Selenosilane-Promoted Selective Mild Transformation of N -Thiophthalimides into Symmetric Disulfides

Article abstract of DOI:10.1055/s-0037-1610354

The reactivity of N -thiophthalimides with silyl chalcogenides is described. Treatment of N -thiophthalimides with bis(trimethylsilyl) sulfide [(Me ₃ Si) ₂ S] leads to the formation of a mixture of the corresponding disulfides and tr

Full text of DOI:10.1055/s-0037-1610354

SYNTHESIS
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© Georg Thieme Verlag Stuttgart · New York
2019, 51, A–F
paper
A
en
C. Viglianisi et al.
Paper
Synthesis
Selenosilane-Promoted Selective Mild Transformation of
N-Thiophthalimides into Symmetric Disulfides
Caterina Viglianisi
Chiara Bonardi
TBAF
O
(0.15 equiv)
Se
S
S
Alkyl/Aryl
Me3Si
+
Aryl/Alkyl
N
SiMe3
Aryl/Alkyl
S
THF, r.t.
Elena Ermini
O
Antonella Capperucci
Stefano Menichetti
Mild conditions
Simple
Versatile
Broad functional groups tolerability
12 examples Up to 91% yield
Damiano Tanini*
0
0
0
0-0
0
0
1-8
9
3
0-
3
5
6
6
Dipartimento di Chimica ‘Ugo Schiff’, Via della Lastruccia 3-13,
50019 Sesto Fiorentino (FI), Italy
damiano.tanini@unifi.it
Received: 22.10.2018
Accepted after revision: 13.11.2018
Published online: 07.01.2019
through a nucleophilic attack of the sulfur atom at the ter-
minal azido nitrogen, with desilylation of the azide–HMDST
complex.4
DOI: 10.1055/s-0037-1610354; Art ID: ss-2018-t0710-op
Despite interest in the chemistry of organosilanes, only
a few examples are described to obtain disulfides through
thiosilanes.5 We also found that unsymmetrical disulfides
can be prepared by treatment of thiolsulfinates with silyl
sulfides.6 However, no example is reported through the re-
action with selenosilanes.
Abstract The reactivity of N-thiophthalimides with silyl chalcogenides
is described. Treatment of N-thiophthalimides with bis(trimethylsilyl)
sulfide [(Me3Si)2S] leads to the formation of a mixture of the corre-
sponding disulfides and trisulfides. On the other hand, N-thiophthalim-
ides react with bis(trimethylsilyl) selenide [(Me3Si)2Se] under TBAF ca-
talysis to smoothly give variously substituted diaryl, divinyl, and dialkyl
disulfides; formation of a selenotrisulfide (dithiaselane, RSSeSR) is ratio-
nalized as an intermediate. Exploiting the different chemical behavior of
silyl chalcogenides, we have disclosed a novel, selective, and operation-
ally simple method to access disulfides in good yields under mild condi-
tions.
Furthermore, N-(alkylthio)- and N-(arylthio)phthalim-
ides (R-SNPht, R = alkyl, aryl, Pht = phthaloyl) have been
used for a long time as sulfur electrophiles able to react
with thiols and amines for the formation of new S–S7 and
S–N8 bonds. In particular, they have been used in the syn-
thesis of complex natural products, such as in the introduc-
tion of the methyl trisulfide moiety into the calicheamicin
skeleton.9 Recently, the reaction of these species with car-
bon nucleophiles has been optimized for the stereoselective
catalytic formation of S–C bonds,10 and for the thionation of
aza-aromatics, such as indanone,11 indoles, and pyrroles.12
Generally, N-thiophthalimides are prepared by reacting po-
tassium phthalimide with the appropriate sulfenyl halide.
However, this procedure suffers from severe limitations due
to poor functional group tolerance, high reactivity, low sta-
bility, and difficulties in storing and handling of many
sulfenyl halides. We have developed and optimized a proce-
dure for the preparation of a variety of N-thiophthalimides
exploiting the reaction of the phthalimidosulfenyl chloride
(PhtNSCl), a stable easily to prepare and handle crystalline
solid sulfenyl chloride, with various carbon nucleophiles,
such as alkynes,13 enolizable ketones,14 phenols,15 and other
electron-rich arenes.16
Key words disulfides, selenosilane, N-thiophthalimides, trisulfides, se-
lenium, sulfur
Organosulfur compounds have been widely investigated
for their importance in many chemical and biochemical
processes. In this field, oligosulfides, such as disulfides1 and
trisulfides,2 represent important and versatile molecules for
their application in organic chemistry, medicinal chemistry,
food chemistry, and material science.
Due to the high interest in these derivatives, novel, effi-
cient, and mild methods to obtain disulfides and trisulfides
with a significant structural diversity are still needed.
Our long dated interest in the reactivity and application
of silyl chalcogenides led us to develop new synthetic pro-
tocols to access a wide range of sulfurated and selenated
compounds.3 We found that silyl sulfides and silyl selenides
were able to behave as efficient nucleophiles toward differ-
ent electrophilic reagents, as carbonyl compounds and ring
strained heterocycles, leading to a clean transfer of the chal-
cogenated moiety under mild conditions. Bis(trimethylsilyl)
sulfide (HMDST, 2) was also able to reduce azides to amines
In this scenario, we planned to study the unexplored re-
activity of silyl chalcogenides with N-thiophthalimides as
electrophilic sulfur-transfer reagents. The results obtained
are described in this communication.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2019, 51, A–F

B
C. Viglianisi et al.
Paper
Synthesis
We began evaluating the reactivity of (Me3Si)2S 2
(HMDST) with selected N-thiophthalimides. Thus, 1a,b
were treated with (Me3Si)2S 2 in the presence of TBAF as
catalyst at room temperature. As reported in Scheme 1, the
reaction afforded a mixture of trisulfides 3a,b and disul-
fides 4a,b in almost comparable amounts. The two products
can be separated by flash chromatography even though, the
very similar chromatographic behavior caused a rather
tricky purification step.
Initially, the reaction was carried out by treating N-(ar-
ylthio)phthalimide 1a with the quite reactive HMDSS 5 in
THF at r.t., in the absence of any catalyst, but no reaction oc-
curred under these conditions. On the other hand, when 1a
was treated with 5 in THF at r.t. in the presence of 15% mol
of TBAF (Scheme 2), the diaryl disulfide 4a was efficiently
formed together with, after an aqueous workup, elemental
selenium and phthalimide (PhtNH) that were easily re-
moved by precipitation from toluene or filtration on silica
gel. Interestingly, no organoselenated side products were
formed in this reaction and only amorphous elemental se-
lenium was observed. Taking into account the very similar
chromatographic behavior of related sulfurated and
selenated derivatives, this was particular favorable as it
simplified the purification of disulfide 4a which was isolat-
ed in 89% yield after an easy filtration over a short pad of
silica gel.
TBAF
(15 mol%)
O
S
S
S
S
Ar
(Me3Si)2S
+
Ar
N
+
Ar
S
Ar
Ar
S
THF
r.t., 2 h
2
3a,b
4a,b
O
(0.5 equiv)
1a,b
OH HO
S
S
S
S
S
S
OH
O
3a
(53%)a
3b
(56%)a
OH
OH
TBAF
(15 mol%)
OH
S
(Me3Si)2Se
+
N
S
S
THF
r.t., 2 h
5
Scheme 1 Synthesis of trisulfides and disulfides from N-thiophthalim-
ides and (Me3Si)2S. a Isolated yield; the corresponding disulfides 4a and
4b were also formed (ca. 40–45%).
OH
O
(0.5 equiv)
4a
(89%)
1a
Scheme 2 Synthesis of disulfide 4a from N-thiophthalimide 1a and
(Me3Si)2Se 5.
We argued that, along with the expected trisulfides 3,
formed by reaction of 2 with two equivalents of 1a and 1b,
the reaction could proceed through the formation of other
oligosulfides that, by extrusion of elemental sulfur, afforded
disulfides 4. Despite many attempts, we were unable to
drive the reaction toward the selective formation of trisul-
fides 3 or disulfides 4. In fact, a roughly 1:1 mixture of 3
and 4 was obtained independent of the reaction conditions
used (stoichiometric ratio of the reagents, reaction tem-
perature, solvent, and amount of catalyst). The results re-
ported in Scheme 1 demonstrate that nucleophilic silyl
chalcogenides and electrophilic N-thiophthalimides can re-
act together. However suitable optimized reaction condi-
tions for the selective formation of a single product were re-
quired to develop a synthetically useful procedure.
This prompted us to investigate the behavior of
bis(trimethylsilyl) selenide [(Me3Si)2Se or HMDSS, 5], the
selenium-containing analogue of HMDST, with R-SNPht, in
order to evaluate whether disulfides could be selectively
achieved. The rationale arose considering the possible for-
mation of mixed oligoseleno sulfides and selenotrisulfides
[dithiaselanes or selenium(II) dithiolates, RSSeSR], that
could easily extrude elemental selenium with the forma-
tion of disulfides as the unique reaction products.
Thus, imagining a similar reaction of HMDST 2 and
HMDSS 5 with R-SNPht 1a, we disclosed a novel synthetic
route to access disulfides exploiting the different stability
of mixed chalcogenides.
In order to evaluate the generality of the reaction, a rep-
resentative series of N-aryl-, N-alkyl-, and N-vinylthioph-
thalimides were treated with HMDSS 5. As shown in
Scheme 3, the mild conditions allowed the preparation of
disulfides in good to high yields with an interesting func-
tional group tolerance.
Arylthio residues bearing different substituents, like
methyl, unprotected hydroxyl, methoxy, amino, and ester
moieties at different positions of the aromatic ring, reacted
smoothly under the reaction conditions reported in Scheme
3 to give the corresponding diaryl disulfides 4a–g. Interest-
ingly the reaction was also efficient with the N-arylthio de-
rivative of δ-tocopherol 1g affording disulfide 4g, contain-
ing two δ-tocopherol units. Similarly, polyfunctionalized
dialkyl and divinyl disulfides 4h–l were efficiently prepared
without any protection, despite the presence of carbonyl
and halogenated groups in the N-thiophthalimide residue.
The synthesis of several of the latter disulfides is worthy of
mention since many of the classical procedures for the
preparation of disulfides appear unfeasible for these sub-
strates. For example, the oxidation of the corresponding thi-
ols appears impractical as these thiols are rather elusive
compounds. On the other hand, the molecular skeletons 4i
and 4j do not tolerate either oxidative or reductive condi-
Indeed, to the best of our knowledge, very few proce-
dures have been reported for the synthesis of RSSeSR deriv-
atives,17 that, despite considered privileged intermediates
for the incorporation of inorganic selenium into living or-
ganisms, are quite unstable and prone to decompose to give
RSSR and Se(0).
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2019, 51, A–F

C
C. Viglianisi et al.
Paper
Synthesis
O
TBAF (15 mol%)
S
S
Ar/R
OH
(Me3Si)2Se
+
R/Ar
N
R/Ar
S
THF
r.t., 2 h
5
4a–l
O
(0.5 equiv)
1a–l
OH
HO
S
S
OAc
S
S
AcO
S
S
HO
HO
OH
4a
(89%)
4b
(86%)a
4c
(79%)
OH
N
MeO
OMe
OAc
OH
S
S
S
S
S
S
OAc
4d
(77%)
N
MeO
OMe
4e
(73%)b
4f
(78%)c
O
O
S
Ph
Cl
O
HO
S
Ph
S
Ph
S
S
S
O
Ph
O
4h
(72%)d
4i
(84%)
HO
Cl
O
4g
(86%)
Cl
O
S
OEt
OH
nPr
nPr
Cl
Ph
S
Cl
S
S
Cl
HO
EtO
S
Cl
S
nPr
nPr
Ph
O
Cl
4j
(53%)
4k
4l
(91%)
(78%)
Scheme 3 Generality and scope of the (Me3Si)2Se mediated synthesis of disulfides from N-thiophthalimides. Spectroscopic data were consistent with
those previously reported: a ref.19 b ref.20 c ref.21 d ref.22
1
tions. Intriguingly, whilst the H NMR spectrum (acquired
in CDCl3) of disulfide 4i displayed only the keto form, exclu-
sively the enol form was observed in the 1H NMR spectrum
of 4j.18
All the reactions were performed under a positive pressure of N2 and
were monitored by TLC using commercially available precoated plates
(silica gel 60 F 254) and compounds were visualized by fluorescence
quenching or by staining the plates with acidic p-anisaldehyde solu-
tion. Silica gel 60, 230–400 mesh, was used for flash column chroma-
tography. Dry solvents were obtained using a Pure Solv™ Micro sys-
tem. Bis(trimethylsilyl) selenide was prepared following a slightly
modified literature reported procedure.25 N-Thiophthalimides 1a–
g,15,16 1h,26 1i–j,14 and 1k,l,13 were prepared as reported in the litera-
ture. Commercially available reagents were used as obtained from
freshly opened containers without further purification.
1H and 13C NMR spectra were recorded in CDCl3 with a Varian Mercu-
ry Plus instrument or with a Varian INOVA instrument at 400 and 100
MHz, respectively. The corresponding residual non-deuterated sol-
vent was used as a reference (δ = 7.26 for 1H and δ = 77.0 for 13C).
Mass spectra (MS) were determined by ESI.
For the all disulfides 4a–l reported in Scheme 3 isola-
tion, after the complete consumption of the starting materi-
als monitored by TLC and aqueous workup, was achieved
after an easy filtration on a short path of silica gel.
The disulfide moiety plays a key role in redox processes,
involving thiol–disulfide interconversion reactions occur-
ring in enzymatic pathways, and the S–S bridge is also pres-
ent in a wide range of polymers and materials.23 For these
reasons, any novel and general synthetic procedures for the
synthesis of variously functionalized disulfides are highly
sought after. Among the many methods available for their
synthesis,24,25 the procedure we reported herein might be
considered as an efficient and convenient alternative to
synthesize a large variety of densely functionalized disul-
fides occurring under mild, metal-free conditions.
6,6′-Trisulfanediylbis(2,4-dimethylphenol) (3a)
A 1 M TBAF in THF solution (30 μL, 0.03 mmol, 0.15 equiv) was added
to a solution of bis(trimethylsilyl) sulfide (2; 18 μL, 0.10 mmol, 0.5
equiv) and N-thiophthalimide 1a (60 mg, 0.20 mmol, 1.0 equiv) in
THF (2 mL) at 0 °C under an inert atmosphere (N2). The mixture was
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2019, 51, A–F

D
C. Viglianisi et al.
Paper
Synthesis
then warmed to r.t. and stirred for 2 h. Afterwards, the mixture was
diluted with Et2O (3 mL) and then sat. aq NH4Cl (3 mL) was added. The
aqueous phase was extracted with Et2O (2 × 5 mL) and the combined
organic phases were washed with brine (1 × 3 mL), dried (Na2SO4), fil-
tered, and concentrated in vacuo. The crude material was purified by
flash chromatography (petroleum ether/Et2O 20:1) to afford trisulfide
3a (18 mg, 53%) as a yellowish glassy solid.
Anal. Calcd for C16H18O2S2: C, 62.71; H, 5.92. Found: C, 62.83; H,
5.89%,.
Disulfanediylbis(4-hydroxy-2,5,6-trimethyl-3,1-phenylene) Diace-
tate (4c)
Following the general procedure using N-thiophthalimide 1c (37 mg,
0.10 mmol) and bis(trimethylsilyl) selenide (5; 12 mg, 0.05 mmol)
gave, after purification by column chromatography (petroleum
ether/Et2O 8:1), 4c (18 mg, 79%) as a pale yellowish glassy solid.
1H NMR (400 MHz, CDCl3): δ = 7.16 (s, 2 H, ArH), 6.99 (s, 2 H, ArH),
6.20 (br s, 2 H, OH), 2.25 (s, 6 H, CH3), 2.22 (s, 6 H, CH3).
13C NMR (100 MHz, CDCl3): δ = 152.6, 135.0, 132.8, 129.9, 125.1,
1H NMR (400 MHz, CDCl3): δ = 6.53 (s, 2 H, OH), 2.30 (s, 6 H, CH3CO),
119.4, 20.2, 16.2.
2.16 (s, 6 H, CH3), 2.06 (s, 6 H, CH3), 1.98 (br s, 6 H, CH3).
MS (ESI positive): m/z (%) = 361 [M + Na]+ (100).
13C NMR (100 MHz, CDCl3): δ = 169.1, 153.5, 141.4, 134.3, 132.1,
121.6, 117.1, 20.4, 14.7, 13.5, 12.7.
MS (ESI positive): m/z (%) = 473 [M + Na]+ (100).
Anal. Calcd for C16H18O2S3: C, 56.77; H, 5.36. Found: C, 56.84; H, 5.33.
1,1′-Trisulfanediylbis(naphthalen-2-ol) (3b)
Anal. Calcd for C22H26O6S2: C, 58.65; H, 5.82. Found: C, 58.73; H, 5.79.
A 1 M TBAF in THF solution (15 μL, 0.015 mmol, 0.15 equiv) was add-
ed to a solution of bis(trimethylsilyl) sulfide (2; 9.0 μL, 0.05 mmol, 0.5
equiv) and N-thiophthalimide 1b (32 mg, 0.10 mmol, 1.0 equiv) in
THF (1 mL) at 0 °C under an inert atmosphere (N2). The mixture was
then warmed to r.t. and stirred for 2 h. Afterwards, the mixture was
diluted with Et2O (3 mL) and then sat. aq NH4Cl (3 mL) was added. The
aqueous phase was extracted with Et2O (2 × 5 mL) and the combined
organic phases were washed with brine (1 × 3 mL), dried (Na2SO4), fil-
tered, and concentrated in vacuo. The crude material was purified by
flash chromatography (petroleum ether/Et2O 20:1) to afford trisulfide
3b (11 mg, 56%) as a pale yellowish glassy solid.
Disulfanediylbis(4-hydroxy-3,5,6-trimethyl-2,1-phenylene) Diace-
tate (4d)
Following the general procedure using N-thiophthalimide 1d (74 mg,
0.20 mmol) and bis(trimethylsilyl) selenide (5; 23 mg, 0.10 mmol)
gave, after purification by column chromatography (petroleum
ether/Et2O 8:1), 4d (35 mg, 77%) as a pale yellowish glassy solid.
1H NMR (400 MHz, CDCl3): δ = 5.57 (s, 2 H, OH), 2.34 (s, 6 H, CH3,
CH3CO), 2.21 (s, 6 H, CH3), 2.16 (s, 6 H, CH3), 2.04 (s, 6 H, CH3).
13C NMR (100 MHz, CDCl3): δ = 169.2, 147.3, 141.2, 128.6, 125.4,
122.0, 117.8, 20.4, 14.0, 13.0, 12.6.
HRMS: m/z [M + Na]+ calcd for C22H26NaO6S2: 473.1068; found:
473.1075.
1H NMR (400 MHz, CDCl3): δ = 8.34 (d, J = 8.5 Hz, 2 H, 4,4′-ArH), 7.75–
7.89 (m, 4 H, 5,5′,8,8′-ArH), 7.60 (apparent t, J = 7.3 Hz, 2 H, 7,7′-ArH),
7.42 ( apparent t, J = 7.3 Hz, 2 H, 6,6′-ArH), 7.27 (d, J = 8.5 Hz, 2 H, 3,3′-
ArH), 7.12 (br s, 2 H, OH).
13C NMR (100 MHz, CDCl3): δ = 156.9, 135.5, 129.7, 128.8, 128.1,
(2S,2′S)-5,5′-Disulfanediylbis{2,8-dimethyl-2-[(4S,8S)-4,8,12-
trimethyltridecyl]chroman-6-ol} (4g)
124.7, 124.2, 117.3, 113.1.
MS (ESI positive): m/z (%) = 405 [M + Na]+ (100).
Following the general procedure using N-thiophthalimide 1g (58 mg,
0.10 mmol) and bis(trimethylsilyl) selenide (5; 12 mg, 0.05 mmol)
gave, after purification by column chromatography (petroleum
ether/Et2O 15:1), 4g (37 mg, 86%) as a pale yellowish oil.
1H NMR (400 MHz, CDCl3): δ = 6.65 (s, 2 H, ArH), 5.97 (br s, 2 H, OH),
2.59–2.67 (m, 2 H, 4,4′-CHaHb), 2.41–2.49 (m, 2 H, 4,4′-CHaHb), 2.13 (s,
6 H, CH3-Ar), 1.15 (s, 6 H, CH3C–O), 1.00–1.63 (m, 46 H), 0.83–0.87 (m,
24 H).
Anal. Calcd for C20H14O2S3: C, 62.80; H, 3.69. Found: C, 62.89; H, 3.67.
Disulfides from N-Thiophthalimides and Bis(trimethylsilyl) Sele-
nide; General Procedure
A 1 M TBAF in THF solution (30 μL, 0.03 mmol, 0.15 equiv) was added
to a solution of bis(trimethylsilyl) selenide (5; 0.10 mmol, 0.5 equiv)
and N-thiophthalimides 1 (0.20 mmol, 1.0 equiv) in THF (2 mL) at 0 °C
under inert atmosphere (N2). After 5 min, the mixture was warmed to
r.t. and stirred for 2 h (monitored by TLC). Afterwards, the mixture
was diluted with Et2O (3 mL) and then sat. aq NH4Cl (3 mL) was added.
The aqueous phase was extracted with Et2O (2 × 5 mL) and the com-
bined organic phases were washed with brine (1 × 3 mL), dried (Na2-
SO4), filtered, and concentrated in vacuo. The crude material was pu-
rified by flash chromatography to afford disulfides 4a–l.
13C NMR (100 MHz, CDCl3): δ = 150.6. 146.0, 132.5, 124.2, 115.5,
115.0, 75.2, 39.8, 39.4, 37.5, 37.4, 37.3, 32.8, 32.7, 31.2, 28.0, 24.8,
24.5, 23.6, 22.7, 22.6, 21.7, 21.0, 19.7, 19.6, 16.6.
MS (ESI positive): m/z (%) = 889 [M + Na]+ (100).
Anal. Calcd for C54H90O4S2: C, 74.77; H, 10.46. Found: C, 74.63; H,
10.50.
2,2′-Disulfanediylbis(1,3-diphenylpropane-1,3-dione) (4i)
6,6′-Disulfanediylbis(2,4-dimethylphenol) (4a)
Following the general procedure, N-thiophthalimide 1i (80 mg, 0.20
mmol) and bis(trimethylsilyl) selenide (5; 23 mg, 0.10 mmol) gave,
after purification by column chromatography (petroleum ether/Et2O
15:1), 4i (43 mg, 84%) as a pale yellowish glassy solid.
1H NMR (400 MHz, CDCl3): δ = 8.00 (apparent d, J = 8.0 Hz, 8 H, ArH-
ortho), 7.54–7.58 (m, 4 H, ArH-para), 7.48–7.51 (m, 8 H, ArH-meta),
6.87 (s, 2 H, CHS).
Following the general procedure using N-thiophthalimide 1a (60 mg,
0.20 mmol) and bis(trimethylsilyl) selenide (5; 23 mg, 0.10 mmol)
gave, after purification by column chromatography (petroleum
ether/Et2O 15:1), 4a (27 mg, 89%) as a colorless glassy solid.
1H NMR (400 MHz, CDCl3): δ = 7.01 (br s, 2 H, 5,5′-ArH), 6.86 (br s, 2 H,
3,3′-ArH), 6.17 (s, 2 H, OH), 2.23 (s, 6 H, CH3), 2.18 (s, 6 H, CH3).
13C NMR (100 MHz, CDCl3): δ = 152.9, 135.2, 133.8, 129.5, 124.7,
119.2, 20.1, 16.3.
MS (ESI positive): m/z (%) = 329 [M + Na]+ (100).
13C NMR (100 MHz, CDCl3): δ = 185.7, 135.6, 132.4, 128.7, 127.2, 93.1.
HRMS: m/z [M + Na]+ calcd for C30H22NaO4S2: 533.0852; found:
533.0871
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Diethyl 2,2′-Disulfanediyl(2E,2′E)-bis(4-chloro-3-hydroxybut-2-
enoate) (4j)
(3) For selected recent reports, see: (a) Tanini, D.; Tiberi, C.; Gellini,
C.; Salvi, P. R.; Capperucci, A. Adv. Synth. Catal. 2018, 360, 3367.
(b) Tanini, D.; Grechi, A.; Dei, S.; Teodori, E.; Capperucci, A. New
J. Chem. 2018, 42, 6077. (c) Menichetti, S.; Capperucci, A.;
Tanini, D.; Braga, A. L.; Botteselle, G. V.; Viglianisi, C. Eur. J. Org.
Chem. 2016, 3097. (d) Capperucci, A.; Tanini, D. Phosphorus,
Sulfur Silicon Relat. Elem. 2015, 190, 1320. (e) Tanini, D.;
Panzella, L.; Amorati, R.; Capperucci, A.; Pizzo, E.; Napolitano,
A.; Menichetti, S.; d’Ischia, M. Org. Biomol. Chem. 2015, 13, 5757.
(f) Tanini, D.; Capperucci, A.; Degl’Innocenti, A. Eur. J. Org. Chem.
2015, 357. (g) Capperucci, A.; Tanini, D.; Borgogni, C.;
Degl’Innocenti, A. Heteroat. Chem. 2014, 25, 678.
Following the general procedure using N-thiophthalimide 1j (68 mg,
0.20 mmol), bis(trimethylsilyl) selenide (5; 23 mg, 0.10 mmol), and 1
M TBAF in THF solution (30 μL, 0.03 mmol) at 0 °C for 45 min gave,
after purification by column chromatography (petroleum ether/Et2O
8:1), 4j (21 mg, 53%) as a yellowish oil.
1H NMR (400 MHz, CDCl3): δ = 13.60 (s, 2 H, OH), 4.48 (s, 4 H, CH2Cl),
4.30 (q, J = 7.1 Hz, 4 H, CH2O), 1.35 (t, J = 7.1 Hz, 6 H, CH3).
13C NMR (100 MHz, CDCl3): δ = 177.7, 172.1, 99.6, 62.6, 40.7, 13.9.
HRMS: m/z [M + Na]+ calcd for C12H16Cl2NaO6S2: 412.9663; found:
(4) Capperucci, A.; Degl’Innocenti, A.; Funicello, M.; Mauriello, G.;
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Clark, M. J.; Tso, C. C. J. Chem. Soc., Perkin Trans. 1 1972, 680.
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Menichetti, S. Gazz. Chim. Ital. 1990, 120, 421. (b) Capozzi, G.;
Capperucci, A.; Degl’Innocenti, A.; Del Duce, R.; Menichetti, S.
Tetrahedron Lett. 1989, 30, 2995.
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(b) Harpp, D. N.; Back, G. T. J. Org. Chem. 1971, 36, 3828.
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114, 10082.
(10) Denmark, S. E.; Juanet, A. J. Org. Chem. 2014, 79, 140; and refer-
ences cited therein.
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Eur. J. 2012, 18, 11531. (b) Cai, Y.; Li, J.; Chen, W.; Xie, M.; Liu,
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643. (b) Capozzi, G.; De Sio, F.; Menichetti, S.; Nativi, C.; Pacini,
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3496.
1,2-Bis[(E)-5-chlorooct-4-en-4-yl]disulfane (4k)
Following the general procedure using N-thiophthalimide 1k (49 mg,
0.15 mmol), bis(trimethylsilyl) selenide (5; 17 mg, 0.075 mmol), and
1 M TBAF in THF solution (23 μL, 0.023 mmol) gave, after purification
by column chromatography (petroleum ether/Et2O 15:1), 4k (21 mg,
78%) as a pale yellowish oil.
1H NMR (400 MHz, CDCl3): δ = 2.66–2.69 (m, 4 H, CH2C=C), 2.56–2.60
(m, 4 H, CH2C=C), 1.51–1.63 (m, 8 H, CH2CH3), 0.94 (t, J = 7.6 Hz, 6 H,
CH3), 0.90 (t, J = 7.6 Hz, 6 H, CH3).
13C NMR (100 MHz, CDCl3): δ = 139.1, 132.4, 38.8, 35.0, 21.5, 20.8,
13.6, 13.2.
HRMS: m/z [M + Na]+ calcd for C16H28Cl2NaS2: 377.0907; found:
377.0923.
1,2-Bis[(E)-1-chloro-1-phenylprop-1-en-2-yl]disulfane (4l)
Following the general procedure using N-thiophthalimide 1l (66 mg,
0.20 mmol), bis(trimethylsilyl) selenide (5; 23 mg, 0.10 mmol), and 1
M TBAF in THF solution (30 μL, 0.03 mmol) gave, after purification by
column chromatography (petroleum ether/Et2O 15:1), 4l (33 mg, 91%)
as a yellowish oil.
1H NMR (400 MHz, CDCl3): δ = 7.32–7.41 (m, 10 H, ArH), 2.04 (s, 6 H,
CH3).
13C NMR (100 MHz, CDCl3): δ = 138.1, 133.2, 130.2, 129.5, 128.8,
128.1, 20.8.
HRMS: m/z [M + Na]+ calcd for C18H16Cl2NaS2: 388.9968; found:
388.9947.
(14) (a) Capozzi, G.; Menichetti, S.; Nativi, C.; Rosi, A.; Valle, G. Tetra-
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G.; Viglianisi, C. Org. Lett. 2016, 18, 5464.
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14, 5747. (b) Menichetti S., Faggi C., Onori M., Piantini S., Fer-
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Eur. J. Org. Chem.; DOI: 10.1002/ejoc.201801493.
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Supporting Information
Supporting information for this article is available online at
https://doi.org/10.1055/s-0037-1610354.
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