A novel application of 2-silylated 1,3-dithiolanes for the synthesis of aryl/hetaryl-substituted ethenes and dibenzofulvenes

Article abstract of DOI:10.3762/bjoc.13.185

Trimethylsilyldiazomethane (TMS-CHN₂) reacts readily with hetaryl thioketones to give sterically crowded 2-trimethylsilyl- 4,4,5,5-tetrahetaryl-1,3-dithiolanes with complete regioselectivity at -75 °C as well as at rt. Thiofluorenone, a relatively stable and highly reactive aryl thioketone, yields upon treatment with TMS-CHN₂at -60 °C the corresponding 1,3,4-thiadiazoline. This unstable cycloadduct undergoes decomposition at ca. -45 °C and the silylated thiocarbonyl S-methanide generated thereby is trapped with complete regioselectivity by aryl or hetaryl thioketones forming also sterically crowded 2-trimethylsilyl-1,3- dithiolanes. The obtained 1,3-dithiolanes, by treatment with an equimolar amount of TBAF in a one-pot procedure, are converted in high yields into hetaryl/aryl-substituted ethenes or dibenzofulvenes, respectively, via a cycloreversion reaction of the intermediate 1,3-dithiolane carbanion. The presented protocol offers a new, highly efficient approach to tetrasubstituted ethenes and dibenzofulvenes bearing aryl and/or hetaryl substituents.

Full text of DOI:10.3762/bjoc.13.185

A novel application of 2-silylated 1,3-dithiolanes for the
synthesis of aryl/hetaryl-substituted ethenes
and dibenzofulvenes
Grzegorz Mlostoń*1, Paulina Pipiak1, Róża Hamera-Fałdyga1 and Heinz Heimgartner2
Full Research Paper
Open Access
Address:
Beilstein J. Org. Chem. 2017, 13, 1900–1906.
1Department of Organic and Applied Chemistry, University of Łódź,
doi:10.3762/bjoc.13.185
Tamka 12, PL 91-403 Łódź, Poland and 2Department of Chemistry,
University of Zürich, Winterthurerstrasse 190, CH-8057 Zürich,
Switzerland
Received: 30 June 2017
Accepted: 24 August 2017
Published: 08 September 2017
Email:
Grzegorz Mlostoń* - gmloston@uni.lodz.pl
Dedicated to Professor Tadeusz Marek Krygowski (Warsaw) on the
occasion of his 80th birthday
*
Corresponding author
Associate Editor: I. R. Baxendale
Keywords:
diazomethanes; 1,3-dipolar cycloadditions; olefination reactions;
reaction mechanisms; thioketones
© 2017 Mlostoń et al.; licensee Beilstein-Institut.
License and terms: see end of document.
Abstract
Trimethylsilyldiazomethane (TMS-CHN2) reacts readily with hetaryl thioketones to give sterically crowded 2-trimethylsilyl-
4
,4,5,5-tetrahetaryl-1,3-dithiolanes with complete regioselectivity at −75 °C as well as at rt. Thiofluorenone, a relatively stable and
highly reactive aryl thioketone, yields upon treatment with TMS-CHN2 at −60 °C the corresponding 1,3,4-thiadiazoline. This
unstable cycloadduct undergoes decomposition at ca. −45 °C and the silylated thiocarbonyl S-methanide generated thereby is
trapped with complete regioselectivity by aryl or hetaryl thioketones forming also sterically crowded 2-trimethylsilyl-1,3-
dithiolanes. The obtained 1,3-dithiolanes, by treatment with an equimolar amount of TBAF in a one-pot procedure, are converted in
high yields into hetaryl/aryl-substituted ethenes or dibenzofulvenes, respectively, via a cycloreversion reaction of the intermediate
1
,3-dithiolane carbanion. The presented protocol offers a new, highly efficient approach to tetrasubstituted ethenes and dibenzoful-
venes bearing aryl and/or hetaryl substituents.
Introduction
Aryl and hetaryl-substituted ethenes form an important class of of substituted ethenes is of great importance and the so-called
organic compounds with a growing number of applications in olefination reactions allow for valuable functional-group trans-
materials chemistry, crystal engineering, photooptics, etc. formations [10-13]. As a general method for the preparation of
Among these, the thiophen-2-yl-substituted ethenes [1-5] as tetrasubstituted ethenes, the McMurry reaction is widely applied
well as dibenzofulvenes-containing compounds [6-9] are of [14]. Another approach, which opens access to diverse ethenes,
special interest. The development of methods for the synthesis is the ‘two-fold extrusion reaction’, which comprises the
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Beilstein J. Org. Chem. 2017, 13, 1900–1906.
[
3 + 2]-cycloaddition of a diazo compound with a thiocarbonyl In a recent publication, similar reactions of TMS-CHN2 with 1a
dipolarophile and subsequent elimination of N2 followed by and some dihetaryl thioketones, e.g., 1d and 1e, were reported
sulfur extrusion [15-17].
[22]. In contrast to CH2N2, TMS-CHN2 reacted with thiobenzo-
phenone (1a) with evolution of N2 even at −75 °C and led to a
In our continuing studies on [3 + 2]-cycloadditions with thioke- mixture of 4,4,5,5-tetraphenyl-1,3-dithiolane 6a and 2,2,3,3-
tones and diazo compounds, we turned our attention to hetaryl tetraphenyl-1,4-dithiane 7 (Scheme 2). This result demon-
thioketones [18]. It turned out that the presence of the hetaryl strated that TMS-CHN2 does not form a stable [3 + 2]-cyclo-
groups strongly influences the reactivity of these dipolarophiles adduct with 1a, but, in analogy to 1b in the reaction with
in reactions with diazomethane (CH2N2, Schönberg reaction) CH2N2, spontaneous elimination of N2 takes place. In another
[
19-21]. For example, in contrast to thiobenzophenone (1a), study, we described a different behaviour of thiofluorenone
phenyl selenophen-2-yl thioketone (1b) does not form the corre- (1c), which reacted with TMS-CHN2 at −60 °C to yield the ex-
sponding 2,5-dihydro-1,3,4-thiadiazole of type 2, and even at pected [3 + 2]-cycloadduct 8, which only at ca. −40 °C extruded
−
70 °C spontaneous elimination of N2 was observed. As prod- N2 [23].
ucts of this reaction, dimer 4 of the intermediate thiocarbonyl
S-methanide 3 and the sterically crowded 4,4,5,5-tetraaryl-1,3- The goal of the present study was the preparation of a series of
dithiolane 5 were obtained (Scheme 1) [20]. The formation of 2-trimethylsilyl-1,3-dithiolanes of type 6, which, after desilyl-
both products was rationalized by the assumption that the in situ ation, should be applied for nucleophilic additions of the 1,3-
formed 3a reacts as a delocalized diradical species.
dithiolane anion with some electrophilic agents. An analogous
Scheme 1: Reactions of diphenyl and phenyl selenophen-2-yl thioketones with diazomethane (CH2N2; Sel = selenophen-2-yl).
Scheme 2: Reaction of diaryl thioketones with trimethylsilyldiazomethane (TMS-CHN2).
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sequence of reactions was described earlier for 2-aryl-2-tri- ucts as tetrasubstituted ethenes 9b,c (Scheme 3, Table 1). The
methylsilyl-1,3-dithiolanes [24,25].
signals for the ethene C=C atoms appeared at 127.7 and
31.2 ppm, respectively. In addition, the melting point deter-
mined for 9b confirmed its identity with the known
1
Results and Discussion
The earlier described protocol for the reaction of thiobenzo- tetrakis(thiophen-2-yl)ethene [1].
phenone (1a) with TMS-CHN2 [22] has been slightly modified
and the reaction was performed at −70 °C using the reagents in The same products 9b,c were obtained in reactions at 0 °C in
a ratio of 3:1. Under these conditions, 1,3-dithiolane 6a was comparable yields, when the initially formed 1,3-dithiolanes
formed almost exclusively with only traces of 1,4-dithiane 7 as 6b,c, without isolation, were treated with equimolar amounts of
revealed by 1H NMR analysis of the crude reaction mixture. TBAF. Using this protocol, the non-symmetrical thioketones
Desilylation of 6a occurred quantitatively and the known 1b,f,g were smoothly converted into the corresponding
tetraphenylethylene (9a) [26] was obtained in 90% yield. tetraarylethenes 9d–f (Table 1). However, in these cases, mix-
tures of (Z)- and (E)-isomers were formed and isolated in
Two symmetric dihetaryl thioketones, 1d and 1e, were reacted 65–75% yield. In all cases, the ratio of isomers was calculated
with TMS-CHN2 in THF at −75 °C, and after the spontaneous to ca. 3:2 (1H NMR); however, the attempted chromatographic
elimination of N2, the sterically crowded 4,4,5,5-tetrahetaryl- separation was unsuccessful.
1
,3-dithiolanes 6b and 6c, respectively, were obtained as exclu-
sive products in high yields [22]. The isolated pure products The results obtained with thiofluorenone (1c) prompted us to
were treated with equimolar amounts of TBAF in THF at room prepare other 2-trimethylsilylated 1,3-dithiolanes of type 6,
temperature and the progress of the reaction was monitored by available via [3 + 2]-cycloaddition of the in situ generated (at
TLC. After ca. 1 h, the crude reaction mixtures obtained after ca. −45 °C) silylated thiocarbonyl S-methanide 10 with thioke-
aqueous work-up were analysed by 1H NMR spectroscopy. tones 1a,c,d,h and i. The obtained products of type 6, without
Unexpectedly, in both cases, only signals of hetaryl rings were isolation, were desilylated at rt to give the expected ethenes
observed. The 13C NMR spectra allowed to identify both prod- 9g–k with a fluorenylidene moiety (Scheme 4, Table 1).
Scheme 3: Formation of tetraaryl/hetarylethenes 9 from the reaction of TMS-CHN2 with diaryl/hetaryl thioketones 1 (for Ar1, Ar2 see Table 1).
Table 1: Synthesis of tetraaryl/hetarylethenes 9a−f and dibenzofulvenes 9g−k from diaryl thioketones 1 and TMS-CHN2.a
1
Ar1
Ar2
6
Ar1
Ar2
9
Ar1
Ar2
Yield [%]b
a
b
d
e
f
Ph
Ph
Thi
Sel
Sel
Ph
Ph
a
f
Ph
Ph
90
71
89
87
65
75
72
70
77
66
62
Sel
Thi
Sel
Fur
Thi
–
Ph
Sel
Thi
Sel
Fur
Thi
Ph
b [8]
Thi
Sel
Thi
Sel
b
c
d
e
g
h
i
Thi
c [8]
–
Sel
Sel
g
c
c
c
c
c
–
Ph
fluorenylidene
fluorenylidene
fluorenylidene
fluorenylidene
fluorenylidene
–
Ph
–
fluorenylidene
Thi
–
Thi
–
j
dibenzosuberenylidene
dibenzosuberylidene
–
k
aPh = Phenyl, Thi = thiophen-2-yl, Sel = selenophen-2-yl, Fur = furan-2-yl. bYield of isolated ethenes 9 from the one-pot reaction.
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Beilstein J. Org. Chem. 2017, 13, 1900–1906.
Scheme 4: Synthesis of dibenzofulvenes 9g–k.
The unexpected formation of tetrasubstituted ethenes 9 from For comparison reasons, two other 2-trimethylsilyl 1,3-dithi-
,3-dithiolanes of type 6 requires a mechanistic explanation. olanes 13a,b with no substituents at C4 and C5 were prepared
1
The behaviour of these dithiolanes under desilylation condi- and tested in desilylation reactions performed with TBAF in
tions differs significantly from that of 4,5-unsubstituted 1,3- THF solutions. In both cases, quenching of the intermediate
dithiolane 13c (Scheme 5). In the latter case, the desilylation carbanions with water led to the corresponding 1,3-dithiolanes
leads to the corresponding carbanion, which can be trapped with 15a and 15b, and no [3 + 2]-cycloreversion of the heterocyclic
an aldehyde to give 14 [24,25]. In contrast, the carbanion 11 ring was observed (Scheme 5). As mentioned before, 1,3-dithi-
undergoes a spontaneous cycloreversion to yield tetraaryl/ olane 13c has been reported as a convenient source of a reac-
hetarylethene 9 and dithioformic acid anion (12).
tive carbanion, which subsequently was trapped with aromatic
Scheme 5: a) Mechanistic explanation for formation of ethenes 9 from dithiolanes of type 6 and b) desilylation reactions of 2-trimethylsilyl-1,3-
dithiolanes 13.
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Beilstein J. Org. Chem. 2017, 13, 1900–1906.
or aliphatic aldehydes as electrophilic agents yielding alcohols High resolution MS measurements were performed with a GCT
1
4, which should be considered as protected forms of corre- Premier Waters instrument. Melting points were determined in
sponding α-hydroxyaldehydes [24,25]. Also in this series, no capillaries with a Stuart SMP30 apparatus with automatic tem-
3 + 2]-cycloreversion of the intermediate carbanion leading to perature monitoring. Microwave-supported syntheses of thioke-
[
the destruction of the heterocyclic ring was observed. These ex- tones 1 were performed using the CEM-focused Microwave-
periments demonstrate that the 4,5-unsubstituted 1,3-dithiolane type Discover SPD reactor.
carbanions generated under mild conditions through desilyl-
ation of the appropriate precursors 13 do not require an elec- Starting materials: Trimethylsilyldiazomethane (TMS-CHN2)
tron-withdrawing substituent for their stabilization [29].
was a commercial reagent which was used in all reactions as
M THF solution without further purification. Thiobenzo-
1
The preparation of 1,3-dithianes and 1,3-dithiolanes, as well as phenone (1a), thiodibenzosuberenone (1h), and thiodibenzo-
the generation of the corresponding carbanions are widely suberone (1i) were prepared from the corresponding ketones by
applied in the umpolung chemistry [27,28] and in the chemistry treatment with Lawesson’s reagent (L.R.) in toluene upon irra-
of protective groups [29,30], but tetrasubstituted ethenes have diation with microwaves (150 W) over 2 min [32]. The most
never been prepared by using this approach.
efficient method for the preparation of thiofluorenone (1c) was
the thionation of fluorenone by simultaneous passing of dry
hydrogen chloride and hydrogen sulfide streams through the
Conclusion
The presented study showed that 2-trimethylsilyl-4,4,5,5- ethanolic solution at 0–5 °C (ice bath cooling) [33]. In analogy
tetraaryl-1,3-dithiolanes, readily available by treatment of to 1a, hetaryl thioketones 1b,d–g were prepared from the corre-
hetaryl thioketones with trimethylsilyl diazomethane (TMS- sponding ketones [34] by treatment with L.R. in toluene solu-
CHN2), are superior substrates for the preparation of tion upon irradiation with microwaves over 2 min [32].
tetraarylethenes. Another group of 2-trimethylsilylated 1,3-
dithiolanes, obtained through the [3 + 2]-cycloaddition of General Procedure for the one-pot synthesis of ethenes 9a–f:
trimethylsilylated thiofluorenone S-methanide with aryl and A hetaryl thioketone 1 (1 mmol) was dissolved in THF
hetaryl thioketones can also be used for this transformation. The (2–3 mL) and the solution was cooled to 0 °C (ice bath). Then,
described protocol opens a new, straightforward access to a the mixture was treated with small portions of an ethereal solu-
series of new dibenzofulvenes [7] containing hetaryl rings, tion of TMS-CHN2 (2 M, 0.5 mL, 1 mmol). The reaction was
which can be of great interest in materials chemistry and related complete after ca. 15 min (TLC, petroleum ether/CH2Cl2 8:2).
sciences. The key intermediate in the reaction is the 1,3-dithi- Then, a solution of TBAF (1 M in THF, 1 mL, 1 mmol) was
olane carbanion, which, in contrast to the 4,5-unsubstituted ana- added. After complete reaction (TLC, petroleum ether/CH2Cl2
logues, undergoes a spontaneous cycloreversion reaction to give 8:2), the solvent was removed under vacuum, and the residue
tetraarylethene and dithioformate anion. This method supple- was subjected to 1H NMR analysis in CDCl3 solution. The
ments the list of preparatively useful olefination reactions and is crude products 9a–f were purified by column chromatography
another proof for the utility of aryl and hetaryl thioketones in (Et2O/CH2Cl2 8:2).
organic synthesis [18]. Another important feature of the
presented system with a potential, practical application to mate- 1,1,2,2-Tetrakis(selenophen-2-yl)ethene (9c): Yield: 236 mg
rials and coordination chemistry is the release of strictly con- (87%); chromatographic purification (petroleum ether/CHCl3
trolled amounts of the dithioformate anion under mild, neutral 8:2). Orange crystals; mp 199–202 °C; IR (KBr) ν: 3085 (w),
conditions [31].
1445 (m), 1429 (m), 1236 (s), 1182 (m), 1116 (m), 1024 (m),
49 (m), 840 (m), 748 (s), 687 (s) cm−1; 1H NMR (600 MHz,
CDCl3) δ 7.14–7.15 (m, 4 Harom), 7.20–7.21 (m, 4 Harom), 8.09
8
Experimental
General information: Solvents and chemicals were purchased (dd, J = 6.0 Hz, 1.2 Hz, 4 Harom) ppm; 13C NMR (150 MHz,
and used as received without further purification. Products were CDCl3) δ 129.1, 133.0, 134.2 (12 CHarom), 131.2 (2 C=), 149.6
purified by standard column chromatography on silica gel (4 Carom) ppm; anal. calcd for C18H12Se4 (544.13): C, 39.73; H,
(
230–400 mesh, Merck). Unless stated otherwise, yields refer to 2.22; found: C, 39.68; H, 2.25.
analytically pure samples. NMR spectra were recorded with a
Bruker Avance III 600 MHz (1H NMR [600 MHz]; 13C NMR 1,2-Diphenyl-1,2-bis(selenophen-2-yl)ethene (9f, mixture of
[
151 MHz]) instrument. Chemical shifts are reported relative to E/Z isomers, ratio 2:1.2). Yield: 156 mg (71%); chromato-
solvent residual peaks (1H NMR: δ 7.26 ppm [CHCl3]; graphic purification (petroleum ether/CHCl3 8:2). Yellow crys-
3C NMR: δ 77.0 ppm [CDCl3]). IR spectra were registered tals; mp 221–223 °C; IR (KBr) ν: 3044 (w), 1483 (w), 1439
with a FTIR NEXUS spectrometer (as film or KBr pellets). (m), 1233 (m), 1201 (w), 1071 (w), 1021 (w), 770 (m), 706 (s),
1
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Beilstein J. Org. Chem. 2017, 13, 1900–1906.
6
85 (s) cm−1; 1H NMR (600 MHz, CDCl3) δ 6.53 (d, J = 3.6 (2 CH2), 58.7 (C(2)), 125.7, 127.4, 127.8 (5 CHarom), 144.6 (1
Hz, 2 Harom), 6.96 (dd, J = 6.0 Hz, 2.4 Hz, 2 Harom), 7.06 (d, J Carom) ppm; anal. calcd for C12H18S2Si (254.49): C, 56.63; H,
3.6 Hz, 2 Harom), 7.11–7.15 (m, 12 Harom), 7.45–7.50 (m, 10 7.13; S, 25.20; found: C, 56.64; H, 7.37; S, 25.31.
=
Harom), 7.80 (d, J = 6.0 Hz, 2 Harom), 8.03 (d, J = 5.4 Hz, 2
Harom) ppm; 13C NMR (150 MHz, CDCl3) δ 126.8, 127.6, Desilylation of 1,3-dithiolanes 13a,b. General procedure: The
1
1
28.3, 128.4, 129.1, 129.4, 130.8, 131.4, 132.2, 132.6, 133.0, corresponding 1,3-dithiolane (0.5 mmol) was dissolved in THF
33.1 (32 CHarom), 135.0, 136.5, 141.5, 142.9, 151.0, 151.7 (8 (2 mL) and the solution was cooled to 0 °C (ice bath). Then, a
Carom, 4 C=) ppm; anal. calcd for C22H16Se2 (438.28): C, solution of TBAF (0.5 mL, 1 M in THF, 0.5 mmol) was added
6
0.29; H, 3.68; found: C, 60.09; H, 3.67.
portion-wise. The progress of the desilylation was controlled by
TLC (petroleum ether/CH2Cl2 7:3). After removal of the sol-
Synthesis of dibenzofulvenes 9g–k: Thiofluorenone (1c, vent under vacuum, the residue was subjected to 1H NMR anal-
8 mg, 0.5 mmol) was dissolved in THF (1.5 mL) and the solu- ysis in CDCl3 solution. The crude products were purified by
9
tion was cooled to −78 °C (dry ice/acetone). Then, the mixture column chromatography (petroleum ether/CH2Cl2, increasing
was treated with small portions of an ethereal solution of TMS- polarity to CH2Cl2).
CHN2 (2 M, 0.25 mL, 0.5 mmol) until the intense colour of 1c
vanished. Next, the mixture was allowed to warm slowly to
Supporting Information
−
45 °C, whereby elimination of N2 was observed. Then, a solu-
tion of thiofluorenone (1c) or di(thiophen-2-yl) thioketone (1d,
.5 mmol) in 1.5 mL of THF was added. After ca. 10 min, the
Supporting Information File 1
0
Experimental data for compounds 9, 13, 15 and copies of
the original 1H and 13C NMR spectra.
cooling bath was replaced by an ice bath (0 °C) and a solution
of TBAF (1 M in THF, 1 mL, 1 mmol) was added to the mix-
ture. After removal of the solvent under vacuum, the residue
was subjected to 1H NMR analysis in CDCl3 solution. The
crude products were purified by column chromatography.
[http://www.beilstein-journals.org/bjoc/content/
supplementary/1860-5397-13-185-S1.pdf]
Acknowledgements
2
,2’-[(9H-Fluoren-9-ylidene)methylene]dithiophene (9i): Financial support by the National Science Centre (NCN,
Yield: 132 mg (77%); chromatographic purification (petroleum Poland) in the framework of the Maestro-3 grant (2012/06A/
ether/CHCl3 7:3). Orange crystals; mp 175–177 °C; IR (KBr) ST5/00219) is gratefully acknowledged.
ν: 3094 (w), 3066(w), 1556 (w), 1445 (m), 1416 (m), 1252 (w),
1
220 (w), 837 (w), 777 (m), 713 (s) cm−1; 1H NMR (600 MHz, References
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.14–7.18 (m, 4 Harom), 7.42–7.43 (m, 2 Harom), 7.59–7.61 (m,
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26.6, 127.4, 128.1, 128.5, 129.2 (14 CHarom), 137.7, 138.4,
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ν: 2952 (m), 2920 (m), 1591 (m), 1496 (m), 1480 (m), 1435
(
m), 1245 (vs), 1078 (m), 1036 (m), 922 (m), 840 (vs), 736 (s), 7. Shimizu, M.; Nagao, I.; Kiyomoto, S.-i.; Hiyama, T. Aust. J. Chem.
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98 (vs), 609 (m), 504 (s) cm–1; 1H NMR (600 MHz, CDCl3)
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7
2
.12–7.15 (m, 1Harom), 7.23–7.26 (m, 2Harom), 7.65–7.68 (m,
Harom) ppm; 13C NMR (150 MHz, CDCl3) δ 2.1 (3 CH3), 38.9
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Beilstein J. Org. Chem. 2017, 13, 1900–1906.
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