Odorless diphenyl diselenide and disulfide: Syntheses and applications

Article abstract of DOI:10.1055/s-2004-837289

Bis[4-(trimethylsilyl)phenyl]diselenide (3) and bis[4-(trimethylsilyl) phenyl]disulfide (31) are found to be odorless equivalents of the commonly used diphenyl diselenide and diphenyl disulfide, respectively. The diselenide 3 is shown to be useful in the preparation of odorless selenium(II) chloride 26 and selenium(IV) trichloride 28 that follow similar reactivity patterns to their phenyl derivatives and can be stored refrigerated under dry conditions. The corresponding selenium(II) bromide had to be prepared fresh from 3 before use. It is also shown that the trimethylsilyl group in the sulfide products can be protodesilylated quantitatively using TFA. Georg Thieme Verlag Stuttgart.

Full text of DOI:10.1055/s-2004-837289

PAPER
447
Odorless Diphenyl Diselenide and Disulfide: Syntheses and Applications
O
dorless
D
iph
r
enyl Dis
a
elenide
a
nd
n
D
isulfide
:
S
a
yntheses
a
b
Manabu Node*
Department of Pharmaceutical Manufacturing Chemistry, Kyoto Pharmaceutical University, Misasagi, Yamashina, Kyoto 607-8414, Japan
Fax +81(75)5954775; E-mail: node@mb.kyoto-phu.ac.jp
Received 8 September 2004; revised 18 October 2004
tempted to replace the commonly used malodorous sulfur
Abstract: Bis[4-(trimethylsilyl)phenyl]diselenide (3) and bis[4-
reagents with odorless equivalents.9 By elongating the
carbon chain or substituting the aromatic ring with n-hep-
tyl or, more effectively, a trimethylsilyl group (in the case
(trimethylsilyl)phenyl]disulfide (31) are found to be odorless equiv-
alents of the commonly used diphenyl diselenide and diphenyl di-
sulfide, respectively. The diselenide 3 is shown to be useful in the
preparation of odorless selenium(II) chloride 26 and selenium(IV) of benzene and benzyl thiols), we found a surprising re-
duction of odor or no odor at all.9f,10 In this paper, we
present our successful approach to replace the foul smell-
trichloride 28 that follow similar reactivity patterns to their phenyl
derivatives and can be stored refrigerated under dry conditions. The
corresponding selenium(II) bromide had to be prepared fresh from
ing diphenyl diselenide and disulfide with bis[4-(trimeth-
3 before use. It is also shown that the trimethylsilyl group in the sul-
ylsilyl)phenyl]diselenide and bis[4-(trimethylsilyl)phen-
fide products can be protodesilylated quantitatively using TFA.
yl]disulfide, respectively. Their syntheses and applica-
tions in various reactions are presented.
Key words: odorless, diselenide, disulfide, elimination
Bis[4-(trimethylsilyl)phenyl]diselenide
The starting 1-bromo-4-(trimethylsilyl)benzene (1) was
either purchased (Aldrich) or prepared according to the re-
ported procedure.11 The Grignard reagent 4-trimethylsi-
lylphenyl magnesium bromide was reacted with selenium
powder (Nacalai Tesque) to provide the organoselenium
intermediate 2 after aqueous work-up. Intermediate 2 was
then reduced with NaBH4 in MeOH to afford the desired
diselenide 3 as a low-melting yellow solid (mp 45 °C) in
65% yield (Scheme 1).
The versatility and the overall synthetic utility of various
reagents containing selenium and sulfur have been exem-
plified in their increasing use in synthesis.1 Especially in
the synthesis of complex natural products, these reagents
have been indispensable.2 During the last three decades
we have seen the literature flooded with papers containing
selenium-based reagents. Why has this exotic element, a
member of the well known family of chalcogens, enjoyed
such interest, even though the known toxicity of orga-
noselenium compounds called for caution and their mal-
odorous reputation made them doubly unattractive to any
chemist who wanted a social life outside the laboratory?
This is due to the mixed metallic and non-metallic nature
of the element, its unique reactivity towards oxidation and
reduction and the capacity of the selenium-based reagents
to perform highly chemoselective transformations.1,3
Among the selenium reagents, diphenyl diselenide is
commonly employed for organoselenylation reactions be-
cause of its versatile reactivity (nucleophilic as well as
electrophilic) depending on the reaction conditions and
thus allows a myriad of transformations through a-seleno
carbanions,4 a-seleno carbeniums5 and a-seleno carbon-
centered radicals.6 Similarly, diphenyl disulfide is an im-
portant and powerful reagent for phenyl sulfanylation and
related reactions that has closely followed the former in
various applications.7 The malodorous nature of these re-
agents has remained a potential drawback and it was only
in 1998 that Nicolaou, Ruhland et al. expedited the poly-
mer-supported selenium reagents that were odorless.8
(CH3)3Si
Mg, 1.5 h
NaBH4, MeOH
0 °C to r.t., 2 h
Ar (Se)n Ar
THF, Se, 3 h
Br
2
1
Si(CH3)3
Se Se
(CH3)3Si
3
Mp: 45 °C
Yield: 65%
Scheme 1 Synthesis of odorless diselenide 3
As expected, the new diselenide 3 was odorless in nature.
Our next venture aimed at its application vis-à-vis the par-
ent diphenyl diselenide and the results are presented in
Table 1.
Thus, 1-bromodecane (4) was treated with the selenolate
derived from diselenide 3 and NaBH4 to afford the decyl
4-(trimethylsilyl)phenyl selenide (5) in quantitative yield
after chromatographic purification. A comparable result
was obtained from the analogous reaction with diphenyl
diselenide (Table 1, entry 1). In entry 2 (Table 1), when
the lithium enolate of lactone 6 was allowed to react with
2 equivalents of diselenide 3, the selenylated lactone 7
was obtained in 85% yield with respect to 83% yield from
the parent diselenide. However, under the similar reaction
condition, butyrophenone (8) did not afford the desired
product 9. Presuming that the corresponding enolate to be
During the last few years, we have systematically studied
and developed odorless thiol and sulfide reagents and at-
SYNTHESIS 2005, No. 3, pp 0447–0457
x
x
.
x
x
.2
0
0
5
Advanced online publication: 16.12.2004
DOI: 10.1055/s-2004-837289; Art ID: F12504SS
© Georg Thieme Verlag Stuttgart · New York

448
P. K. Patra et al.
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Table 1 Reaction with Bis[4-(trimethylsilyl)phenyl]diselenide (3)
Entry
1
Substrate
Conditions
Producta
Yield (%)
93
Yieldb (%)
96
3 (1.0 equiv), NaBH4 (2 equiv), EtOH,
0 °C, 3 h
n-C9H19
SeAr
n-C9H19
Br
5
4
2
1) LDA (1.5 equiv), THF,
–78 °C, 20 min
85
83
SeAr
2) 3 (2.0 equiv), 2 h
O
O
O
O
6
7
3
1) LDA (1.5 equiv), THF,
–78 °C, 20 min
77
79
O
O
2) 3 (0.7 equiv), Br2 (0.7 equiv), 1 h
SeAr
OEt
8
9
4
5
1) NaH (1.2 equiv), THF,
0 °C, 20 min
2) 3 (0.6 equiv), Br2 (0.6 equiv), 1 h
93
83
98
81
O
O
O
SeAr
O
OEt
10
11
1) NaH (1.2 equiv), THF,
0 °C, 20 min
O
O
ArSe
2) 3 (0.6 equiv), Br2 (0.6 equiv), 1 h
O
O
O
O
O
12
14
16
13
6
7
8
3 (0.5 equiv), NaBH4 (2 equiv), EtOH,
0 °C–r.t.–reflux, 3 h
95
95
88e
80c
95d
98f
OH
SeAr
15
3 (0.6 equiv), DDQ (0.6 equiv), CH3CN,
24 h
OH
O
O
O
SeAr
17
3 (0.5 equiv), (NH4)2S2O8, CH3CN,
OH
SeAr
70 °C, 5 h
O
O
O
O
18
18
19
9
3 (0.5 equiv), (NH4)2S2O8, CH3CN,
70 °C, 17 h
95
–
O
20
a SeAr = 4-Trimethylsilylphenyl selenide.
b Using diphenyl diselenide.
c Starting material 14 (19%) was recovered when the reaction was carried at r.t., while the reaction under reflux for 3 h gave 71% of the desired
product.
d Ref.12
e Starting material remained.
f Ref.13
unreactive towards less electrophilic diselenide 3, freshly 11 in 93% yield. Under the same reaction conditions, re-
generated 4-(trimethylsilyl)phenylselenium bromide (pre- action of 10 using the diphenyl diselenide afforded 98%
pared from 1:1 equivalents of 3 and Br2 in THF) was add- yield of the product (Table 1, entry 4). Reaction of 2-
ed to the lithium enolate of 8 to achieve the a-selenylated acetyl-g-butyrolactone (12) similarly yielded the corre-
butyrophenone 9 in 77% yield. The same reaction from sponding a-selenolactone 13 (83% yield from 3 and 81%
diphenyl diselenide afforded 79% yield of the correspond- yield from diphenyl diselenide). We next performed the
ing butyrophenone-2-phenyl selenide (Table 1, entry 3). ring opening of epoxide 14 using the selenolate anion (de-
The sodium enolate of ethyl 2-cyclohexanone carboxylate rived from 3 in the presence of NaBH4 in EtOH) to get the
(10) was reacted smoothly with the freshly prepared sele- corresponding selenoalcohol 15 in 95% yield (Table 1,
nium bromide from 3 to give the corresponding ketoester entry 6). Following the procedure developed by Tiecco
Synthesis 2005, No. 3, 447–457 © Thieme Stuttgart · New York

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Odorless Diphenyl Diselenide and Disulfide: Syntheses and Applications
449
and co-workers,12 the reaction of 4-pentenoic acid (16) 4). The a-seleno-a-acetyl lactone 13 similarly afforded 25
with odorless diselenide 3 in the presence of DDQ yielded in moderate yield (Table 2, entry 5).
the corresponding lactone 17 in equally quantitative yield
(Table 1, entry 7). When 3-hexenoic acid (18) was sub-
Phenylselenium chloride and the corresponding trichlo-
ride are also very useful reagents to introduce electro-
jected to react with 3 in the presence of (NH4)2S2O8, after
five hours we obtained the desired 3-selenylated g-lactone
19 in 88% isolated yield (TLC of the reaction mixture
showed the presence of starting materials).13 Interestingly,
when the reaction mixture was allowed to stir-heat longer
(17 hours), the deselenylated lactone 20 was observed as
the only product and isolated in 95% yield (Table 1, entry
9).14
philic selenium into an organic molecule.17,18 We
attempted to produce their odorless variants by preparing
the corresponding selenium chloride 26 and trichloride 28
starting from odorless diselenide 3 following a reported
procedure using SO2Cl2.18 Although the corresponding se-
lenium(II) bromide had to be prepared fresh before each
reaction (Table 1, entries 3–5), the chloride 26 could be
stored19 under anhydrous conditions in a freezer (–20 °C).
Oxidative elimination15 of the selenium species were car- The corresponding selenium(IV) trichloride 28 was simi-
ried out for a few selected examples given below in larly stable enough and could be stored for several months
Table 2. Thus, substrate 9 in a CH2Cl2 solution was added at –20 °C. The a-selenylation reaction of acetone was per-
to pyridine (two equivalents) followed by aqueous 30% formed by stirring freshly prepared chloride 26 in acetone
hydrogen peroxide after 20 minutes to afford the corre- for one hour to yield 27 (47% yield). As further proof of
sponding pure a,b-unsaturated ketone 21 in 97% yield the reactivity of 26, the reaction of 3-hexenoic acid (18)
(Table 2, entry 1). The a-seleno lactone 7 was similarly cleanly afforded 19 (91% yield) after one hour.20 Follow-
reacted without base, yielding 22 (96% yield) within 45 ing an elegant report by Engman and co-workers,18b the
min.
seleno–Pummerer reaction of acetone starting from dise-
lenide 3 via the corresponding trichloride 28 afforded 29
in 71% yield (Scheme 2, three steps).
When excess aqueous hydrogen peroxide (10 equivalents)
was used under similar reaction conditions (two hours) to
oxidize a-seleno keto ester 11, the product that was ob- Bis[4-(trimethylsilyl)phenyl]disulfide
tained exclusively after purification was the correspond-
Diphenyl disulfide is the reagent of choice as far as phe-
ing epoxide 2316 (Table 2, entry 3). The same reaction for
a shorter time (30 minutes) using aqueous H2O2 (three
equivalents), however, afforded the desired ethyl cyclo-
hexenone carboxylate (24) in 72% yield (Table 2, entry
nylsulfanylation is concerned. Apart from traditional re-
actions, it offers chemo- and regioselective reactions that
have been increasingly applied in various total syntheses.
Therefore, in our quest for developing odorless sulfur re-
Table 2 Oxidative Removal of 4-(Trimethylsilyl)phenyl Selenide
Entry
1
Substrate
Conditions
Product
Yield (%)
97
9
Pyr (2.0 equiv), 30% aq H2O2 (3.0 equiv),
CH2Cl2, 0 °C–r.t., 20 min.
O
21
2
3
7
30% aq H2O2 (5.0 equiv), CH2Cl2
0 °C–r.t., 45 min.
96
91
O
O
22
11
30% aq H2O2 (10.0 equiv), CH2Cl2
0 °C–r.t., 2 h.
O
O
O
OEt
OEt
23
4
5
11
13
30% aq H2O2 (3.0 equiv), CH2Cl2
0 °C–r.t., 30 min.
72
64
O
O
24
O
30% aq H2O2 (2.0 equiv), CH2Cl2
0 °C–r.t., 15 min.
O
O
25
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450
P. K. Patra et al.
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19
RSe
with odorless methyl 6-morpholinohexyl sulfoxide
(MMSO)9a in the presence of hexamethyldisilazane
(HMDS) as shown in Scheme 3.
a
O
1 equiv
Ar
Cl
b
Se
26
Cl
27
SO2Cl2
Table 3 presents selected reactions of 31 to prove its use-
fulness relative to the diphenyl disulfide. Thus, reaction of
nonyl bromide (32) and thiolate anion (derived from di-
sulfide 31 and NaBH4) afforded 98% yield of the expected
sulfide 33 (Table 3, entry 1). Entries 2 and 3 demonstrate
the reactions of samarium sulfenate derived from 31 with
acid chlorides 34 and 36, respectively.22 The reaction of
indole (38) with 31 in the presence of NaH provided 3-
3
CHCl3
30 min
O
3 equiv
c
RSe
Ar Se Cl
Cl
Ar = 4-Si(CH3)3Ph
Cl
28
29
Scheme 2 4-(Trimethylsilyl)phenylselenium chloride (26) and tri-
chloride (28). Reagents and conditions: a: 18, CH2Cl2, 1 h, 91%; b:
(CH3)2CO, 1 h, 47%; c: i) (CH3)2CO (1.5 equiv), 10 min, ii) pyr (5
equiv), CH2Cl2, 1 h, 71% (three steps).
MMSO (3 equiv)
)
2
(CH3)3Si
S
(CH3)3Si
SH
agents,9,10 this became an obvious choice to replace the
malodorous diphenyl disulfide with its odorless equiva-
lent, 31.21 The synthesis involves oxidation of our previ-
ously reported odorless 4-trimethylsilylthiophenol (30)9f
HMDS (1.2 equiv)
30
31
Yield: 89 %
Scheme 3 Synthesis of bis[4-(trimethylsilyl)phenyl]disulfide (31)
Table 3 Reaction with Bis[4-(trimethylsilyl)phenyl]disulfide (31)
Entry
1
Substrate
Conditions
Producta
Yield (%)
98
Yieldb (%)
99
31 (0.5 equiv), NaBH4 (2 equiv),
EtOH, 0 °C–r.t.–reflux, 3 h
n-C8H17
Br
Cl
n-C8H17
SAr
32
33
2
3
31 (0.5 equiv), SmI2 (1.5 equiv),
THF, r.t., 2 h
73
86
72c
87c
O
O
n-C11H23
SAr
SAr
n-C11H23
35
34
31 (0.5 equiv), SmI2 (1.5 equiv),
THF, r.t., 2 h
O
O
Cl
36
38
37
39
4
NaH (1.2 equiv),
31 (1.1 equiv), DMF, r.t., 18 h
91
89d
SAr
N
N
H
H
5
6
1) LHMDS (1.5 equiv),
THF, –78 °C, 20 min
2) 31 (2 equiv), 4 h
81
78
80
80
SAr
O
O
O
O
6
40
1) LDA (1.2 equiv),
THF, –78 °C, 20 min
2) 31 (2 equiv), 4 h
CN
CN
SAr
H3CO
H3CO
41
42
7
8
31 (0.5 equiv),
NaBH4 (2 equiv), EtOH,
0 °C–r.t.–reflux, 3 h
94
94
OH
O
SAr
14
43
45
31 (3 equiv), n-Bu3P (3 equiv),
THF, r.t., 4 h
100
100
OH
SAr
44
a SAr = 4-Trimethylsilylphenyl sulfide.
b Using diphenyl disulfide.
c Ref.22
d Ref.23
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Odorless Diphenyl Diselenide and Disulfide: Syntheses and Applications
451
phenylsulfanylated indole 39 in high yield.23 The lithium
enolate of 2-methyl-g-lactone (6) reacted with two equiv-
alents of disulfide 31 to yield the corresponding a-sulfa-
nylated lactone 40 in 81% yield. The analogous reaction
with diphenyl disulfide afforded 2-methyl-2-phenylsulfa-
nyl-g-lactone also in equivalent yield (Table 3, entry 5).
Similarly, the lithium anion of 4-methoxyphenylacetoni-
trile (41) reacted with 31 and the parent disulfide in simi-
lar efficiencies to afford the corresponding a-sulfanylated
products in 78% and 80% yields, respectively. In entry 7
(Table 3), the ring opening of cyclohexene oxide (14) was
performed excellently using thiolate anion derived from
31 and in entry 8 (Table 3), to further substantiate the re-
actions of 31, the Hata reaction24 of alcohol 44 afforded
the corresponding sulfide 45 in quantitative yield. Finally,
the protodesilylation to regenerate the phenylthio deriva-
tives were conveniently carried out using TFA to afford
46–49 in 89–93% yields (Scheme 4).9f Thus, we have
shown that these newly developed odorless selenide and
sulfide derivatives perform typical reactions of commonly
used malodorous diphenyl diselenide and disulfide with
equal efficiency. This is the first report on these reagents
that are odorless but not resin-bound. Due to the extensive
use of selenium and sulfur reagents in organic synthesis,
it is very important to have their equivalents that provide
a totally odorless environment. We believe that these re-
agents can greatly serve the chemical community in pre-
serving the benignity, especially where large-scale
syntheses are concerned.
mixture was added selenium powder (700 mg, 8.81 mmol) at 45 °C
and vigorously stirred for 3 h. The reaction mixture was cooled and
filtered through a celite pad. The filtrate was poured into cold aq
NH4Cl solution (75 mL) and extracted with EtOAc (3 × 50 mL).
The organic extracts were washed with brine (2 × 25 mL) and water
(25 mL), dried (Na2SO4) and concentrated. The crude residue (1.49
g) was dissolved in MeOH (20 mL) and NaBH4 (740 mg, 19.52
mmol) was added slowly at 0 °C. The reaction mixture was stirred
at the same temperature for 1.5 h, poured into water (100 mL) and
extracted with EtOAc (3 × 50 mL), washed with brine (2 × 30 mL),
dried (Na2SO4) and concentrated. Column chromatography using
hexane afforded the diselenide 3 as a yellow solid (mp 44–45 °C,
1.10 g, 65%).
IR (CHCl3): 2955, 1715, 1600, 1575, 1540, 1375, 1250 cm–1.
1H NMR (400 MHz, CDCl3): d = 7.60 (AB, J = 8.2 Hz, 4 H, Ar-H),
7.41 (AB, J = 8.2 Hz, 4 H, Ar-H), 0.25 [s, 18 H, 2 × Si(CH3)3].
13C NMR (50 MHz, CDCl3): d = 139.7 (Cq-Ar), 134.0 (C-Ar), 131.9
(Cq-Ar), 130.1 (C-Ar), –1.1 [2 × Si(CH3)3].
MS (EI, 70 eV): m/z = 458 (39) [M+], 456 (36), 215 (20), 214 (48),
91 (42), 73 (100).
HRMS (EI): m/z calcd for C18H26Se2Si2: 457.9903; found:
457.9902.
1-(4-Trimethylsilylphenyl)selenodecane (5)
To a stirred solution of diselenide (3, 62 mg, 0.14 mmol) in absolute
EtOH (5 mL) at 0 °C was added NaBH4 (11.0 mg, 0.27 mmol) in
portions. After the reaction mixture became colorless (5–7 min), 1-
bromodecane (4, 30 mg, 0.14 mmol) in EtOH (2 mL) was added
dropwise. The reaction mixture was stirred for 3 h at r.t. Solvent was
reduced in vacuo and the reaction mixture was poured into sat. aq
NH4Cl solution (75 mL). The reaction mixture was extracted with
EtOAc (3 × 30 mL), washed with brine (2 × 20 mL) and water (25
mL), dried over Na2SO4 and concentrated. Column chromatography
using hexane–EtOAc (20:1) afforded 5 (47 mg, 94%) as a light yel-
low oil.
S
S
TFA
R
R
0 °C, 4–8 h
Si(CH3)3
33, 35, 37, 45
IR (CHCl3): 2930, 2855, 1605, 1250, 840 cm–1.
R = CH3-(CH2)8- (93%) 46
CH3-(CH2)10-CO- (92%) 47
Ph-CO- (91%) 48
1H NMR (400 MHz, CDCl3): d = 7.45 (AB, J = 8.2 Hz, 2 H, Ar-H),
7.38 (AB, J = 8.2 Hz, 2 H, Ar-H), 2.92 (t, J = 7.3 Hz, 2 H, CH2),
1.71 (quintet, J = 7.3 Hz, 2 H, CH2), 1.40 (quintet, J = 7.3 Hz, 2 H,
CH2), 1.34–1.22 (m, 12 H, CH2), 0.88 (t, J = 7.3 Hz, 3 H, CH3), 0.27
[s, 9 H, Si(CH3)3].
13C NMR (50 MHz, CDCl3): d = 138.3 (Cq-Ar), 133.8 (C-Ar), 131.9
(Cq-Ar), 131.1 (C-Ar), 31.9, 30.2, 29.9, 29.6, 29.5, 29.3, 29.1, 27.6,
22.7 (CH2), 14.1 (CH3), –1.2 [Si(CH3)3].
Ph-(CH2)3- (89%) 49
Scheme 4 Protodesilylation of 33, 35, 37, and 45
All reagents and starting materials were purchased from commer-
cial sources and used as received. All reactions were performed un-
der anhyd N2 atmosphere unless otherwise stated. Reaction solvents
such as THF, CH2Cl2, CHCl3 were dried prior to use. Analytical
TLC was done on pre-coated (0.25 mm) silica gel plates. Column
chromatography was conducted with 230–400 mesh silica gel. The
1H and 13C NMR spectra were recorded in CDCl3 using TMS as the
internal standard on a Varian Unity INOVA-400 or a Varian
GEMINI 2000/200 spectrometer. IR spectra were measured on a
Shimadzu FTIR-8300 spectrometer. The a,b-unsaturated products
21,15 22,15 23,16 24,25 2526 derived via selenoxide eliminations and
protodesilylated products 4722 and 4822 were identical to literature
data.
MS (EI, 70 eV): m/z = 370 (100) [M+], 368 (51), 355 (36), 215 (57),
230 (21), 73 (79), 55 (82).
HRMS (EI): m/z calcd for C19H34SeSi: 370.1595; found: 370.1599.
Anal. Calcd for C19H34SeSi: C, 61.76; H, 9.27. Found: C, 61.97; H,
9.18.
In an identical fashion, the corresponding phenylselenodecane was
prepared starting from 4 (80 mg, 0.36 mmol), diphenyl diselenide
(113 mg, 0.36 mmol) and NaBH4 (27.4 mg, 0.72 mmol) as a color-
less oil (103 mg, 96%).
IR (CHCl3): 2955, 2930, 2855, 1580, 1475, 1435 cm–1.
1H NMR (400 MHz, CDCl3): d = 7.49–7.47 (m, 2 H, Ar-H), 7.27–
7.21 (m, 3 H, Ar-H), 2.91 (t, J = 7.6 Hz, 2 H, CH2), 1.70 (quintet,
J = 7.6 Hz, 2 H, CH2), 1.40 (br quintet, J = 7.2 Hz, 2 H, CH2), 1.31–
1.25 (m, 12 H, CH2), 0.88 (t, J = 6.8 Hz, 3 H, CH3).
13C NMR (100 MHz, CDCl3): d = 132.3 (C-Ar), 130.7 (Cq-Ar),
128.9 (C-Ar), 126.5 (C-Ar), 31.9, 30.2, 29.8, 29.5, 29.4, 29.3, 29.1,
27.9, 22.6 (CH2), 14.1 (CH3).
Bis[4-(trimethylsilyl)phenyl]diselenide (3)
To a stirred suspension of Mg (268 mg, 11.01 mmol) and I2 (ca 5
mg) in anhyd THF (7 mL) at r.t. was added few drops of 1-bromo-
4-trimethylsilylbenzene (1, 1.68 g, 7.34 mmol) until the disappear-
ance of iodine color. The remaining 1 was diluted in THF (20 mL)
and added dropwise to the reaction mixture. The reagent was al-
lowed to stir for complete reaction at r.t. for 1.5 h. To the reaction
MS (EI, 60 eV): m/z = 298 (24) [M+], 254 (4), 158 (61), 57 (100).
Synthesis 2005, No. 3, 447–457 © Thieme Stuttgart · New York

452
P. K. Patra et al.
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HRMS (EI): m/z calcd for C16H26Se: 298.1199; found: 298.1197.
ane–EtOAc (10:1) afforded 11 (130.4 mg, 93%) as light yellow
crystals [mp 94–96 °C (hexane)].
3-Methyl-3-(4-trimethylsilylphenylselenyl)-3H-dihydrofuran-
2-one (7)
IR (CHCl3): 3030, 2955, 1710, 1605, 1240, 1200 cm–1.
1H NMR (400 MHz): d = 7.54 (AB, J = 8.0 Hz, 2 H, Ar-H), 7.44
(AB, J = 8.0 Hz, 2 H, Ar-H), 4.17 (q, J = 7.2 Hz, 2 H, OCH2), 2.67–
2.62 (m, 1 H), 2.40–2.50 (m, 2 H), 2.05–2.00 (m, 1 H), 1.92 (ddd,
J = 4.0, 9.2, 12.8 Hz, 1 H), 1.80–1.48 (m, 3 H), 1.21 (t, J = 7.2 Hz,
3 H, CH3), 0.26 [s, 9 H, Si(CH3)3].
13C NMR (50 MHz): d = 203.8 (CO), 169.1 (CO), 142.0 (Cq-Ar),
137.3, 133.4 (C-Ar), 126.4 (Cq-Ar), 62.5 (Cq), 61.8 (OCH2), 40.9,
38.0, 27.1, 23.8 (CH2), 14.0 (CH3), –1.1 [Si(CH3)3].
To a solution of LDA (1.5 equiv) at –78 °C, was added 2-methyl-g-
butyrolactone (6, 27.2 mg, 0.27 mmol, 1.0 equiv) in THF (2 mL)
dropwise. After 20 min, to the reaction mixture was added a solu-
tion of 3 (249 mg, 0.54 mmol) and stirred for 1 h at the same tem-
perature. The reaction mixture was quenched with sat. aq NH4Cl
solution (100 mL), extracted with EtOAc (3 × 30 mL), washed with
brine (2 × 30 mL) and water (50 mL), dried (Na2SO4) and concen-
trated. Column chromatography using hexane–EtOAc (10:1) af-
forded pure compound as a light yellow oil (76 mg, 85%). The first
fractions contained recovered diselenide 3 (180 mg, 72%).
MS (EI, 70 eV): m/z = 398 (64) [M+], 396 (31), 215 (46), 123 (53),
95 (74), 73 (100), 55 (65).
IR (CHCl3): 3025, 3015, 1760, 1465, 1380, 1225 cm–1.
HRMS (EI): m/z calcd for C18H26O3SeSi: 398.0816; found:
398.0823.
1H NMR (400 MHz): d = 7.63 (AB, J = 8.4 Hz, 2 H, Ar-H), 7.48
(AB, J = 8.4 Hz, 2 H, Ar-H), 4.23 (ddddd, J = 2.8, 6.8, 8.0, 9.2, 15.6
Hz, 2 H, CH2), 2.36 (ddddd, J = 2.8, 6.8, 8.0, 9.2, 14.4 Hz, 2 H,
CH2), 1.65 (s, 3 H, CH3), 0.27 [s, 9 H, Si(CH3)3].
13C NMR (50 MHz): d = 177.5 (CO), 142.6 (Cq-Ar), 136.8, 133.9
(C-Ar), 126.3 (Cq-Ar), 64.9 (OCH2), 44.0 (Cq), 37.7 (CH2), 24.2
(CH3), –1.1 [Si(CH3)3].
Under identical reaction conditions, the corresponding ethyl phe-
nylselenylcyclohexan-2-one carboxylate was obtained as a color-
less oil (280 mg, 98%) starting from 10 (150 mg, 0.88 mmol) and
diphenyl diselenide (165 mg, 0.53 mmol).
IR (CHCl3): 3005, 2945, 1710, 1435, 1245 cm–1.
1H NMR (200 MHz): d = 7.58–7.56 (m, 2 H, Ar-H), 7.42–7.27 (m,
3 H, Ar-H), 4.19 (q, J = 7.2 Hz, 2 H, OCH2), 2.67–2.61 (m, 1 H),
2.46–2.37 (m, 2 H), 2.10–1.40 (m, 5 H), 1.22 (t, J = 7.2 Hz, 3 H,
CH3).
MS (EI, 70 eV): m/z = 328 (50) [M+], 326 (25), 313 (14), 215 (100),
213 (56), 149 (14), 135 (13), 91 (48), 83 (34), 73 (34), 55 (22).
HRMS (EI): m/z for C14H20O2SeSi: 328.0397; found: 328.0400.
13C NMR (50 MHz): d = 203.8 (CO), 169.0 (CO), 142.0 (Cq-Ar),
138.2, 129.3, 128.6 (C-Ar), 125.7 (Cq-Ar), 62.5 (Cq), 61.8 (OCH2),
40.9, 38.0, 27.1, 23.7 (CH2), 14.0 (CH3).
MS (EI, 70 eV): m/z = 326 (46) [M+], 157 (34), 141 (31), 123 (30),
113 (34), 95 (84), 67 (100).
1-Phenyl-2-(4-trimethylsilylphenylselenyl)-1-butanone (9)
To a solution of LDA (1.5 equiv) at –78 °C, was added n-butyrophe-
none (8, 32.5 mg, 0.22 mmol) in THF (2 mL) dropwise. After 20
min, to the reaction mixture was added a solution of 3 (70.5 mg,
0.15 mmol) and Br2 (8 mL, 0.15 mmol) in THF (3 mL) and stirred
for 1 h at the same temperature. The reaction mixture was quenched
with sat. aq NH4Cl solution (100 mL), extracted with EtOAc (3 × 30
mL), washed with brine (2 × 30 mL) and water (50 mL), dried
(Na2SO4) and concentrated. Column chromatography using hex-
ane–EtOAc (20:1) afforded pure compound 9 as a light yellow oil
(64 mg, 77%).
HRMS (EI): m/z calcd for C15H18O3Se: 326.0421; found: 326.0414.
3-Acetyl-3-(4-trimethylsilylphenylselenyl)-3H-dihydrofuran-2-
one (13)
Following the above-mentioned procedure for the preparation of 11,
the sodium enolate of 12 (50 mg, 0.39 mmol) was reacted with 3
(110 mg, 0.24 mmol) to yield 13 as a light yellow oil (115 mg,
83%).
IR (CHCl3): 2960, 1675, 1600, 1580, 1450, 1250, 1200 cm–1.
1H NMR (400 MHz): d = 7.86 (dd, J = 1.2, 8.4 Hz, 2 H, Ar-H), 7.55–
7.51 (m, 1 H, Ar-H), 7.43–7.38 (m, 6 H, Ar-H), 4.43 (t, J = 7.2 Hz,
1 H, CH), 2.08 (quintet, J = 7.2 Hz, 1 H, CH2), 1.91 (quintet, J = 7.2
Hz, 1 H, CH2), 1.05 (t, J = 7.2 Hz, 3 H, CH3), 0.26 [s, 9 H, Si(CH3)3].
13C NMR (100 MHz): d = 196.0 (CO), 141.3, 136.4 (Cq-Ar), 135.4,
133.8, 132.7, 128.4, 128.3 (C-Ar), 128.0 (Cq-Ar), 47.7 (CH), 24.4
(CH2), 12.8 (CH3), –1.2 [SiCH3)3].
IR (CHCl3): 3040, 2955, 1760, 1700, 1575, 1375, 1250 cm–1.
1H NMR (400 MHz): d = 7.49 (br s, 4 H, Ar-H), 4.37–4.24 (m, 2 H,
CH2), 2.77 (ddd, J = 6.4, 9.2, 14.4 Hz, 1 H, CH2), 2.62 (s, 3 H, CH3),
2.10 (ddd, J = 3.2, 9.2, 14.4 Hz, 1 H, CH2), 0.27 [s, 9 H, Si(CH3)3].
13C NMR (50 MHz): d = 199.0 (CO), 172.1 (CO), 143.7 (Cq-Ar),
136.0, 134.3 (C-Ar), 126.1 (Cq-Ar), 65.4 (OCH2), 56.3 (Cq), 30.9
(CH2), 26.1 (CH3), –1.2 [Si(CH3)3].
MS (EI, 70 eV): m/z = 376 (19) [M+], 374 (12), 271 (12), 215 (7),
214 (9), 105 (57), 91 (27), 73 (100).
MS (EI, 70 eV): m/z = 356 (19) [M+], 354 (12), 314 (31), 312 (16),
234 (33), 233 (66), 215 (19), 214 (30), 131 (83), 83 (97), 73 (100).
HRMS (EI): m/z calcd for C19H24OSeSi: 376.0761; found:
376.0757.
HRMS (EI): m/z calcd for C15H20O3SeSi: 356.0347; found:
356.0344.
Anal. Calcd for C19H24OSeSi: C, 60.78; H, 6.44. Found: C, 61.19;
H, 6.80.
Anal. Calcd for C15H20O3SeSi: C, 50.70; H, 5.67. Found: C, 50.71;
H, 5.60.
Ethyl 1-(4-Trimethylsilylphenylselenyl)cyclohexan-2-one Car-
boxylate (11)
In a similar fashion, the reaction of diphenyl diselenide (292 mg,
0.94 mmol) with 12 (200 mg, 1.56 mmol) afforded 3-acetyl-3-phe-
nylselenyl-3H-dihydrofuran-2-one as a colorless oil (357.6 mg,
81%).
To a solution of NaH (14.5 mg of 70% emulsion, 0.42 mmol) at 0
°C, was added ethyl 1-cyclohexanone carboxylate (10, 60 mg, 0.35
mmol) in THF (5 mL) dropwise. After 15 min, to the reaction mix-
ture was added a solution of 3 (96.8 mg, 0.21 mmol) and Br2 (10.80
mL, 0.21 mmol) in THF (3 mL) and stirred for 30 min–1 h at the
same temperature. The reaction mixture was quenched with water
(50 mL), extracted with EtOAc (3 × 30 mL), washed with sat. aq
NaHCO3 (20 mL), brine (2 × 30 mL) and water (50 mL), dried
(Na2SO4) and concentrated. Column chromatography using hex-
IR (CHCl3): 3040, 3005, 1775, 1700, 1440, 1370, 1240 cm–1.
1H NMR (200 MHz): d = 7.58–7.30 (m, 5 H, Ar-H), 4.40–4.20 (m,
2 H, CH2), 2.77 (ddd, J = 6.4, 9.2, 14.4 Hz, 1 H, CH2), 2.65 (s, 3 H,
CH3), 2.09 (ddd, J = 3.2, 9.2, 14.4 Hz, 1 H, CH2).
Synthesis 2005, No. 3, 447–457 © Thieme Stuttgart · New York

PAPER
Odorless Diphenyl Diselenide and Disulfide: Syntheses and Applications
453
13C NMR (50 MHz): d = 199.0 (CO), 172.1 (CO), 137.2, 130.5,
129.6 (C-Ar), 125.5 (Cq-Ar), 65.4 (OCH2), 56.4 (Cq), 31.0 (CH2),
26.2 (CH3).
MS (EI, 70 eV): m/z = 284 (18) [M+], 242 (51), 161 (100), 117 (40),
105 (50), 77 (72).
Trans-5-ethyl-4-(4-trimethylsilylphenylselenyl)-3H-dihydrofu-
ran-2-one (19)
A solution of 3-hexenoic acid (18, 30 mg, 0.26 mmol), 3 (60.2 mg,
0.13 mmol) and (NH4)2S2O8 (72 mg, 0.32 mmol) in anhyd CH3CN
(7 mL) was stirred at 70 °C for 5 h (17 h in the case of entry 9). Sol-
vent was reduced in vacuo and the reaction mixture was poured into
aq NaHCO3 solution. The reaction mixture was extracted with Et2O
(3 × 25 mL), washed with water (25 mL) and dried over Na2SO4 and
concentrated. Column chromatography using hexane–EtOAc (1:1)
afforded 19 (79 mg, 88%).
HRMS (EI): m/z calcd for C12H12O3Se: 283.9951; found: 283.9956.
Trans-2-(4-trimethylsilylphenylselenyl)cyclohexanol (15)
To a stirred solution of diselenide 3 (128.3 mg, 0.28 mmol) in abso-
lute EtOH (5 mL) at 0 °C was added NaBH4 (19.3 mg, 0.51 mmol)
in portions. After the reaction mixture became colorless (5–7 min)
the cyclohexene oxide (14, 50 mg, 0.51 mmol) was added in EtOH
(2 mL) dropwise. The reaction mixture was stirred for 2 h at r.t. and
heated at 75 °C for 1 h. Solvent was reduced in vacuo and the reac-
tion mixture was poured into sat. aq NH4Cl solution (75 mL). The
reaction mixture was extracted with EtOAc (3 × 30 mL), washed
with brine (2 × 20 mL) and water (25 mL), dried over Na2SO4 and
concentrated. Column chromatography using hexane–EtOAc (10:1)
afforded 15 (159 mg, 95%).
IR (CHCl3): 3010, 1775, 1250, 1240, 1200 cm–1.
1H NMR (400 MHz): d = 7.52 (AB, J = 8.0 Hz, 2 H, Ar-H), 7.42
(AB, J = 8.0 Hz, 2 H, Ar-H), 4.33 (ddd, J = 4.0, 4.0, 7.6 Hz, 1 H,
CHO), 3.51 (ddd, J = 7.6, 8.4, 9.2 Hz, 1 H, CH), 2.93 (ABX, dd, J =
8.4, 18.0 Hz, 1 H, CH2), 2.59 (ABX, dd, J = 9.2, 18.0 Hz, 1 H, CH2),
1.80–1.88 (m, 1 H, CH2), 1.62–1.70 (m, 1 H, CH2), 1.01 (t, J = 7.2
Hz, 3 H, CH3), 0.26 [s, 9 H, Si(CH3)3].
13C NMR (50 MHz): d = 174.6 (CO), 141.6 (Cq-Ar), 134.9, 134.2
(C-Ar), 126.7 (Cq-Ar), 87.0 (OCH), 38.5 (CH-Se), 36.5, 26.8 (CH2),
9.8 (CH3), –1.2 [Si(CH3)3].
IR (CHCl3): 3010, 2940, 2860, 1575, 1450, 1250, 1235 cm–1.
1H NMR (400 MHz): d = 7.58 (AB, J = 8.0 Hz, 2 H, Ar-H), 7.43
(AB, J = 8.0 Hz, 2 H, Ar-H), 3.35 (ddd, J = 4.0, 9.6, 15.6 Hz, 1 H,
CH), 2.89–2.96 (m, 2 H, CH, OH), 2.12–2.23 (m, 2 H, CH2), 1.22–
1.76 (m, 6 H, CH2), 0.26 [s, 9 H, Si(CH3)3].
13C NMR (50 MHz): d = 140.3 (Cq-Ar), 134.8 (C-Ar), 133.8 (C-Ar),
127.6 (Cq-Ar), 72.4 (CHOH), 53.7 (CHSe), 33.9, 33.5, 26.9, 24.5
(CH2), –1.1 [Si(CH3)3].
MS (EI, 70 eV): m/z = 342 (35) [M+], 283 (7), 215 (100), 73 (82).
HRMS (EI): m/z calcd for C15H22O2SeSi: 342.0554; found:
342.0562.
Anal. Calcd for C15H22O2SeSi: C, 52.77; H, 6.50. Found: C, 53.05;
H, 6.52.
Oxidative Removal of 4-Trimethylsilylphenyl Selenide; Gener-
al Procedure
MS (EI, 70 eV): m/z = 328 (43) [M+], 326 (22), 230 (52), 215 (100),
81 (95), 73 (40), 55 (28).
To a solution of a-selenyl compound (0.30 mmol) in CH2Cl2 (2
mL), at 0 °C was added dropwise a solution of 30% aq H2O2 in wa-
ter (2 mL). The reaction mixture was stirred for 20 min–2 h (moni-
tored by TLC), quenched with aq NaHCO3 (10%, 25 mL) and
extracted with CH2Cl2 (2 × 20 mL), washed with aq NaHCO3 (2 ×
50 mL) and brine (20 mL) and dried (Na2SO4). Crude material was
purified by chromatography if required using hexane–EtOAc. Data
are comparable to literature values.
HRMS (EI): m/z calcd for C15H24OSeSi: 328.0761; found:
328.0761.
Anal. Calcd for C15H24OSeSi: C, 55.03; H, 7.39. Found: C, 55.29;
H, 7.46.
5-[(4-Trimethylsilylphenylselenyl)methyl]-3H-dihydrofuran-2-
one (17)
1-Phenylbut-2-en-1-one (21)15
A solution of pentenoic acid (16, 38 mg, 0.38 mmol), 3 (104.3 mg,
0.23 mmol) and DDQ (51.7 mg, 0.23 mmol) in anhyd CH3CN (7
mL) was stirred at r.t. for 24 h. Solvent was reduced in vacuo and
the reaction mixture was poured into 10% aq Na2CO3 solution. The
reaction mixture was extracted with Et2O (3 × 25 mL), washed with
water (25 mL) and dried over Na2SO4 and concentrated. Column
chromatography using hexane–EtOAc (1:1) afforded pure 17 (119
mg, 95%).
To a solution of 9 (112 mg, 0.30 mmol) in CH2Cl2 (2 mL), at 0 °C
was added pyridine (48.40 mL, 0.60 mmol) followed by dropwise
addition of a solution of 30% aq H2O2 (102 mg, 0.90 mmol) in water
(2 mL). The reaction mixture was stirred for 5 min at 0 °C and at r.t.
for 25 min (monitored by TLC). The reaction mixture was diluted
with CH2Cl2 (20 mL) and the organic layer was washed with 1 N
HCl (25 mL), aq NaHCO3 (10%, 2 × 25 mL), brine (20 mL) and
dried (Na2SO4). The crude material was purified by column chro-
matography using hexane–EtOAc (4:1) to obtain 21 (45 mg, 97%).
IR (CHCl3): 2955, 1770, 1580, 1380, 1250, 1170 cm–1.
1H NMR (400 MHz): d = 7.51 (AB, J = 8.0 Hz, 2 H, Ar-H), 7.42
(AB, J = 8.0 Hz, 2 H, Ar-H), 4.62–4.68 (m, 1 H, CH), 3.32 (dd, J =
4.8, 12.8 Hz, 1 H, CH2), 3.01 (dd, J = 8.2, 12.8 Hz, 1 H, CH2), 2.50–
2.64 (m, 2 H, CH2), 2.38–2.50 (m, 1 H, CH2), 1.92–2.02 (m, 1 H,
CH2), 0.26 [s, 9 H, Si(CH3)3].
13C NMR (100 MHz): d = 176.3 (CO), 140.0 (Cq-Ar), 134.2 (C-Ar),
132.1 (C-Ar), 129.8 (Cq-Ar), 79.3 (OCH), 31.5, 28.8, 27.7 (CH2),
–1.2 [Si(CH3)3].
3-Methyl-5H-furan-2-one (22)15
To a solution of 7 (62 mg, 0.19 mmol) in CH2Cl2 (2 mL), at 0 °C
was added dropwise a solution of 30% aq H2O2 (108 mg, 0.95
mmol) in water (2 mL). The reaction mixture was stirred for 45 min
at 0 °C–r.t. (monitored by TLC). The reaction mixture was worked
up following the general procedure to afford 22 (17.3 mg, 96%) that
was pure in NMR.
MS (EI, 70 eV): m/z = 328 (4) [M+], 326 (2), 215 (3), 149 (4), 83
(100), 73 (8), 55 (14).
Ethyl 7-Oxabicyclo[4.1.0]heptane-2-oxo-1-carboxylate (23)16
To a solution of 11 (109.7 mg, 0.27 mmol) in CH2Cl2 (5 mL), at 0
°C was added dropwise a solution of 30% aq H2O2 (2 mL) in water
(2 mL). The reaction mixture was stirred for 2 h at 0 °C–r.t. The re-
action mixture, after work-up according to general procedure and
purification by column chromatography (hexane–EtOAc, 4:1), af-
forded the corresponding epoxide 23 (46 mg, 91%) as a colorless
oil.
HRMS (EI): m/z calcd for C14H20SeSi: 328.0397; found: 328.0400.
Anal. Calcd for C14H20SeSi: C, 51.37; H, 6.16. Found: C, 51.65; H,
6.24.
Synthesis 2005, No. 3, 447–457 © Thieme Stuttgart · New York

454
P. K. Patra et al.
PAPER
Preparation of 4-Trimethylsilylphenylselenium Trichloride
Ethyl 6-Oxo-cyclohex-1-enecarboxylate (24)25
To a solution of 11 (41 mg, 0.10 mmol) in CH2Cl2 (2 mL), at 0 °C
was added dropwise a solution of 30% aq H2O2 (35 mg, 0.31 mmol)
in water (2 mL). The reaction mixture was stirred for 30 min at 0
°C–r.t. Work-up was followed according to the general procedure
and the crude residue was purified by column chromatography
(hexane–EtOAc, 4:1) to yield 24 (12.5 mg, 72%).
(28) and its Reaction with Acetone: Synthesis of 1-Chloro-1-(4-
Trimethylsilylphenylselenyl)propan-2-one (29)
To a solution of 3 (194 mg, 0.42 mmol) in anhyd CHCl3 (5 mL) at
5–10 °C was added SO2Cl2 (102 mL, 1.27 mmol) dropwise. While
addition, the color of the reaction mixture changed gradually from
deep red to light brown to colorless ensuring complete formation of
the corresponding trichloride 28.18 The reaction mixture was stirred
at the same temperature for 30 min before being concentrated in
vacuo. The light yellow crystals of 28 (mp 65–67 °C, Et2O) were
taken in anhyd Et2O (3 mL) and acetone (92.5 mL, 1.26 mmol) was
added. The reaction mixture was stirred for 10–15 min at r.t. during
which time the solution became homogenous. The solvent was re-
moved in vacuo and the residue was diluted with CH2Cl2 (5 mL). At
10 °C to the reaction mixture was added pyridine (340 mL, 4.20
mmol) dropwise and stirred for 1 h while warming to r.t. The reac-
tion mixture was poured into aq 1 N HCl (20 mL), diluted with
CH2Cl2 (15 mL) and the organic layer was washed successively
with aq 1 N HCl (2 × 15 mL), brine (10 mL) and water (10 mL) and
dried (Na2SO4). After concentration in vacuo and purification by
column chromatography using hexane–EtOAc (10:1) as the eluent,
29 was obtained (191 mg, 71%) as a light yellow oil.
3-Acetyl-2(5H)-furanone (25)26
To a solution of 13 (77 mg, 0.22 mmol) in CH2Cl2 (2 mL), at 0 °C
was added dropwise a solution of 30% aq H2O2 (50 mg, 0.44 mmol)
in water (2 mL). The reaction mixture was stirred for 15 min at 0 °C.
Following the general procedure, the reaction mixture was worked
up and purified (silica gel column; hexane–EtOAc, 4:1) to afford 25
(18 mg, 64%) as a colorless liquid.
Preparation of 4-Trimethylsilylphenylselenium Chloride (26)
and its Reaction with Acetone: Synthesis of 1-(4-Trimethylsi-
lylphenylselenyl)propan-2-one (27)
To a solution of 3 (126 mg, 0.275 mmol) in anhyd CHCl3 (1 mL) at
5–10 °C was added SO2Cl2 (22.1 mL, 0.275 mmol) dropwise. While
addition the color of the reaction mixture changed to deep red indi-
cating the formation of the corresponding monochloride 26. After
30 min stirring under Ar, the solvent was evaporated in vacuo to af-
ford 26 (200 mg) as dark red liquid (Caution: The removal of sol-
vent CHCl3 should be carried out under anhydrous condition and the
chloride 26 if required can be stored dry under Ar at –20 °C).19 The
mass spectra of which contained 26 (264, M+) along with the dise-
lenide 3 (458, M+).
IR (CHCl3): 3025, 2960, 1720, 1375, 1250 cm–1.
1H NMR (200 MHz): d = 7.60 (AB, J = 8.0 Hz, 2 H, Ar-H), 7.49
(AB, J = 8.4 Hz, 2 H, Ar-H), 5.53 (s, 1 H, CH), 2.37 (s, 3 H, CH3),
0.27 [s, 9 H, Si(CH3)3].
13C NMR (50 MHz): d = 197.1 (CO), 142.6 (Cq-Ar), 134.7, 134.2
(C-Ar), 126.8 (Cq-Ar), 60.8 (CH), 25.3 (CH3), –1.1 [Si(CH3)3].
MS (EI, 70 eV): m/z = 320 (54) [M+], 305 (16), 277 (16), 214 (29),
169 (51), 91 (58), 73 (100).
MS (EI, 20 eV): m/z = 264 (37) [M+], 249 (60), 229 (12), 149 (12),
91 (30), 73 (100).
HRMS (EI): m/z calcd for C6H13SeSiCl: 263.9640; found:
263.9645.
HRMS (EI): m/z calcd for C12H17ClOSeSi: 319.9902; found:
319.9901.
To the chloride 26 (145 mg, 0.55 mmol) in anhyd Et2O (2 mL) was
added acetone (1 mL). During the addition rapid decolorization was
observed and the mixture was stirred for 1 h at 10 °C. The reaction
mixture was poured into water (10 mL), extracted with Et2O (3 × 15
mL) and washed with brine (2 × 10 mL) and dried (Na2SO4). The
solvent was removed in vacuo and the residue was purified by col-
umn chromatography using hexane–EtOAc (10:1) to afford 27 (73
mg, 47%) as a colorless liquid.
Bis[4-(trimethylsilyl)phenyl]disulfide (31)
To a solution of 4-trimethylsilylthiophenol (30, 45 mg, 0.25 mmol)
and MMSO (175 mg, 0.75 mmol) in CH3CN (2 mL) was added
HMDS (63 mL, 0.3 mmol) at r.t. followed by stirring for 1 h (moni-
tored by TLC). The solvent was removed under vacuum and the re-
action was quenched with aq NaOH (10%, 2 mL). It was then
extracted with EtOAc (3 × 10 mL). The combined organic extracts
were thoroughly washed with aq 1 N HCl (3 × 15 mL), water (2 ×
15 mL), brine (15 mL) and dried (Na2SO4). Solvent was removed
under vacuum and the crude disulfide was purified by silica gel col-
umn chromatography using hexane as the eluent to afford 31 (40
mg, 89%) as a colorless solid [mp 47–48 °C (n-hexane); lit.21 mp
62–63 °C].
IR (CHCl3): 3015, 2960, 1700, 1575, 1375, 1250 cm–1.
1H NMR (400 MHz): d = 7.49 (AB, J = 8.4 Hz, 2 H, Ar-H), 7.42
(AB, J = 8.4 Hz, 2 H, Ar-H), 3.60 (s, 2 H, CH2), 2.29 (s, 3 H, CH3),
0.25 [s, 9 H, Si(CH3)3].
13C NMR (50 MHz): d = 203.4 (CO), 140.1 (Cq-Ar), 134.1, 131.9
(C-Ar), 129.5 (Cq-Ar), 36.6 (CH2), 28.1 (CH3), –1.1 [Si(CH3)3].
IR (CHCl3): 3030, 1575, 1250, 1115 cm–1.
MS (EI, 70 eV): m/z = 286 (9) [M+], 271 (4), 254 (4), 214 (4), 149
(7), 123 (9), 83 (100).
1H NMR (400 MHz): d = 7.48 (AB, J = 8.4 Hz, 4 H, Ar-H), 7.42
(AB, J = 8.4 Hz, 4 H, Ar-H), 0.24 [s, 18 H, 2 × Si(CH3)3].
HRMS (EI): m/z calcd for C12H18OSeSi: 286.0292; found:
286.0295.
13C NMR (100 MHz): d = 139.2, 137.8 (Cq-Ar), 133.9, 126.2 (C-
Ar), –1.2 [2 × Si(CH3)3].
MS (EI, 70 eV): m/z = 362 (34) [M+], 347 (24), 166 (31), 151 (9),
91 (14), 83 (100).
Reaction of 26 with 18: Synthesis of 19
To the chloride 26 [obtained from 3 (89 mg, 0.19 mmol) and SO2Cl2
(16 mL, 0.19 mmol)] in anhyd CH2Cl2 (3 mL) was added 18 (48.7
mg, 0.43 mmol) and the mixture was stirred for 1 h at 10 °C. The
reaction mixture was poured into water (10 mL), extracted with
EtOAc (3 × 15 mL) and washed with aq NaHCO3 (2 × 20 mL), brine
(10 mL) and dried (Na2SO4). The solvent was removed in vacuo and
the residue was purified by column chromatography using hexane–
EtOAc (10:1) to afford 19 (133.5 mg, 91%) as a colorless liquid.
Spectral data of 19 is mentioned above.
HRMS (EI): m/z calcd for C18H26S2Si2: 362.1015; found: 362.1014.
Anal. Calcd for C18H26S2Si2: C, 59.65; H, 7.24. Found: C, 59.28; H,
7.19.
1-(4-Trimethylsilylphenyl)thiononane (33)
To a solution of 32 (58 mg, 0.28 mmol) and 31 (54 mg, 0.14 mmol)
in EtOH (5 mL) was added NaBH4 (22 mg, 0.56 mmol) at 0 °C and
the mixture was stirred at 80 °C for 3 h. The solvent was removed
under vacuum and the residue was quenched with sat. aq NH4Cl so-
lution (20 mL) and extracted with EtOAc (3 × 20 mL). The com-
Synthesis 2005, No. 3, 447–457 © Thieme Stuttgart · New York

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Odorless Diphenyl Diselenide and Disulfide: Syntheses and Applications
455
bined organic extracts were washed with water (2 × 30 mL), brine
(20 mL), dried (Na2SO4) and concentrated. The crude product was
purified by silica gel column using hexane as the eluent to afford 33
(82.4 mg, 98%) as a colorless oil.
1H NMR (400 MHz): d = 8.06–8.02 (m, 2 H, Ar-H), 7.63–7.58 (m,
3 H, Ar-H), 7.51–7.46 (m, 4 H, Ar-H), 0.29 [s, 9 H, Si(CH3)3].
13C NMR (100 MHz): d = 190.2 (CO), 142.4, 136.7 (Cq-Ar), 134.2,
134.0, 133.6, 128.7 (C-Ar), 127.8 (Cq-Ar), 127.5 (C-Ar), –1.2
[Si(CH3)3].
IR (CHCl3): 2930, 1580, 1455, 1250, 1080 cm–1.
1H NMR (400 MHz): d = 7.41 (AB, J = 8.4 Hz, 2 H, Ar-H), 7.28
(AB, J = 8.4 Hz, 2 H, Ar-H), 2.92 (t, J = 7.2 Hz, 2 H, CH2), 1.69–
1.62 (m, 2 H, CH2), 1.48–1.38 (m, 2 H, CH2), 1.34–1.28 (m, 10 H,
CH2), 0.88 (t, J = 7.2 Hz, 3 H, CH3), 0.25 [s, 9 H, Si(CH3)3].
MS (EI, 70 eV): m/z = 286 (3) [M+], 105 (100), 91 (6), 85 (11), 83
(14), 77 (30), 71 (10), 57 (14).
HRMS (EI): m/z calcd for C16H18OSiS: 286.0848; found: 286.0845.
13C NMR (100 MHz): d = 138.1, 137.1 (Cq-Ar), 133.7, 127.5 (C-
Ar), 32.9, 31.9, 29.5, 29.3, 29.2, 29.1, 28.9, 22.7 (CH2), 14.1 (CH3),
–1.1 [Si(CH3)3].
MS (EI, 70 eV): m/z = 308 (82) [M+], 293 (100), 167 (37), 165 (10),
91 (18), 83 (13), 73 (48).
Indole-3-(4-trimethylsilylphenyl) Sulfide (39)
To a suspension of NaH (13 mg, 70% NaH dispersion in mineral oil,
0.38 mmol) in anhyd DMF (1.5 mL) under N2, indole (38, 29 mg,
0.25 mmol) was added in portions and the mixture was stirred at r.t.
for 10 min. To the reaction mixture was added 31 (100 mg, 0.27
mmol) and this was stirred at r.t. for 18 h. The reaction mixture was
diluted with water (10 mL) and extracted with Et2O (3 × 15 mL).
The combined Et2O extracts were washed with water (2 × 15 mL),
brine (15 mL) and dried (Na2SO4). The solvent was removed under
vacuum and the product was purified by silica gel column using
hexane–EtOAc (4:1) as the eluent to yield 39 (67 mg, 91%) as a col-
orless solid; mp 152 °C (EtOAc).
HRMS (EI): m/z calcd for C18H32SSi: 308.1994; found: 308.1992.
In a similar fashion, the reaction of diphenyl disulfide (31 mg, 0.14
mmol) with 32 (58 mg, 0.28 mmol) yielded phenylthiononane (46)
as a colorless oil (65.2 mg, 99%).
IR (CHCl3): 2925, 2955, 2850, 1585, 1480, 1440, 1090 cm–1.
1H NMR (400 MHz): d = 7.34–7.24 (m, 4 H, Ar-H), 7.18–7.13 (m,
1 H, Ar-H), 2.91 (t, J = 7.2 Hz, 2 H, CH2), 1.64 (quintet, J = 7.2 Hz,
2 H, CH2), 1.44–1.38 (m, 2 H, CH2), 1.34–1.20 (m, 10 H, CH2), 0.88
(t, J = 6.8 Hz, 3 H, CH3).
13C NMR (100 MHz): d = 137.0 (Cq-Ar), 128.8, 125.6 (C-Ar), 33.5,
31.8, 29.4, 29.2, 29.1, 29.0, 28.8, 22.6 (CH2), 14.1 (CH3).
MS (EI, 70 eV): m/z = 236 (32) [M+], 126 (7), 123 (18), 110 (100),
85 (6).
IR (CHCl3): 3425, 3020, 1645, 1450, 1230 cm–1.
1H NMR (400 MHz): d = 8.38 (br s, 1 H, NH), 7.64–7.61 (m, 1 H,
Ar-H), 7.46–7.41 (m, 2 H, Ar-H), 7.29 (AB, J = 8.4 Hz, 2 H, Ar-H),
7.27–7.24 (m, 1 H, Ar-H), 7.18–7.14 (m, 1 H), 7.07 (AB, J = 8.4 Hz,
2 H, Ar-H), 0.20 [s, 9 H, Si(CH3)3].
13C NMR (100 MHz): d = 140.4, 136.5, 136.2 (Cq-Ar), 133.6, 130.7
(C-Ar), 129.2 (Cq-Ar), 124.9, 123.1, 120.9, 119.7, 111.5 (C-Ar),
102.5 (Cq-Ar), –1.2 [Si(CH3)3].
HRMS (EI): m/z calcd for C15H24S: 236.1599; found: 236.1600.
MS (EI, 70 eV): m/z = 297 (100) [M+], 282 (98), 207 (11), 149 (17),
148 (12), 141 (46), 119 (16), 111 (12), 99 (12), 97 (18), 85 (28).
Syntheses of Thioesters 35 and 37; General Procedure
A solution of 31 (54 mg, 0.15 mmol) in THF (1 mL) was added to
SmI2 (4.5 mL, 0.1 M solution in THF, 0.45 mmol) under N2. The
deep blue color of the solution gradually became brown in 1 h. A
solution of the corresponding acid chloride 34 or 36 (0.45 mmol) in
THF (2 mL) was added to the mixture and stirred at r.t. for 1 h. The
reaction mixture was diluted with Et2O (20 mL) and filtered. The
filtrate was washed with water (2 × 10 mL), brine (10 mL) and dried
over Na2SO4. The crude products were purified by PTLC using hex-
ane as the eluent.
HRMS (EI): m/z calcd for C17H19NSSi: 297.1007; found: 297.1006.
3-Methyl-3-(4-trimethylsilylphenylsulfanyl)-3H-dihydrofuran-
2-one (40)
To a stirred solution of 6 (25 mg, 0.25 mmol) in THF (2 mL), was
added LHMDS (0.38 mL, 1 M solution in THF, 0.38 mmol) at –78
°C and the reaction mixture was stirred at –78 °C. After 20 min, to
the reaction mixture was added a solution of 31 (181 mg, 0.5 mmol)
in THF (5 mL) at –78 °C. The reaction mixture was stirred at –78
°C for 2 h, warmed to –20 °C (1 h), followed by warming to r.t. (1
h). The reaction mixture was quenched with aq NH4Cl solution (25
mL) and extracted with EtOAc (3 × 20 mL). The combined EtOAc
layers were washed with water (2 × 30 mL), brine (30 mL) and dried
(Na2SO4) and concentrated. The residue was purified by silica gel
column using hexane–EtOAc (9:1) as the eluent to afford 40 (56.7
mg, 81%) as a colorless oil.
Dodecyl 4-Trimethylsilylphenyl Thiocarboxylate (35)
Yield: 79.1 mg (73%).
IR (CHCl3): 2990, 2930, 2855, 1700, 1485, 1380, 1265, 1250, 1115
cm–1
1H NMR (400 MHz): d = 7.55 (AB, J = 8.4 Hz, 2 H, Ar-H), 7.38
(AB, J = 8.4 Hz, 2 H, Ar-H), 2.65 (t, J = 7.2 Hz, 2 H, CH2), 1.76–
1.62 (m, 2 H, CH2), 1.40–1.20 (m, 16 H, CH2), 0.88 (t, J = 6.8 Hz,
3 H, CH3), 0.27 [s, 9 H, Si(CH3)3].
13C NMR (100 MHz): d = 197.9 (CO), 142.2 (Cq-Ar), 134.4, 133.8
(C-Ar), 128.8 (Cq-Ar), 44.1, 32.2, 29.9, 29.8, 29.7, 29.6, 29.3, 25.9,
23.0 (CH2), 14.5 (CH3), –0.9 [Si(CH3)3].
IR (CHCl3): 2960, 1765, 1445, 1380, 1250, 1185, 1085, 1030 cm–1.
1H NMR (400 MHz): d = 7.54–7.48 (m, 4 H, Ar-H), 4.27–4.22 (m,
2 H, CH2), 2.42–2.37 (m, 2 H, CH2), 1.52 (s, 3 H, CH3), 0.27 [s, 9
H, Si(CH3)3].
13C NMR (100 MHz): d = 176.7 (CO), 142.9 (Cq-Ar), 136.1, 133.9
(C-Ar), 129.9 (Cq-Ar), 64.8 (CH2), 49.8 (Cq), 37.2 (CH2), 23.3
(CH3), –1.3 [Si(CH3)3].
MS (EI, 70 eV): m/z = 364 (7) [M+], 184 (15), 182 (88), 167 (52),
95 (22), 91 (14), 85 (30), 83 (18), 71 (45), 69 (15), 57 (100).
MS (EI, 70 EV): m/z = 280 (54) [M+], 265 (34), 207 (24), 167 (100),
91 (23), 83 (18), 75 (15).
HRMS (EI): m/z calcd for C21H36OSSi: 364.2256; found: 364.2255.
Anal. Calcd for C14H20O2SSi: C, 59.98; H, 7.20. Found: C, 59.94;
H, 7.20.
Phenyl 4-Trimethylsilylphenyl Thiocarboxylate (37)
Yield: 73.6 mg (86%).
Similarly, the reaction of lithium enolate of 6 (100 mg, 1.0 mmol)
with diphenyl disulfide (437 mg, 2.0 mmol) afforded 3-methyl-3-
phenylsulfanyl-3H-dihydrofuran-2-one as a colorless oil (166 mg,
80%).
IR (CHCl3): 3065, 1675, 1580, 1555, 1450, 1380, 1250, 1175, 1115,
1080 cm–1.
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456
P. K. Patra et al.
PAPER
IR (CHCl3): 2920, 1770, 1695, 1650, 1570, 1560, 1390, 1230, 1030
cm–1.
1H NMR (400 MHz): d = 7.58–7.54 (m, 2 H, Ar-H), 7.46–7.41 (m,
1 H, Ar-H), 7.39–7.34 (m, 2 H, Ar-H), 4.28–4.17 (m, 2 H, CH2),
2.42–2.37 (m, 2 H, CH2), 1.51 (s, 3 H, CH3).
13C NMR (100 MHz): d = 176.6 (CO), 137.1, 130.0 (C-Ar), 129.5
(Cq-Ar), 128.9 (C-Ar), 64.7 (CH2), 49.8 (Cq), 37.1 (CH2), 23.3
(CH3).
1H NMR (400 MHz): d = 7.46–7.43 (m, 4 H, Ar-H), 3.38–3.32 (m,
1 H, CH), 2.96 (br s, 1 H, OH), 2.85–2.79 (m, 1 H, CH), 2.18–2.08
(m, 2 H, CH2), 1.78–1.64 (m, 2 H, CH2), 1.42–1.20 (m, 4 H, CH2),
0.26 [s, 9 H, Si(CH3)3].
13C NMR (100 MHz): d = 139.9 (Cq-Ar), 133.8, 133.6 (C-Ar), 132.4
(Cq-Ar), 72.2, 56.3 (CH), 33.8, 32.7, 26.1, 24.3 (CH2), –1.2
[Si(CH3)3].
MS (EI, 70 eV): m/z = 280 (35) [M+], 182 (24), 169 (11), 167 (100),
149 (11).
MS (EI, 70 eV): m/z = 208 (18) [M+], 131 (8), 110 (20), 85 (60), 83
(100).
HRMS (EI): m/z calcd for C15H24OSSi: 280.1317; found: 280.1318.
HRMS (EI): m/z calcd for C11H12O2S: 208.0558; found: 208.0556.
Anal. Calcd for C15H24OSSi: C, 64.26; H, 8.63. Found: C, 63.98; H,
8.33.
1-(4-Trimethylsilyl)phenylthio-1-(4-methoxyphenyl)acetoni-
trile (42)
In a similar manner, the reaction of diphenyl disulfide (31 mg, 0.14
mmol) with 14 (28 mg, 0.28 mmol) afforded 2-phenylsulfanylcy-
clohexanol (54.6 mg, 94%).
To a solution of LDA (0.17 mmol) in THF (2 mL), was added a so-
lution of 41 (19 mg, 0.13 mmol) in THF (1 mL) at –78 °C. After 20
min, a solution of 31 (94 mg, 0.26 mmol) in THF (2 mL) was added
to the reaction mixture and stirring was continued at –78 °C for 2 h,
followed by warming to r.t. in 2 h. The reaction mixture was
quenched with aq NH4Cl solution (10 mL) and extracted with
EtOAc (3 × 20 mL). The combined EtOAc layers were washed with
water (2 × 30 mL), brine (30 mL) and dried (Na2SO4) and concen-
trated. It was purified by silica gel column using hexane–EtOAc
(9:1) as the eluent to provide 42 (33 mg, 78%) as a colorless liquid.
IR (CHCl3): 3500, 3000, 2860, 1580, 1540, 1450, 1445, 1385, 1270
cm–1.
1H NMR (400 MHz): d = 7.50–7.46 (m, 2 H, Ar-H), 7.34–7.28 (m,
3 H, Ar-H), 3.36–3.29 (m, 1 H, CH), 3.00 (br s, 1 H, OH), 2.81–2.75
(m, 1 H, CH), 2.16–2.06 (m, 2 H, CH2), 1.76–1.64 (m, 2 H, CH2),
1.38–1.18 (m, 4 H, CH2).
13C NMR (100 MHz): d = 133.7 (C-Ar), 132.5 (Cq-Ar), 128.9, 127.7
(C-Ar), 71.9 (CH), 56.4 (CH), 33.8, 32.6, 26.1, 24.2 (CH2).
MS (EI, 70 eV): m/z = 208 (17) [M+], 110 (60), 98 (10), 85 (70), 83
(100), 81 (16).
IR (CHCl3): 3444, 1635, 1251, 1232 cm–1.
1H NMR (400 MHz): d = 7.52–7.46 (m, 4 H, Ar-H), 7.30 (AB, J =
8.8 Hz, 2 H, Ar-H), 6.89 (AB, J = 8.8 Hz, 2 H, Ar-H), 4.94 (s, 1 H,
CH), 3.82 (s, 3 H, OCH3), 0.27 [s, 9 H, Si(CH3)3].
HRMS (EI): m/z calcd for C12H16OS: 208.0922; found: 208.0918.
13C NMR (100 MHz): d = 160.1, 142.6 (Cq-Ar), 134.2, 133.7 (C-
Ar), 131.4 (Cq-Ar), 129.2 (C-Ar), 124.3 (Cq-Ar), 118.1 (CN), 114.4
(C-Ar), 55.4 (OCH3), 41.1 (CH), –1.3 [Si(CH3)3].
MS (EI, 70 eV): m/z = 327 (2) [M+], 146 (100), 91 (10), 85 (12), 83
(21), 77 (5).
1-Phenyl-3-(4-Trimethylsilylphenyl)thiopropane (45)
To a solution of 3-phenylpropan-1-ol (44, 12 mg, 0.09 mmol) and
31 (100 mg, 0.28 mmol) in THF (5 mL) was added tri-n-butylphos-
phine (70 mL, 0.28 mmol) and stirred at r.t. for 4 h. The reaction
mixture was quenched with sat. aq NH4Cl solution (20 mL) and ex-
tracted with EtOAc (3 × 20 mL). The combined EtOAc layers were
washed with water (2 × 10 mL), brine (10 mL) and dried (Na2SO4)
and concentrated. The crude product thus obtained was purified by
PTLC using hexane as the eluent to yield 45 (27.8 mg, 100%) as a
colorless liquid.
HRMS (EI): m/z calcd for C18H21NOSSi: 327.1113; found:
327.1114.
Following similar procedure, 41 (19 mg, 0.13 mmol) was treated
with diphenyl disulfide (57 mg, 0.26 mmol) to afford 4-methoxy-
phenylphenylthioacetonitrile as a light yellow oil (25.6 mg, 80%).
IR (CHCl3): 2850, 2425, 1630, 1560, 1470, 1300, 1095 cm–1.
1H NMR (400 MHz): d = 7.50–7.48 (m, 2 H, Ar-H), 7.42–7.30 (m,
3 H, Ar-H), 7.26 (AB, J = 8.8 Hz, 2 H, Ar-H), 6.86 (AB, J = 8.8 Hz,
2 H, Ar-H), 4.94 (s, 1 H, CH), 3.81 (s, 3 H, CH3).
IR (CHCl3): 3500, 1715, 1575, 1080 cm–1.
1H NMR (400 MHz): d = 7.42–7.39 (m, 2 H, Ar-H) , 7.30–7.26 (m,
4 H, Ar-H), 7.21–7.15 (m, 3 H, Ar-H), 2.93 (t, J = 7.2 Hz, 2 H, CH2),
2.76 (t, J = 7.2 Hz, 2 H, CH2), 1.98 (quintet, J = 7.2 Hz, 2 H, CH2),
0.25 [s, 9 H, Si(CH3)3].
13C NMR (100 MHz): d = 160.0 (Cq-Ar), 135.2 (C-Ar), 130.5 (Cq-
Ar), 129.8, 129.3, 129.2 (C-Ar), 124.3 (Cq-Ar), 118.0 (CN), 114.3
(C-Ar), 55.4 (CH3), 41.2 (CH).
13C NMR (100 MHz): d = 141.3, 137.6, 137.4 (Cq-Ar), 133.8, 128.5,
128.4, 127.8, 125.9 (C-Ar), 34.7 (CH2), 32.3 (CH2), 30.6 (CH2),
–1.2 [Si(CH3)3].
MS (EI, 20 eV): m/z = 255 (3) [M+], 254 (3), 147 (13), 146 (100),
MS (EI, 70 eV): m/z = 300 (90) [M+], 285 (83), 182 (55), 167 (100),
135 (7), 110 (24), 85 (8).
166 (24), 118 (26), 117 (25), 91 (87), 77 (11).
HRMS (EI): m/z calcd for C15H13NOS: 255.0718; found: 255.0722.
HRMS (EI): m/z calcd for C18H24SSi: 300.1368; found: 300.1369.
In an identical manner, diphenyl disulfide (66 mg, 0.30 mmol) was
treated with 44 (13.5 mg, 0.10 mmol) to afford 1-phenylthio-3-phe-
nylpropane (49) as a colorless oil (22.6 mg, 100%).
IR (CHCl3): 3000, 1600, 1580, 1495, 1450, 1380, 1200 cm–1.
1H NMR (400 MHz): d = 7.32–7.14 (m, 10 H, Ar-H), 2.92 (t, J = 7.2
Hz, 2 H, CH2), 2.76 (t, J = 7.2 Hz, 2 H, CH2), 1.97 (quintet, J = 7.2
Hz, 2 H, CH2).
13C NMR (100 MHz): d = 141.3, 136.5 (Cq-Ar), 129.1, 128.8, 128.5,
128.4, 125.9, 125.8 (C-Ar), 34.7, 32.9, 30.6 (CH2).
MS (EI, 70 eV): m/z = 228 (17) [M+], 123 (3), 119 (4), 118 (30), 117
(24), 110 (12), 109 (6), 91 (18), 87 (10), 85 (63), 83 (100).
Trans-2-(4-trimethylsilylphenylsulfanyl)cyclohexanol (43)
To a solution of 14 (28 mg, 0.28 mmol) and 31 (54 mg, 0.14 mmol)
in EtOH (5 mL) at 0 °C was added NaBH4 (22 mg, 0.56 mmol) and
the mixture was stirred at 80 °C for 3 h. The solvent was removed
under vacuum and the residue was quenched with sat. aq NH4Cl so-
lution (20 mL) and extracted with EtOAc (3 × 15 mL). The com-
bined organic extracts were washed with water (2 × 15 mL), brine
(15 mL), dried (Na2SO4) and concentrated. The crude product was
purified by silica gel column chromatography using hexane–EtOAc
(9:1) as the eluent to yield 43 (73.1 mg, 94%) as a colorless oil.
IR (CHCl3): 3445, 2940, 2250, 1635, 1575, 1450, 1380, 1250, 1200
cm–1.
Synthesis 2005, No. 3, 447–457 © Thieme Stuttgart · New York

PAPER
Odorless Diphenyl Diselenide and Disulfide: Syntheses and Applications
457
HRMS (EI): m/z calcd for C15H16S: 228.0973; found: 228.0972.
Oshima, K.; Nozaki, H. Tetrahedron Lett. 1981, 22, 1609.
(e) Marchand, E.; Morel, G.; Foucaud, A. Synthesis 1978,
360.
Protodesilylation of 4-Trimethylsilylphenyl Derivatives 33, 35,
37, and 45 using TFA; General Procedure
(8) (a) Nicolaou, K. C.; Pastor, J.; Barluenga, S.; Winssinger, N.
Chem. Commun. 1998, 39, 1947. (b) Ruhland, T.;
Andersen, K.; Pedersen, H. J. Org. Chem. 1998, 63, 9204.
(c) First report on polymer-supported odorless selenium
reagents: Michels, R.; Kato, M.; Heitz, W. Makromol.
Chem. 1976, 177, 2311.
A solution of 4-trimethylsilylphenyl derivatives 33, 35, 37 or 45
(0.26 mmol) in TFA (0.4 mL) was stirred at 0 °C for 4–8 h (moni-
tored by NMR). The reaction mixture was quenched with aq
NaHCO3 (10 mL) and extracted with EtOAc (3 × 10 mL). The com-
bined organic layers were washed with water (2 × 10 mL), brine (10
mL) and dried (Na2SO4). After concentration, the residue was puri-
fied by column chromatography using hexane–EtOAc as the eluent
to afford 46 (93%), 47 (92%), 48 (91%), or 49 (89%), respectively.
The analytical data of 46 and 49 are presented above and those of
47 and 48 are compared with the literature.22
(9) (a) Nishide, K.; Patra, P. K.; Matoba, M.;
Shanmugasundaram, K.; Node, M. Green Chem. 2004, 6,
142. (b) Patra, P. K.; Nishide, K.; Fuji, K.; Node, M.
Synthesis 2004, 1003. (c) Ozeki, M.; Nishide, K.; Teraoka,
F.; Node, M. Tetrahedron: Asymmetry 2004, 15, 895.
(d) Nishide, K.; Ozeki, M.; Kunishige, H.; Shigeta, Y.; Patra,
P. K.; Hagimoto, Y.; Node, M. Angew. Chem. Int. Ed. 2003,
42, 4515. (e) Ohsugi, S.; Nishide, K.; Oono, K.; Okuyama,
K.; Fudesaka, M.; Kodama, S.; Node, M. Tetrahedron 2003,
59, 8393. (f) Nishide, K.; Miyamoto, T.; Kumar, K.; Ohsugi,
S.; Node, M. Tetrahedron Lett. 2002, 43, 8569. (g)Nishide,
K.; Ohsugi, S.; Fudesaka, M.; Kodama, S.; Node, M.
Tetrahedron Lett. 2002, 43, 5177. (h) Nishide, K.; Ohsugi,
S.; Shiraki, H.; Tamakita, H.; Node, M. Org. Lett. 2001, 3,
3121. (i) Node, M.; Kumar, K.; Nishide, K.; Ohsugi, S.;
Miyamoto, T. Tetrahedron Lett. 2001, 42, 9207.
(10) (a) Node, M. Foods Food Ingredients J. Jpn. 2004, 209, 88.
(b) Nishide, K.; Ohsugi, S.; Miyamoto, T.; Kumar, K.; Node,
M. Monatsh. Chem. 2004, 135, 189.
Acknowledgment
PKP thanks the JSPS for financial support.
References
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Synthesis 2005, No. 3, 447–457 © Thieme Stuttgart · New York