of Synthetic
Organic Chemistry, 33:9, 1489-1497, DOI: 10.1081/SCC-120018767
To link to this article: http://dx.doi.org/10.1081/SCC-120018767
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SYNTHETIC COMMUNICATIONSÕ
Vol. 33, No. 9, pp. 1489–1497, 2003
Chemical Oxidation Studies of b-Hydroxy-
sulfides with tris(4-Bromophenyl)aminium
Hexachloroantimonate: Diastereoselective
Sulfoxide Obtaining and Pinacol-Type
Rearrangement
*
Claudio Luis Donnici, Sibele Guimaraes,
and Angelita Cristine de Melo
Departmento de Quımica, Universidade Federal de
Minas Gerais, Brazil
ABSTRACT
The chemical oxidation of some b-hydroxy-sulfides in the presence of
tris(4-bromo-phenyl)aminium hexachloroantimonate (TBPA) is
reported. The oxidation of 2-ethylsulfanyl-cyclohexan-l-ol (cis- and
trans-) resulted the corresponding sulfoxides with good diastereoselect-
ivity (d.e. ꢀ50%) and for2-methyl-2-ethylsulfanyl-cyclohexan-l-ol
*Correspondence: Claudio Luis Donnici, Depto. de Quımica, Universidade
Federal de Minas Gerais, Av. Antonio Carlos, 6627, Brazil-31270-901;
E-mail: cdonnici@apolo.qui.ufmg.br.
1489
DOI: 10.1081/SCC-120018767
Copyright & 2003 by Marcel Dekker, Inc.
0039-7911 (Print); 1532-2432 (Online)
www.dekker.com

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1490
Donnici, Guimaraes, and de Melo
and 2-ethylsulfanyl-1,2-diphenyl-ethanol, the corresponding non-
sulfanylated ketones (61–75%) and ethyl ethanethiolsulfonate
(51–65%) were obtained via oxidative cleavage and pinacol-type
rearrangement.
The b-keto-sulfides and their derivatives are very useful and versatile
‘‘synthons’’ due to the regioselectivity and stereoselectivity they can pre-
sent.[1] Much more attention has recently been paid to the application of
chiral b-keto- and b-hydroxy-sulfoxides in asymmetric synthesis.[2] These
useful b-keto-sulfides derivatives with different oxidation states can be
achieved through chemical methods.[2] Despite of the increasing interest
on organic electrosynthesis, as an useful tool for organic transformations,
few works have been reported on the direct electrochemical oxidation[3,4]
orreduction [5] studies of b-keto-[3] and b-hydroxy sulfides.[4,5] Even fewer
indirect electrochemical studies, through electrogenerated oxidants, with
b-hydroxy sulfides have been related. a-phenyl-b-hydroxy-sulfides, for
instance, suffer eletrooxidation in the presence of chloride ions (electro-
generated chloronium ion ‘‘in situ’’) resulting in a novel pinacol-type
rearrangement to give the corresponding 2-phenyl substituted ketones.[6]
a,a-bisphenylthio-b-phenyl-b-hydroxy compounds when indirectly oxi-
dized (with tris(4-bromo-phenyl)aminium electrogenerated ‘‘in situ’’)
lead to the corresponding ketones with phenyl rearrangement[7]; in
similarconditions a-phenylthio-ketones generated the corresponding
a-hydroxy-ketone.[7] In a previous work, we reported that b-hydroxy
sulfides through indirect anodic oxidation (tris(4-bromo-phenyl)aminium
electrogenerated ‘‘in situ’’) yielded the corresponding sulfoxides with
good diastereoselectivity (d.e. ffi50%).[8]
However, the tris(4-bromophenyl)aminium can be chemically pre-
pared by some usual methods showing interesting reactivity as oxidant
agent[9] and as Diels-Aldercatalyst.
[10]
Forexample, the chemical oxida-
tion of some ketones, with tris(4-bromophenyl)aminium hexachloroanti-
monate, to their corresponding a-hydroxy derivatives is related.[11]
Nevertheless, no chemical oxidation investigation with b-hydroxy sulfides
using the tris(4-bromophenyl)aminium hexachloroantimonate, commer-
cially available (AldrichÕ) has been made yet. As part of this
research, we now describe the chemical oxidation study of some
b-hydroxy sulfides such as: cis- (1) and trans-2-ethylsulfanyl-cyclo-
hexan-1-ol (2), cis-2-methyl-2-ethylsulfanyl-cyclohexan-1-ol (3), and
2-ethylsulfanyl-1,2-diphenyl-ethanol (4) with tris(4-bromophenyl)ami-
nium hexachloroantimmonate, TBPA (5).

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Chemical Oxidation Studies of b-Hydroxy-sulfides
1491
The desired b-hydroxy-sulfides 1–4 and TBPA were prepared in good
yields by classical methods[12–15] (Sch. 1).
The chemical oxidation of cis- (1) and trans-2-ethylsulfanyl-cyclohex-
anol (2) with TBPA, and sodium carbonate (1:2:4 mol/mol) in aceto-
nitrile/water (9:1 v/v) yielded (63–69%) the corresponding diastereomeric
sulfoxides (1a and 1b, 2a and 2b) in good diastereoselectivity (ca. 75:25%)
(Sch. 2a). The same condition of 2-methyl-2-ethylsulfanyl-cyclohexanol
(3), an a-alkyl-b-hydroxy-sulfide generated (69%) 2-methyl cyclohexa-
none (3a), and ethyl ethanethiolsulfonate (56–61%) (Sch. 2a).
Nevertheless, when similar conditions were used to bisaromatic derivative
4, benzaldehyde (4a) (75%) and ethylethane thiolsulfonate were obtained
through an oxidative cleavage route (Sch. 2b).
The mechanism of the chemical oxidation forthe b-hydroxy-sulfides
1, 2, 3, and 4 with TBPA can be suggested (Sch. 3). This way, at
first, it must occur an oxidation of the sulfur atom which can
lead to the corresponding sulfoxide (Sch. 3, A1). Then, if there is an
a-alkyl-substituent oran a-phenyl substituent, the following and slowest
step might be the subsequent cleavage of the carbon–sulfur bond (C–S)
Scheme 1.

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1492
Donnici, Guimaraes, and de Melo
Scheme 2a.
Scheme 2b.
Scheme 3.
and a carbocationic species formation, which undergoes the pinacol-type
rearrangement (Sch. 3, A2) forand a cleavage mechanism for 4 (Sch. 3,
B). It is noteworthy that on the mechanism of oxidation for (similar to the
pinacolinic rearrangement); heteroatoms such as nitrogen, sulfur, and
selenium have evereve been used by genearting cationic intemr ediates
to direct this kind of rearrangment.[6]
The different reactivity observed in the chemical oxidation of
b-hydroxy-sulfides with TBPA in comparison to the using of generated

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Chemical Oxidation Studies of b-Hydroxy-sulfides
1493
chloronium ‘‘in situ’’ can be briefly discussed. At first the known anodic
potential of TBPA formation is lower, then the oxidation with TBPA
might be milder, more selective, and more efficient. In fact, diastereo-
meric sulfoxides can be obtained in medium yields via an easy
oxidative method. Besides, the common phenyl group neighboring
effect, as in 4, favors the carbon–carbon cleavage and the presence of
an alpha-alkyl group, as in 3, favors the pinacol-type rearrangement.
Similar rearrangement occurs with a-phenyl-b-hydroxy-sulfides with gen-
erated chloronium ‘‘in situ’’[6] orwith a,a-bisphenylthio-b-phenyl-b-
hydroxy compounds with electrogenerated TBPA.[7]
In summary, the tris(4-bromophenyl)aminium hexachloroanti-
monate (5) showed to be an interesting reagent to provide a sulfide
diastereoselective oxidation method to sulfoxide obtaining from non
a-alkyl-substituted b-hydroxy-sulfides. The observed pinacol-type
rearrangement is also interesting due to the fact that it should be a
selective method foroxidative ketone obtaining form or
hydroxy-sulfides using a commercial and simple reagent, the TBPA.
a-phenyl-b-
EXPERIMENTAL
Melting points were determined on a Mettler apparatus and were
uncorrected. 1H and 13C NMR spectra were recorded on a Bruker instru-
ment (AC-200 MHz) in CDCl3 using tetramethylsilane as an internal
standard. FT–IR spectra were recorded on a Mattson instrument model
Galaxy 3000. The microanalysis were performed on a Perkin–Elmer 240B
elemental analyzer. Chromatography was performed on SiO2 (Merck,
70–230 mesh, Kieselgel 60).
Compounds 1–5 were obtained through the usual procedures[12,13]
indicated in the Sch. 1. TBPA tris(4-bromophenyl)aminium hexachloro-
antimonate (5), was prepared as described starting from trisphenyl
amine[14,15]; TBPA and tris(4-bromophenyl)amine were also purchased
from Aldrich for comparison and the results were exactly the same.
Synthesis of cis-2-Ethylsulfanyl-cyclohexanol (1)
Preparation of cis-2-ethylsulfanyl-cyclohexanone[12a]: Yield 89%, light
yellow oil; b.p. 107–109ꢁC/9 torr (lit[12a]: 119–121ꢁC/30 torr). IR ꢀmax
1
(KBr, cmÀ1): 170 (C¼O). H NMR (CDCl3): 3.20 (m, 1H), 2.43 (q, 2H,
J ¼ 7 Hz), 3.20–1.30 (m, 8H), 1.20 (t, 3H, J ¼ 7 Hz). 13C NMR (CDCl3):
207.11, 51.40, 36.60, 32.47, 26.38, 25.11, 21.10, 13.84.

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1494
Donnici, Guimaraes, and de Melo
cis-2-Ethylsulfanyl-cyclohexanol (1): Yield 69%, light yellow oil; b.p.
81–82ꢁC/0.8 torr. IR ꢀmax (KBr, cmÀ1): 3200 (O–H). H NMR (CDCl3):
3.20 (m, 1H), 2.43 (q, 2H, J ¼ 7 Hz), 2.30 (m, 1H), 2.20–1.30 (m, 8H), 1.20
(t, 3H, J ¼ 7 Hz). 13C NMR CDCl3) 66.81, 49.85, 33.43, 31.17, 24.53,
23.97, 20.30, 14.61. Anal. calcd. forC 8H16OS: C 59.97, H 10.05;
Found: C 59.91, H 9.98.
1
Preparation of trans-2-ethylsulfanyl-cyclohexanol (2)[12b]
: Yield
59%, light yellow oil; b.p. 95–97ꢁC/1 torr (lit[11]: 93–100ꢁC/1 torr).
1
IR ꢀmax (KBr, cmÀ1): 3200 (O–H). H NMR (CDCl3): 3.30 (m, 1H),
2.63 (q, 2H, J ¼ 7 Hz). 2.30–1.30 (m, 8H), 2.32 (m, 1H), 1.27 (t, 3H,
J ¼ 7 Hz). 13C NMR (CDCl3): 71.81, 52.45, 32.43, 28.03, 25.75, 23.61,
20.30, 14.91. Anal. calcd. forC 8H16OS: C 59.97, H 10.05; Found:
C 59.90, H 9.94.
Synthesis of 2-Ethylsulfanyl-2-methyl-cyclohexanol (3)
Preparation of 2-chloro-2-methyl-cyclohexanone[12c]: Yield 74%,
yellow oil; b.p. 90–92ꢁC/20 torr, (lit[12c]: 90ꢁC/20 torr). IR ꢀmax (KBr,
1
cmÀ1): 1730 (C¼O). H NMR (CDCl3): 3.40–1.40 (m, 8H), 1.58 (s, 3H).
Preparation of 2-ethylsulfanyl-2-methyl-cyclohexanone: Yield 73%,
light yellow oil; b.p. 53–54ꢁC/1 torr. IR ꢀmax (KBr, cmÀ1): 1725
1
(C¼O). H NMR (CDCl3): 2.30 (q, 3H, J ¼ 7 Hz), 3.40–1.60 (m, 8H),
1.40 (s, 3H), 1.15 (t, 3H, J ¼ 7 Hz). 13C NMR (CDCl3): 206.13, 53.04
39.81, 35.83, 26.32, 23.01, 21.50, 20.57, 13.54. Anal. calcd. for
C9H16OS: C 62.79, H 9.30; Found: C 62.80 H 9.35.
2-Ethylsulfanyl-2-methyl-cyclohexanol (3): Yield 68%, light yellow
oil; b.p. 77–78ꢁC/1 torr. IR ꢀmax (KBr, cmÀ1): 3200 (O–H). H NMR
1
(CDCl3): 3.3. (q, 1H, J1 ¼ 10 Hz, J2 ¼ 5 Hz), 2.58 (m, 3H, 2H with
D2O), 2.00–1.10 (m, 11H), 1.39 (s, 3H). 13C NMR (CDCl3): 73.18,
51.91, 34.94, 28.74, 24.42, 21.48, 21.04, 20.17, 14.23. Anal. calcd. for
C9H18OS: C 62.12, H 10.40; Found: C 62.32, H 10.54.
Synthesis of 2-Ethylsulfanyl-1,2-diphenyl-ethanol (4)
Preparation of benzoin[13a]: Yield 80%, colorless crystals; m.p.
135–137ꢁC (lit[13a]: 137ꢁC). IR ꢀmax (KBr, cmÀ1): 3230 (O–H), 167
1
(C¼O). H NMR (CDCl3): 8.10–7.70 (m, 2H), 7.60–7.05 (m, 8H), 5.86
(s, 1H), 4.30 (s, 1H).
Preparation of desyl chloride(2-chloro-1,2-diphenyl-ethanone)[13b]
:
Yield 80%, colorless crystals; m.p. 64–66ꢁC (lit[13a]: 65–66ꢁC). IR ꢀmax

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Chemical Oxidation Studies of b-Hydroxy-sulfides
1495
1
(KBr, cmÀ1): 1680 (C¼O). H NMR (CDCl3): 7.70–7.40 (m, 8H), 6.06
(s, 1H).
2-Ethylsulfanyl-1,2-diphenyl-ethanone[13]
:
Yield 73%, colorless
crystals; m.p. 75–77ꢁC (lit[13]: 74.1–75.5ꢁC). IR ꢀmax (KBr, cmÀ1): 1685
(C¼O). 1H NMR (CDCl3): 8.05–7.60 (m, 2H), 7.60–7.05 (m, 8H), 5.46 (s,
1H), 2.46 (q, 2H, J ¼ 8 Hz), 1.18 (t, 3H, J ¼ 8 Hz). 13C NMR (CDCl3):
195.02, 136.79, 135.89, 132.89, 128.77, 128.71, 128.65, 128.44, 127.68,
55.10, 25.41, 14.09. Anal. calcd. forC 16H16OS: C 75.00, H 6.25;
Found: C 74.92, H 6.24.
2-Ethylsulfanyl-1,2-diphenyl-ethanol (4): Yield 83%, colorless
crystals; m.p. 145–147ꢁC. IR ꢀmax (KBr, cmÀ1): 3320 (O–H). H NMR
1
(CDCl3): 6.75–6.70 (m, 7H), 6.46–6.55 (m, 3H), 4.60 (d, 1H, J ¼ 7 Hz),
3.76 (d, 1H, J ¼ 7 Hz), 3.05–2.85 (s, 1H, absent in D2O), 2.09 (q, 2H,
J ¼ 8 Hz), 1.06 (t, 3H, J ¼ 8 Hz). 13C NMR (CDCl3): 140.95, 139.50,
129.29, 128.82, 128.39, 127.85, 127.65, 127.55, 76.89, 59.55, 25.67, 14.39.
Anal. calcd. forC 16H18OS: C 74.42, H 6.98; Found: C 74.54, H 6.86.
Synthesis of tris(4-Bromophenyl)aminium
Hexachloroantimonate-TBPA (5)
Preparation of tris(4-bromophenyl)amine[14]: Yield 86%; light green
crystals; m.p. 144–146ꢁC (lit[14]: 144.5–146.5ꢁC). H NMR (CDCl3): 7.30
1
(d, 6H), 6.85 (d, 6H). 13C NMR (CDCl3): 146.00, 132.49, 125.53, 116.08.
Obtention of tris(4-bromophenyl)aminium hexachloroantimonate
(5)[15]: Yield 96%; deep blue powder; m.p. 141–142ꢁC (decomposition).
UV–Vis ꢁmax (CH2Cl2): 725 nm.
Chemical Oxidation of b-Hydroxy-sulfides with TBPA.
Typical Procedure
To a solution of 1.0 mmol of the b-hydroxy-sulfide and 0.05 g of
sodium bicarbonate in anydrous acetonitrile (5 mL) was slowly added
under magnetic stirring, 2.0 mmol (for 1 and 2) to 4.0 mmol (for 3 and
4) of TBPA. The resultant deep blue solution became colorless and then
water was added (1.0 mL). After 120 min, under magnetic stirring the
reactional mixture generated a green solid (tris-bromophenyl-amine)
and a yellow solution, which was poured into 50 mL of cold methanol;
then all the brominated amine was filtered off. After the filtration, the
resulting solution was poured into a saturated cold aqueous solution with
NaCl, the aqueous phase was extracted with dichloromethane

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1496
Donnici, Guimaraes, and de Melo
(3 ꢂ 50 mL) and dried over anhydrous sodium sulfate. After the removal
of solvent under reduced pressure and treatment the residue on purifica-
tion by column chromatography on silica gel, using hexane/ethyl acetate
(8:2 v/v) as the eluent, gave the purified products after the evaporation.
1
All the compounds produced were characterized by H and 13C NMR
and FT–IR spectra and elemental analysis.
cis-2-Ethylsulfinyl-cyclohexanol (1a/b): Yield 63% (1a and 1b), oil.
After another chromatographic separation on SiO2 (hexane/ethyl acetate
(9:1 v/v 1a and 1b were isolated)). (1a): Yield 33%, oil. IR ꢀmax (KBr, cmÀ1):
1
3300 (O–H), 1020 (S¼O). H NMR (CDCl3): 4.25 (m, 1H), 4.06 (m, 1H,
absent in D2O), 2.95–2.65 (m, 3H), 2.10–1.70 (m, 4H), 1.35 (t, 3H),
1.69–1.22 (m, 4H). 13C NMR (CDCl3): 67.50, 60.45, 42.38, 32.80,
24.29, 19.40, 18.40, 7.05. Anal. calcd. forC H16O2S: C 54.55, H 9.09;
8
Found: C 54.60, H 9.15. (1b): Yield 16%, oil. IR ꢀmax (KBr, cmÀ1): 3300
(O–H), 1020 (S¼O). 13C NMR (CDCl3): 64.36, 60.70, 42.58, 32.73, 24.83,
21.80, 19.35, 6.78. Anal. calcd. forC 8H16O2S: C 54.55, H 9.09; Found: C
54.62, H 9.16.
trans-2-Ethylsulfinyl-cyclohexanol (2a/b): Yield 69% (2a and 2b), oil.
After another chromatographic separation on SiO2 (hexane/ethyl acetate
(9:1 v/v 2a and 2b were isolated)). (2a): Yield 35%, light yellow crystals;
m.p. 43–46ꢁC. IR ꢀmax (KBr, cmÀ1): 3300 (O–H), 1020 (S¼O). H NMR
1
(CDCl3): 5.03 (m, 1H), 3.99 (m, 1H), 2.79–2.65 (m, 3H), 2.05–1.74 (m,
4H), 1.32 (t, 3H), 1.39–1.17 (m, 4H). 13C NMR (CDCl3): 71.05, 62.55,
44.08, 34.10, 24.90, 24.50, 23.40, 6.25. Anal. calcd. forC 8H16O2S: C
54.55, H 9.09; Found: C 54.50, H 8.95. (2b): Yield 18%, colorless crystals;
M.p 80–82ꢁC. IR ꢀmax (KBr, cmÀ1): 3300 (O–H), 1020 (S¼O). 13C NMR
(CDCl3): 68.46, 63.10, 42.08, 35.33, 24.34, 23.68, 21.15, 7.51. Anal. calcd.
forC H16O2S: C 54.55, H 9.09; Found: C 54.49, H 8.96.
8
Benzaldehyde (4a) (also identified as its corresponding 2,4-dinitro-
phenyl-hydrazone) and 2-methyl cyclohexanone (3a) were identified
spectroscopically, in full agreement, by comparison with commercial
samples (Aldrich). 3a and 4a were also quantified chromatographically.
Ethylethanethiolsulfonate was identified by comparing to the authentic
sample prepared as indicated.[15]
ACKNOWLEDGMENTS
The authors wish to thank Pro-Reitoria de Pesquisa
(PRPQ/UFMG), Fundacao de Amparo a Pesquisa do Estado de
Minas Gerais (FAPEMIG), Programa de Apoio Desenvolvimento

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Chemical Oxidation Studies of b-Hydroxy-sulfides
1497
Cientifico e Tecnologico (PADCT), and Conselho Nacional de
Desenvolvimento Cientıfico e Tecnologico (CNPq) forfinancial support.
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Received in the UK July 19, 2001

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