Regio- And stereoselective synthesis of new ensembles of diversely functionalized 1,3-thiaselenol-2-ylmethyl selenides by a double rearrangement reaction

Article abstract of DOI:10.3762/bjoc.16.47

The reaction of 2-(bromomethyl)-1,3-thiaselenole with potassium selenocyanate proceeded via a rearrangement with ring expansion, leading to a six-membered 2,3-dihydro-1,4-thiaselenin-2-yl selenocyanate (kinetic product) which in turn underwent rearrangement with ring contraction to a 1,3-thiaselenol-2-ylmethyl selenocyanate (thermodynamic product). These rearrangements occurred by a nucleophilic attack of the selenocyanate anion at two different carbon atoms of the seleniranium intermediate. The efficient regioselective synthesis of alkyl, allyl, 2-propynyl, benzyl, 4-fluorobenzyl, and 2-pyridinylmethyl 1,3-thiaselenol-2-ylmethyl selenides was developed based on the generation of sodium 1,3-thiaselenol-2-ylmethylselenolate from 1,3-thiaselenol-2-ylmethyl selenocyanate or bis(1,3-thiaselenol-2-ylmethyl) diselenide followed by nucleophilic substitution reactions. Sodium 1,3-thiaselenol-2-ylmethylselenolate underwent nucleophilic addition to alkyl propiolates in a regio- and stereoselective manner affording 1,3-thiaselenol-2-ylmethyl vinyl selenides in high yields predominantly with Z-configuration. Not a single representative of the 1,3-thiaselenol-2-ylmethyl selenide scaffold has been previously described in the literature.

Full text of DOI:10.3762/bjoc.16.47

Regio- and stereoselective synthesis of new ensembles of
diversely functionalized 1,3-thiaselenol-2-ylmethyl selenides
by a double rearrangement reaction
Svetlana V. Amosova*, Andrey A. Filippov, Nataliya A. Makhaeva, Alexander I. Albanov
and Vladimir A. Potapov
Full Research Paper
Open Access
Address:
Beilstein J. Org. Chem. 2020, 16, 515–523.
A. E. Favorsky Irkutsk Institute of Chemistry, SD RAS, 1 Favorsky
Str., 664033 Irkutsk, Russian Federation
doi:10.3762/bjoc.16.47
Received: 01 November 2019
Accepted: 09 March 2020
Published: 27 March 2020
Email:
Svetlana V. Amosova* - amosova@irioch.irk.ru
* Corresponding author
Associate Editor: T. J. J. Müller
Keywords:
© 2020 Amosova et al.; licensee Beilstein-Institut.
License and terms: see end of document.
2-(bromomethyl)-1,3-thiaselenole; nucleophilic addition; nucleophilic
substitution; rearrangement; seleniranium intermediate
Abstract
The reaction of 2-(bromomethyl)-1,3-thiaselenole with potassium selenocyanate proceeded via a rearrangement with ring expan-
sion, leading to a six-membered 2,3-dihydro-1,4-thiaselenin-2-yl selenocyanate (kinetic product) which in turn underwent rear-
rangement with ring contraction to a 1,3-thiaselenol-2-ylmethyl selenocyanate (thermodynamic product). These rearrangements
occurred by a nucleophilic attack of the selenocyanate anion at two different carbon atoms of the seleniranium intermediate. The
efficient regioselective synthesis of alkyl, allyl, 2-propynyl, benzyl, 4-fluorobenzyl, and 2-pyridinylmethyl 1,3-thiaselenol-2-
ylmethyl selenides was developed based on the generation of sodium 1,3-thiaselenol-2-ylmethylselenolate from 1,3-thiaselenol-2-
ylmethyl selenocyanate or bis(1,3-thiaselenol-2-ylmethyl) diselenide followed by nucleophilic substitution reactions. Sodium 1,3-
thiaselenol-2-ylmethylselenolate underwent nucleophilic addition to alkyl propiolates in a regio- and stereoselective manner
affording 1,3-thiaselenol-2-ylmethyl vinyl selenides in high yields predominantly with Z-configuration. Not a single representative
of the 1,3-thiaselenol-2-ylmethyl selenide scaffold has been previously described in the literature.
Introduction
The regio- and stereoselective synthesis of organoselenium The important trend in the field of organoselenium chemistry
compounds based on selenium-centered electrophilic reagents within the last 15 years was the involvement of selenium
has been one of the most important and effective directions in dihalides in the synthesis of organoselenium compounds
organoselenium chemistry for half a century [1-12].
[13,14]. The first synthesis of organoselenium compound from
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Beilstein J. Org. Chem. 2020, 16, 515–523.
selenium dihalides was the preparation of 1,4-selenasilaful- The structure of compound 1 suggests the possibility of forma-
venes by cyclization reaction with diethynyldimethylsilane tion of both seleniranium 2 and thiiranium 3 cations, whose par-
[15,16]. The creation of new methodologies for the synthesis of ticipation in the nucleophilic substitution reaction will lead to
new classes of organoselenium compounds and especially sele- two different reaction products (Scheme 1).
nium heterocycles, with promising biological activity based on
affordable and environmentally friendly materials is another im-
portant trend in organoselenium chemistry [17]. Reviews on the
biological activity of organoselenium compounds reported ex-
amples exhibiting high antitumor, antiviral, antimicrobial, and
neuroprotective activities [12,18,19]. A number of organosele-
nium compounds including selenoglutathion [20], trans-3,4-
dihydroxyselenolane [21], and ascorbyl selenoesters [22] exhib-
it high glutathione peroxidase-like activity [12,18,19].
Scheme 1: Possible formation of reaction products starting from 1 via
seleniranium 2 or thiiranium cations 3.
A series of novel approaches to functionalized organoselenium
compounds was developed recently [23-29]. Among these is an
elegant, highly effective approach that led to β-hydroxy, However, particularly, the reaction proceeds via an intermedi-
β-mercapto, and β-amino-substituted diorganyl diselenides and ate seleniranium cation 2. This is explained by the high
selenides. This was accomplished by the opening of three-mem- anchimeric assistance effect of the selenium atom which is
bered oxygen-, sulfur- and nitrogen-containing heterocycles more than one order of magnitude greater than the effect of the
under the action of bis(trimethylsilyl)selenide [23]. The meth- sulfur atom. This was established based on the determination of
odology based on bis(trimethylsilyl)selenide was also success- the absolute and relative rates of nucleophilic substitution of
fully applied to the synthesis of functionalized asymmetric chlorine in 2,6-dichloro-9-selenabicyclo[3.3.1]nonane and 2,6-
alkyl- and vinyl selenides, including cyclic disubstituted 1,3- dichloro-9-thiabicyclo[3.3.1]nonane [36].
thiaselenolane and trisubstituted thiaselenane [26,27]. Vinyl
selenides represent a very interesting class of compounds with a The nucleophilic substitution reactions in thiaselenole 1 with O-
wide range of synthetic applications [28,29].
and S-centered nucleophiles proceeded regioselectively in an
unusual manner at two centers of the seleniranium cation 2: the
The anchimeric assistance effect, also known as the participa- selenium atom and the carbon atom C2. The classical nucleo-
tion of neighbouring groups, is usually considered mainly as a philic substitution reaction at the carbon atom C3 did not occur
factor accelerating the rate of nucleophilic substitution reac- (Scheme 2).
tions. At present, we are observing a new manifestation of this
effect, consisting in the promotion of new rearrangements The high anchimeric assistance effect of the selenium atom in
leading to the selective formation of various selenium-contain- thiaselenole 1 is the driving force for the generation of the
ing unsaturated linear and heterocyclic compounds. This effect seleniranium intermediate 2. A fundamental approach to the
works in 2-(bromomethyl)-1,3-thiaselenole (1) – a unique regio- and stereoselective synthesis of unsaturated functionali-
reagent, which exhibits unusual properties in nucleophilic reac- zed organoselenium compounds was developed during the last
tions. This reagent was obtained [30-32] in high yield and with ten years based on new directions for nucleophilic substitution
high purity by a one-pot synthesis from divinyl sulfide [33-35] reactions proceeding via intermediate seleniranium cations 2
and selenium dibromide.
generated from thiaselenole 1.
Scheme 2: Unusual regio- and stereoselective nucleophilic reactions of thiaselenole 1 at two centers of the seleniranium cation 2.
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Beilstein J. Org. Chem. 2020, 16, 515–523.
Scheme 3: Reactions of thiaselenole 1 with С- and S-centered nucleophiles affording new families of linear unsaturated (Z)-2-
[(organylsulfanyl)selanyl]ethenyl vinyl sulfides [31,37-40].
We have carried out new regioselective reactions of thiase- [31], thiourea [32], alcohols [42], functionalized organic acids
lenole 1 with dithiocarbamates [31], ketones [37], thiols [43,44], functionalized pyridines [45], ammonium thiocyanate
[38,39], dithiols [38], and mercapto benzazoles [40]. These are [46], and mercapto benzazoles [40] were developed
the first examples of a nucleophilic attack at the selenium atom (Scheme 4).
of the seleniranium cation 2 with the generation of a new Se–S
bond, yielding new families of linear unsaturated (Z)-2- The new methodology of a regioselective nucleophilic substitu-
[(organylsulfanyl)selanyl]ethenyl vinyl sulfides (Scheme 3). tion at three different centers of a seleniranium intermediate 2
in reactions of thiaselenole 1 with mercapto benzazoles contain-
Cascade regio- and stereoselective reactions of thiaselenole 1 ing various combinations of heteroatoms (N, O and S) was de-
with water and ethylene glycol resulted in the formation of the veloped (Scheme 5). The reaction proceeded with the forma-
first representatives of the new family of polyfunctional 2,3- tion of a new family of 2,3-dihydro-1,4-thiaselenines (up to
dihydro-1,4-thiaselenines [41]. The regioselective nucleophilic 96% yields) – products of rearrangement with ring expansion,
substitution reactions in thiaselenole 1 proceeding at the C2 car- which in turn underwent rearrangement with ring contraction,
bon atom of the seleniranium cation 2 with dithiocarbomates forming a new family of 1,3-thiaselenoles in up to 99% yield.
Scheme 4: The reactions of thiaselenole 1 with the formation of polyfunctionalized 2,3-dihydro-1,4-thiaselenines.
Scheme 5: The synthesis of new 1,3-thiaselenole ensembles by reactions of thiaselenole 1 with mercapto benzazoles.
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Beilstein J. Org. Chem. 2020, 16, 515–523.
The article was included in the RSC themed web collection It was suggested that the reaction proceeds via an intermediate
"The chemistry of Selenium & Tellurium at the beginning of six-membered selenocyanate 5, which could be observed at a
the 3rd millennium" [40].
lower temperature. Indeed, monitoring the reaction by 1H NMR
spectroscopy using the same conditions as in the synthesis of
Our short preliminary publication reported the formation of 1,3- the selenocyanate 4, but at 0 °C confirmed this assumption
thiaselenol-2-ylmethyl selenocyanate (4) in the reaction thiase- (Scheme 6).
lenole 1 with selenocyanate [47].
Results and Discussion
In this work the nucleophilic substitution reaction of thiase-
lenole 1 with potassium selenocyanate was studied in detail. We
found that the reaction of thiaselenole 1 with KSeCN at room
temperature afforded a five-membered heterocycle, seleno-
cyanate 4, in a quantitative yield. This result was unusual since
Scheme 6: The formation of product 4 via compound 5 by the reac-
tion of thiaselenole 1 with potassium selenocyanate.
previously studied substitution reactions of thiaselenole 1 with
various nucleophiles (Scheme 4) were accompanied by ring The monitoring results are presented in Figure 1 and Table 1.
expansion leading to six-membered functionalized dihydrothia- The reaction was studied in the time interval from 0.25 to 6 h.
selenines. Furthermore, the reaction of thiaselenole 1 with am- Having assigned the 1H NMR data for compounds 1 and 4, we
monium thiocyanate also gave the six-membered 2,3-dihydro- found signals of an unknown compound, which was easily iden-
1,4-thiaselenin-2-yl thiocyanate (Scheme 4) [46].
tified after 0.5 h (at 46% conversion of thiaselenole 1) as the
Figure 1: Monitoring the reaction of thiaselenole 1 with KSeCN by 1H NMR spectroscopy (in accordance with the data of Table 1). Reaction condi-
tions: compound 1 (0.5 mmol), KSeCN (0.5 mmol), MeCN (2.5 mL), 0 °C.
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Beilstein J. Org. Chem. 2020, 16, 515–523.
Table 1: Results the reaction of thiaselenole 1 with KSeCN based on 1H NMR spectroscopy monitoring (Figure 1).a
entry
time, h
molar ratio (%)
conversion of 1 (%)
1
5
4
1
2
3
4
5
6
7b
8с
0.25
0.5
1
2
4
63
54
33
16
6
0
0
0
37
46
61
71
80
59
14
0
0
0
6
13
14
41
86
100
37
46
67
84
94
100
100
100
6
4 + 1
6 + 1
aReaction conditions: compound 1 (0.5 mmol), KSeCN (0.5 mmol), MeCN (2.5 mL), 0 °C. b4 h at 0 °C and 1 h without cooling. с6 h at 0 °C and 1 h
without cooling.
six-membered selenocyanate 5 (Table 1, entry 2). The vinyl The formation of the six-membered heterocycle of 2,3-dihydro-
proton signals of the SeCH= groups (6.63 ppm, 3JН,H = 6.3 Hz, 1,4-thiaselenin-2-yl selenocyanate 5 was confirmed, inter alia,
compound 1; 6.67 ppm, 3JН,H = 6.3 Hz, compound 4; 6.53 ppm, by the observation of two doublets corresponding to the
3JН,H = 9.9 Hz, compound 5) were used to estimate the com- olefinic protons of the SCH=CHSe group with 3J = 9.9 Hz
pounds ratios. The signals of the two protons of the SeCH2 in the 1H NMR spectrum (Table 1, entry 2). In the case
group in the six-membered ring 5 are not equivalent. As conse- of five-membered compounds 1 and 4, the coupling constant
quence they are observed in the 1H NMR spectrum as two of the olefinic protons of the SCH=CHSe group would
doublets of doublets with geminal and vicinal coupling con- be 3JH,H = 6.3 Hz [32,40]. The SCHSe group of the hetero-
stants with the SCH-proton in the same ring (3.79 ppm, 2JН,Н = cycle 5 was characterized by a doublet of doublets at
12.4 Hz, 3JН,Н = 2.1 Hz; 3.33 ppm, 2JН,Н = 12.4 Hz, 3JН,Н = 5.21 ppm (3J = 2.1 and 3J = 6.6 Hz). This was the result of cou-
6.6 Hz). The maximum content of compound 5 (80%) was pling with the nonequivalent protons of the CH2Se group.
reached after 4 h at a molar ratio of 1:5:4 = 6:80:14, Table 1, Similar spectral characteristics were observed for other six-
entry 5). Afterwards, the content of compound 5 dropped membered 2,3-dihydro-1,4-thiaselenin-2-yl derivatives
sharply with an increase of the content of compound 4 from 14 [31,32,38,40].
to 41% and the complete conversion of thiaselenole 1 at molar
ratio of 1:5:4 = 0:59:41, Table 1, entry 6). The comparison of
entries 5 and 6 (Table 1) clearly indicates that compound 4 was
formed due to a rearrangement of selenocyanate 5 rather than
by the “classical” nucleophilic substitution of bromine in thiase-
lenole 1. The rearrangement of selenocyanate 5 to compound 4
proceeded already at 0 °C, and therefore we were not able to
isolate compound 5 under these conditions.
Thus, the reaction of thiaselenole 1 with potassium seleno-
cyanate led to the six-membered thiaselenine 5 (kinetic
product), which underwent a rearrangement to a five-mem-
bered thiaselenole selenocyanate 4 (thermodynamic product).
These rearrangements proceeded by a nucleophilic attack of the
selenocyanate anion on two different carbon atoms of the selen-
iranium intermediate 2 (Scheme 7).
Scheme 7: The reaction pathway for the formation of compounds 4 and 5.
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Beilstein J. Org. Chem. 2020, 16, 515–523.
The formation of thiaselenole 4 was the result of two rearrange- The 1,3-thiaselenol-2-ylmethylselenolate anion generated from
ments, rather than a “classical” nucleophilic substitution of the selenocyanate 4 was also subjected to a nucleophilic addition
bromine atom in thiaselenole 1.
reaction with activated acetylenes (Scheme 9). The reaction of
the 1,3-thiaselenol-2-ylmethylselenolate anion with alkyl propi-
Similar rearrangements were found and studied in the reactions olates proceeded in a regio- and stereoselective manner
of thiaselenole 1 with mercaptobenzazoles [40].
affording alkyl 3-[(1,3-thiaselenol-2-ylmethyl)selanyl]-2-
propenoates 7a (Z/E = 94:6) and 7b (Z/E = 93:7) in 94% and
Having established the synthesis of heterocycle 4 this unsatu- 90% yields, respectively.
rated five-membered S,Se-containing compound was used as a
starting material for the synthesis of novel ensembles of sele- The one-pot synthesis of hitherto unknown bis(1,3-thiaselenol-
nium heterocycles with promising biological activity.
2-ylmethyl) diselenide (8) in 90% yield from thiaselenole 1 was
developed (Scheme 10). The reaction proceeded via the forma-
The treatment of 4 with organyl halides resulted in the efficient, tion of thiaselenole selenocyanate 4, which was in situ con-
regioselective synthesis of hitherto unknown organyl 1,3-thiase- verted into diselenide 8. This compound consisted of two dia-
lenol-2-ylmethyl selenides 6a–l in high yields (Scheme 8). The stereomers, and two signals corresponding to each of them were
synthesis was based on the generation of sodium 1,3-thiase- observed in the 77Se NMR spectrum.
lenol-2-ylmethylselenolate by the reaction of NaBH4 with com-
pound 4 in methanol followed by nucleophilic substitution reac- Diselenide 8 was used as a starting material for the synthesis of
tions with organyl halides. Various substrates were involved in 1,3-thiaselenol-2-ylmethylselanyl derivatives. Compounds 6a–j
the reaction, providing the introduction of alkyl, benzyl, allyl, were prepared in 78–90% yields via the generation of sodium
and 2-propynyl moieties as well as pharmacophores as 1,3-thiaselenol-2-ylmethylselenolate through reduction of the
2-pyridylmethyl and 4-fluorobenzyl. A possibility for the syn- Se–Se bond with NaBH4 followed by nucleophilic substitution
thesis of compounds containing two 1,3-thiaselenol-2- with alkyl halides (Scheme 11).
ylmethylselanyl heterocycles connected by a carbon bridge was
demonstrated (e.g., compound 6k containing two 1,3-thiase- Thus, two efficient methods for the preparation of novel 1,3-
lenol-2-ylmethylselanyl heterocycles connected by a six-car- thiaselenol-2-ylmethylselanyl derivatives 6a–l from seleno-
bon bridge).
cyanate 4 and diselenides 8 were developed. Selenocyanate 4
Scheme 8: Synthesis of new ensembles of 1,3-thiaselenol-2-ylmethyl selenides 6a–l (77Se NMR data are included).
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Scheme 9: The synthesis of vinyl selenides 7a,b through nucleophilic addition of 1,3-thiaselenol-2-ylmethylselenolate anion to alkyl propiolates
(77Se NMR data are included).
Scheme 10: One-pot synthesis of diselenide 8 from thiaselenole 1 (77Se NMR data are included).
Scheme 11: Synthesis of compounds 6a–j from diselenide 8.
and diselenide 8 were shown to be the synthons of the 1,3- Two doublets of the olefinic protons of the SCH=CHSe group
thiaselenol-2-ylmethylselenolate anion, which was involved in with 3J = 6.3–6.6 Hz were observed in the 1H NMR spectra
the nucleophilic substitution reactions and regio- and stereose- of heterocycles 4, 6a–l, 7a,b and 8. These values are typical
lective nucleophilic additions to activated acetylenes. However, for five-membered 1,3-thiaselenoles [31,32]. The structure of
the method to generate the 1,3-thiaselenol-2-ylmethylselenolate 1,3-thiaselenol-2-ylmethyl derivatives 4, 6a–l, 7a,b
anion from selenocyanate 4 seemed to be more efficient, and and 8 was confirmed, inter alia, by the spin–spin coupling
the yields of the thiaselenol-2-ylmethylselanyl derivatives 6a–l constants between the selenium atom and the carbon
from selenocyanate 4 were slightly higher compared to that of atom of the SCHSe group in the ring. The observed values
the method based on diselenide 8.
(66.1–68.2 Hz) were characteristic for direct coupling con-
stants (1JSe-C).
The structures of compounds 6a–l, 7a,b and 8 were proved by
1H, 13C, 15N, 19F and 77Se NMR and mass spectrometry. The The signals of the selenium atoms in the 77Se NMR spectra
composition of the products was confirmed by elemental analy- of the synthesized compounds 6a–l, 7a,b, and 8 were seen
sis. Molecular ions of the synthesized compounds were ob- in the region of 526.41–534.48 ppm (for the ring) and
served in their mass spectra.
148.82–401.09 ppm (in the side chain).
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Conclusion
The reaction of 2-(bromomethyl)-1,3-thiaselenole (1) with
potassium selenocyanate was found to occur with a rearrange-
ment and ring expansion leading to six-membered 2,3-dihydro-
1,4-thiaselenin-2-yl selenocyanate 5, which at room tempera-
ture underwent rearrangement and ring contraction to 1,3-
thiaselenol-2-ylmethyl selenocyanate 4. These rearrangements
proceeded via a seleniranium cation 2 that is attacked by the
nucleophilic selenocyanate anion at two different carbon atoms
of the three-membered ring.
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of diverse 1,3-thiaselenol-2-ylmethyl selenides 6a–l, 7a,b and
diselenide 8 in high yields was developed based on the genera-
tion of a 1,3-thiaselenol-2-ylmethylselenolate anion, which was
involved in three different reactions: nucleophilic substitution
with a wide range of organic halides, regio- and stereoselective
nucleophilic addition to activated acetylenes and oxidation.
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A high selectivity, mild reaction conditions and very simple
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The obtained compounds represent novel ensembles of functio-
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sulfur atom and two selenium atoms of different nature
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Supporting Information
doi:10.2174/1385272819666150810222454
14.Abakumov, G. A.; Piskunov, A. V.; Cherkasov, V. K.; Fedushkin, I. L.;
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Averin, A. D.; Bochkarev, M. N.; Trifonov, A. A.; Dzhemilev, U. M.;
Dyakonov, V. A.; Egorov, M. P.; Vereshchagin, A. N.;
Syroeshkin, M. A.; Jouikov, V. V.; Muzafarov, A. M.; Anisimov, A. A.;
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Supporting Information File 1
Experimental section and 1H, 13C, 15N, 19F and 77Se NMR
spectra of all synthesized compounds.
[https://www.beilstein-journals.org/bjoc/content/
supplementary/1860-5397-16-47-S1.pdf]
Acknowledgements
The authors thank Baikal Analytical Center SB RAS for provid-
ing the instrumental equipment for structural investigations.
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ORCID® iDs
Svetlana V. Amosova - https://orcid.org/0000-0002-2874-3725
Nataliya A. Makhaeva - https://orcid.org/0000-0002-8808-0994
Vladimir A. Potapov - https://orcid.org/0000-0002-3151-6726
Khim. Geterotsikl. Soed. 2003, 39, 633–634.
16.Potapov, V. A.; Amosova, S. V. Russ. J. Org. Chem. 2003, 39,
1373–1380. doi:10.1023/b:rujo.0000010549.08131.18
Zhurn. Org. Khim. 2003, 39, 1449-1455.
17.Lippolis, V.; Santi, C. New J. Chem. 2019, 43, 11032–11033.
doi:10.1039/c9nj90092f
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