Synthesis of alkynyltellurides mediated by K3PO4 and DMSO

Article abstract of DOI:10.1039/c9nj01995b

In the present work, a simple method for the synthesis of alkynyltellurides is described by the reactions of terminal alkynes with diorganyl ditellurides in the presence of a catalytic amount of K₃PO₄. In both substrates, it was possible to vary the aryl and alkyl groups, obtaining the products of interest in short reaction times and in yields ranging from 30 to 93%. This methodology, different from those already reported in the literature, has the advantage of using a catalytic amount of a weak base and no use of metallic catalysts.

Full text of DOI:10.1039/c9nj01995b

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Jason B. Benedict et al.
The role of atropisomers on the photo-reactivity and fatigue of
diarylethene-based metal–organic frameworks
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Synthesis of alkynyltellurides mediated by K3PO4 and DMSO
Manoela do Sacramento,a Larissa Menezes,a Bruna Goldani,a Gelson Perin,a Marcio S. Silva,a
Thiago Barcellosb and Diego Alvesa*
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
In the present work, a simple method for the synthesis of alkynyltellurides is described by the reactions of terminal alkynes
with diorganyl ditellurides in the presence of catalytic amount of K3PO4. In both substrates, it was possible to vary the aryl
and alkyl groups, obtaining the products of interest in short reaction time and in yields ranging from 30 to 93%. This
methodology, differently from those already reported in literature, has the advantage of the use of catalytic amount of a
www.rsc.org/
weak
base
and
no
use
of
metallic
catalysis.
synthesis methodologies have been described in the
literature that do not use
Introduction
Several methodologies have been developed for the
synthesis of organic compounds containing the tellurium
atom, since they are present in construction of new
carbon-carbon bonds,1 in the synthesis of natural
products,2 and more recently their biological potential.3
Among these compounds, alkynyltellurides are of great
importance in organic synthesis, which can be used in [3 +
2] cycloaddition reactions.4 Thus, the synthesis of
alkynyltellurides have great significance and their biological
potential range from antioxidant5 to antidepressive-like6
and anxiolytic-like activities.7
metallic catalysis, but rather a strong base in catalytic
amounts.11
In view of the importance of the synthesis of organic
tellurium compounds and considering that the
methodologies described for the synthesis of
alkynyltellurides use transition metals as catalysts, the
present study describes a new synthetic methodology to
obtain this class of compounds from terminal alkynes 1 and
diorganoyl ditellurides 2, promoted by a weak base
(Scheme 1).
The preparation of alkynyltellurides generally requires
terminal alkynes or haloalkynes as precursors in the
presence of different tellurium reagents.1a-c The most
conventional methodologies for the synthesis of this class
of compounds involve the deprotonation of terminal
alkynes with strong base and subsequent capture of the
generated anion with electrophilic tellurium species or
even elemental tellurium.1a-c, 8
TeR1
K3PO4 (5 mol%)
R1TeTeR1
+
R
H
DMSO, 25 °C
open flask
R
1
2
3
R = R1 = aryl, alkyl
Scheme 1. General scheme of the reaction.
Alternatively, alkynyltellurides can be synthesized by
methodologies using transition metals as catalysts.9
Although the use of metal represents some limitations
about sustainability and green chemistry, copper salts are
the most studied until then, appearing in several
publications in the literature.10 Moreover, only a few
Recently, our research group published the synthesis of
selanylalkynes through the reaction between diorganoyl
diselenides and terminal alkynes in the presence of silver
nitrate as a catalyst, using dichloromethane as solvent
(Scheme 2, Eq. (1)).12 Therefore, the initial proposal for the
present work would be extend this methodology for the
synthesis of alkynyltellurides. Thus, phenylacetylene 1a (0.5
mmol), diphenyl ditelluride 2a (0.25 mmol) and AgNO3 (10
mol%) were added in CH2Cl2 (1.5 mL) and the reaction
mixture was stirred at 25 °C in open flask. Under these
reaction conditions, product 3a was not obtained, even
after 24 h (Scheme 2, Eq. (2)). Similarly, by changing the
silver catalyst to AgOTf, Ag2SO4 and Ag2CO3, no product 3a
a.
Laboratório de Síntese Orgânica Limpa - LASOL - CCQFA - Universidade Federal
de Pelotas - UFPel - P.O. Box 354 - 96010-900, Pelotas, RS, Brazil.
Laboratory of Biotechnology of Natural and Synthetic Products, University of
Caxias do Sul, Caxias do Sul, RS, Brazil.
† Corresponding author e-mail: diego.alves@ufpel.edu.br.
Electronic Supplementary Information (ESI) available: General experimental
procedures, characterization details, and 1H and 13C NMR spectra of compounds.
See DOI: 10.1039/x0xx00000x
b.
was
obtained.
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Eq. (1)
SeSe
Ph
Ph
TeTe
Ph Ph
Silver salt (10 mol%)
CH2Cl2, 25 °C, air
2a
Eq. (2)
Ph
Ph
AgNO3 (10 mol%)
CH2Cl2, 25 °C, air
Ph
H
Te
Ph
Se
Ph
3a
not obtained
95%
8
Silver salt = AgNO3, AgOTf, Ag2SO4, Ag2CO3
9
Scheme 2. Silver-catalysed direct chalcogenylation of terminal alkynes with diorganyl dichalcogenides
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Results and discussion
After an analysis of the literature, we found that most of
Table 1. Reaction conditions optimization using phenylacetylene
1a and diphenyl ditelluride 2a.a)
the transition metal-based synthesis of alkynyl tellurides
requires the use of a base, such as Cs2CO3, K2CO3, K3PO4,
CsOH, and DMSO as a solvent in the reaction media.9,10,13
Thus, a mixture of substrates 1a (0.5 mmol) and 2a (0.25
mmol) in DMSO (1.5 mL) was stirred at 25 °C in the presence
of 10 mol% of AgNO3 and K2CO3 (1 equiv), providing the
telluride 3a in 95% yield after 5 h (Table 1, entry 1). To our
delight, the yield of telluride 3a remains the same when the
reaction was performed without silver catalyst (Table 1,
entry 2).
H
Te
Te
Base
Te
+
Solvent, r.t.
1a
2a
3a
Yield
3a
(%)b)
95
95
-
Time
(h)
Entry
Base
Solvent
1c
2
3
4
5
6
7
8
9
K2CO3 (1 equiv)
K2CO3 (1 equiv)
-
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
CH2Cl2
EtOH
EtOAc
toluene
acetone
1,4-
5
5
24
5
After checking that it was not necessary the use silver
catalyst for the formation of telluride 3a, the reaction was
carried out in the absence of K2CO3 and after 24 h of
reaction, no product 3a was obtained (Table 1, entry 3).
Consequently, in view of these results, we decide to perform
an optimization reaction for this base promoted reaction.
Firstly, we evaluated the amount of base required and
reactions were carried out with catalytic amounts (20, 10, 5 and
3 mol%) of K2CO3 (Table 1, entries 4-7). In all of these performed
reactions, the desired product 3a was obtained in good yields
and it was observed that when 5 mol% of K2CO3 was used an
excellent yield of product 3a was obtained after 5 h of reaction
(Table 1, entry 6). Subsequently, some solvents were evaluated,
such as CH2Cl2, EtOH, EtOAc, toluene, acetone, 1,4-dioxane and
DMF (Table 1, entries 8-14). According our results, none of these
tested solvents proved efficient for this reaction. However, only
DMF proved adequate for the reaction, even if the yield was not
so good and the reaction time was longer compared with that
using DMSO (Table 1, entry 6 vs 14). The reaction was then
screened using different bases (Table 1, entries 15-20).
Analyzing the variety of tested inorganic and organic bases, we
observed that excellent results were obtained using 5 mol% of
K2CO3, Cs2CO3 and K3PO4 (Table 1, entries 6, 16 and 18).
Therefore, K3PO4 was chosen for further studies in view of its
lower price and/or readily available compared to the K2CO3 and
Cs2CO3. Interestingly, when the reaction is carried out under N2
atmosphere, only 55% of the product 3a is formed, evidencing
the necessity of an oxidizing medium in the reaction (Table 1,
entry 21).
K2CO3 (20 mol%)
K2CO3 (10 mol%)
K2CO3 (5 mol%)
K2CO3 (3 mol%)
K2CO3 (5 mol%)
K2CO3 (5 mol%)
K2CO3 (5 mol%)
K2CO3 (5 mol%)
K2CO3 (5 mol%)
94
5
5
5
24
24
24
24
24
93
93
79
-
10
-
10
11
12
-
-
13
K2CO3 (5 mol%)
24
-
dioxane
14
15
16
17
18
19
20
21d
K2CO3 (5 mol%)
Na2CO3 (5 mol%)
Cs2CO3 (5 mol%)
Et3N (5 mol%)
K3PO4 (5 mol%)
NaOAc (5 mol%)
NaOH (5 mol%)
K3PO4 (5 mol%)
DMF
24
24
3
24
3
24
3
3
90
88
94
45
93
33
89
55
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
a) Reactions were performed using phenylacetylene 1a (0.5 mmol)
and diphenyl ditelluride 2a (0.25 mmol), using 1.5 mL of solvent in
an open flask and were monitored by TLC until total disappearance
c
of starting materials. b Yields are given for isolated products. The
d
reaction was performed in the presence of AgNO3 (10 mol%).
Reaction was performed under N2 atmosphere.
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Table 2. Variability in the synthesis of alkynyltellurides 3a-s.a)
TeR1
3a r
6
7
8
9
K3PO4 (5 mol%)
R1TeTeR1
R
H
+
DMSO, 25 °C
open flask
2a e
-
R
1a n
-
-
R = R1 = aryl, alkyl
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Product 3
(Yield) b)
Te
Entry
1
Terminal Alkyne 1
Ditelluride 2
Time (h)
Te
Te
3
6
H
1a
3a (93%)
2a
Te
Te
Te
2
3
4
H
1a
2b
3b (93%)
O
Te
Te
Te
8
4
O
H
O
1a
3c (86%)
2c
Cl
Te
Te
Te
Cl
H
Cl
1a
3d (89%)
2d
Te
S
Te
Te
S
S
5
22
24
H
2e
1a
3e (62%)
Te
Te
Te
6c
2f
H
1a
3f (40%)
Te
H
Te
Te
7
22
O
O
2a
3g (89%)
1b
Te
H
Te
Te
8
9
21
8
3h (81%)
Te
2a
1c
Te
Te
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H
2a
3i (90%)
DOI: 10.1039/C9NJ01995B
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8
1d
1e
H
Te
Te
Te
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3j (86%)
2a
H
Te
Te
Te
6
2a
1f
3k (73%)
3l (86%)
Te
Cl
Te
Te
12
6
Cl
H
2a
1g
1h
Te
Te
Te
13
14
8
H
3m (89%)
2a
Te
Te
Te
24
H
3n (63%)
3o (71%)
2a
1i
1j
Te
Te
Te
15
16
17
18
24
H
2a
Te
Te
24
Te
H
1k
3p (30%)
2a
O
O
Te
Te
O
O
10
H
Te
1l
3q (80%)
2a
HO
Te
HO
Te
H
7
Te
1m
3r (64%)
2a
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HO
HO
Te
Te
19
10
H
Te
1n
3s (54%)
2a
8
9
a) Reactions are performed using alkynes 1 (0.5 mmol), diorganoyl ditelluride 2 (0.25 mmol), K3PO4 (5 mol%) in DMSO (1.5 mL) at
25 °C in an open flask for the time indicated above. Yields are given for isolated products. The reaction was performed under N2
atmosphere.
b)
c)
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The substrate scope of this reaction was then investigated obtained in all cases. When we used 2-ethynylnaphthalene 1h
under the optimized reaction conditions (Table 2). Initially, we as a substrate, the desired product 3m was obtained in 89%
evaluated the reactivity of phenylacetylene 1a in reactions with yield after 8 h (Table 2, entry 13). We extended the scope of
different functionalized diorganyl ditellurides 2a-f (Table 2, reaction checking the reactivity of non-arylic alkynes, such as 1-
entries 1-6). Substituted diaryl ditellurides 2b-d were efficiently ethynylcyclohexene 1i, 1-heptyne 1j and 3,3-dimethylbut-1-yne
reacted with phenylacetylene 1a and the reactions are not 1k. After 24 h of reaction, we obtained the desired products 3n-
sensitive to the electronic effect of the aromatic ring in the p in 63, 71 and 30%, respectively (Table 2, entries 14-16). A
aryltellanyl moiety. Reactions with diaryl ditellurides 2b and 2c good result was also achieved when ethyl propiolate 1l was
containing electron-donating groups (EDG) at the aromatic ring used as a starting material (Table 2, entry 17).
gave almost the same yield than reaction with diaryl ditelluride
Interesting results were obtained using propargylic alcohol
2d containing electron-withdrawing group (EWG) (Table 2, 1m and mebynol 1n, and the desired alkynyltellurides 3r-s were
entries 2-3 vs 4). 1,2-Di(thiophen-2-yl) ditelluride 2e reacted obtained in moderated yields (64 and 54% yield, respectively)
efficiently with phenylacetylene 1a giving the product 3e in 62% (Table 2, entries 18-19).
yield (Table 2, entry 5). In addition, dibutyl ditelluride 2f was
Because of the mild reaction conditions, the use of a weak
reacted with phenylacetylene 1a yielding the desired product in and cheap base/catalyst, and a great substrate scope, our
40% after 24 h (Table 2, entry 6). It is important to note that this methodology represents an advance with respect to the
reaction was performed under N2 atmosphere to prevent methodology using CsOH as a catalyst.11b
decomposition of the product.14
In addition, under the optimized reaction conditions, the
Under the same optimized reaction conditions, we next possibility of performing the reaction with other diphenyl
evaluated the reactivity of diphenyl ditelluride 2a using different dichalcogenides, such as diphenyl diselenide and diphenyl
functionalized terminal alkynes 1b-n (Table 2, entries 7-19). disulfide was also investigated (Scheme 3). However, when the
When the reaction of diphenyl ditelluride 2a was carried out phenylacetylene 1a (0.5 mmol) reacted with diphenyl diselenide
with a range of terminal aryl alkynes 1b-g bearing both electron- (0.25 mmol), the expected product 4 was not obtained and only
donating groups (EDG) and electron-withdrawing groups (EWG), the product 4’ was obtained in 23% yield as a mixture of (E)- and
the desired alkynyltellurides 3g-l were obtained in moderate to (Z)-isomers (E/Z ratio = 8:92). Unfortunately, the reaction
good yields (Table 2, entries 7-12). Interestingly, EDG and EWG performed with diphenyl disulfide (0.25 mmol) did not provide
present in the aryl group of the terminal alkynes did not the formation of desired alkynylsulfide 5 and the starting
influence the reactivity, with good yields of products being materials
were
recovered.
Ph
Ph
Se
Ph
SeSe
Ph
Ph
+
Se
Ph
Se
Ph
4
(traces)
E/Z : 8/92
Ph
K3PO4 (5 mol%)
4'
23%
DMSO, 25 °C, 24 h
open flask
H
1a
Ph
SS
Ph Ph
S
Ph
5
Scheme 3. Reactions with other dichalcogenides.
Since that, our mechanistic studies of this base-mediated
synthesis alkynyltellurides in DMSO are not complete, we
suggest in Figure 1 a plausible mechanism for the product 3
formation from terminal alkynes 1 and diorganyl ditellurides 2.
R1Te
B
R
TeR1
R
+
R1TeTeR1
A
1
3
Product
2
H-Base
Base
H
[O]
HTeR1
C
R
DMSO
air
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Figure 1. A plausible mechanism of the reaction.
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reference. Coupling constants (J) are reporteVdiew iAnrticleHOenrltinze.
DOI: 10.1039/C9NJ01995B
Abbreviations to denote the multiplicity of a particular signal are
Reversible deprotonation of the terminal alkyne 1 generates
an acetylide A,15 which acts as a nucleophile to attack the
tellurium atom of the diorganyl ditelluride 2, furnishing the
desired product 3 and tellurolate B. Tellurolate B reacts with
protonated base (H-Base) generating tellurol C and the base.
s (singlet), d (doublet), t (triplet), q (quartet), quin (quintet), sex
(sextet) and
m (multiplet). Carbon-13 nuclear magnetic
resonance spectra (13C NMR) were obtained at 100 MHz on
Bruker Avance HD III spectrometer. Chemical shifts are reported
in ppm, referenced to the solvent peak of CDCl3. Low-resolution
mass spectra were obtained with a Shimadzu GCMS-QP 2010
Plus mass spectrometer. High-resolution mass spectra (HRMS)
were recorded on a Bruker Micro TOF-QII spectrometer 10416.
9
Finally, tellurol
C can be easily oxidized under the air
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atmosphere and DMSO,16 regenerating diorganyl ditelluride 2 in
the catalytic cycle, that is supported by the influence of an inert
atmosphere. The proposed mechanism indicates that this
process is able to use both groups on diorganyl ditelluride.
In order to verify if the mechanism really proceeds through
an anionic pathway, we employed our optimized reaction
conditions to prepare alkynyltelluride 3a in the presence of 1
equiv of 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO) as a
radical inhibitor (Scheme 4). Thus, reaction performed with
TEMPO provided the alkynyltelluride 3a in the same yield as
that obtained for the reaction in the absence of the radical
inhibitor. This result corroborates with the anionic pathway
suggested as a plausible mechanism of the reaction.
General procedure for the synthesis of alkynyltellurides 3a-r:
To a 5 mL Schlenk tube equipped with a small magnetic stirring
bar containing a solution of an appropriated terminal alkyne
(1a-n, 0.5 mmol) in DMSO (1.5 mL), K3PO4 (5 mol%) and the
corresponding diorganyl ditelluride (2a-e, 0.25 mmol) were
added. The mixture was stirred at 25 °C for the time indicated in
Table 2. The mixture was then extracted using ethyl acetate (10
mL) and washed with water (3 × 10 mL). The organic layer was
dried over anhydrous MgSO4 and concentrated under vacuum to
yield the crude product, which was purified by flash
chromatography on silica gel using a hexane or a mixture of
hexane/ethyl acetate as the eluent. Spectral data for the
products prepared are listed below.
Phenyl(phenylethynyl)tellane (3a): Yield: 0.143 g (93%); yellow
oil. 1H NMR (CDCl3, 400 MHz) δ (ppm) = 7.73-7.68 (m, 2H); 7.45-
7.43 (m, 2H); 7.31-7.21 (m, 6H). 13C NMR (CDCl3, 100 MHz) δ
(ppm) = 135.0 (2C), 131.8 (2C), 129.6 (2C), 128.5, 128.2 (2C),
127.8, 123.2, 114.1, 113.1, 47.6. MS (relative intensity) m/z: 308
(M+, 6), 178 (100), 101 (14), 77 (15), 44 (18). HRMS calculated
for C14H10Te [M + H]+: 308.9923. Found: 308.9915.
H
Te
K3PO4 (5 mol%)
Te
TEMPO
(1 equiv)
Te
+
DMSO, 25 °C, 3 h
open flask
3a
93%
1a
2a
Scheme 4. Reaction with a radical inhibitor.
Conclusions
In summary, a simple, efficient and transition metal-free
methodology for the synthesis of alkynyltellurides was
described. The reactions proceed under mild conditions,
reacting a range of terminal alkynes with different diorganyl
ditellurides using K3PO4 as a catalyst, DMSO as a solvent under
air atmosphere at 25 °C. The proposed base-mediated
methodology was performed with terminal alkynes and
ditellurides bearing electron-withdrawing and electron-donating
groups affording the corresponding alkynyltellurides in
moderated to excellent yields. Due to the mild reaction
conditions and to the use of a weak and cheap base/catalyst,
this new methodology represents an advance with respect to
reported methodologies to access alkynyltellurides.
(Phenylethynyl)(p-tolyl)tellane (3b): Yield: 0.150
g (93%);
yellow solid; mp 61 - 64 °C. 1H NMR (CDCl3, 400 MHz) δ (ppm) =
7.63 (d, J = 8.2 Hz, 2H); 7.44-7.42 (m, 2H); 7.32-7.26 (m, 3H);
7.08-7.06 (m, 2H); 2.33 (s, 3H). 13C NMR (CDCl3, 100 MHz) δ
(ppm) = 138.1, 135.7 (2C), 131.8 (2C), 130.6 (2C), 128.4, 128.2
(2C), 123.4, 113.6, 108.6, 47.6, 21.1. MS (relative intensity) m/z:
322 (M+, 13), 192 (100), 189 (12), 101 (13), 65 (10). HRMS
calculated for C15H12Te [M]+: 322.0001. Found: 322.0016.
(4-Methoxyphenyl)(phenylethynyl)tellane (3c): Yield: 0.146 g
(86%); yellow solid; mp 67 - 68 °C. H NMR (CDCl3, 400 MHz) δ
1
(ppm) = 7.70 (d, J = 8.8 Hz, 2H); 7.43-7.40 (m, 2H); 7.30-7.26 (m,
3H); 6.82 (d, J = 8.8 Hz, 2H); 3.77 (s, 3H). 13C NMR (CDCl3, 100
MHz) δ (ppm) = 160.0, 138.2 (2C), 131.8 (2C), 128.4, 128.1 (2C),
123.4, 115.6 (2C), 113.0, 101.3, 55.1, 47.9. MS (relative
intensity) m/z: 338 (M+, 9), 208 (100), 193 (37), 165 (24), 101
(10), 75 (6). HRMS calculated for C15H13OTe [M + H]+: 339.0029.
Found: 339.0011.
Experimental
General Information: The reactions were monitored by TLC
carried out on Merck silica gel (60 F254) by using UV light as
visualizing agent and 5% vanillin in 10% H2SO4 and heat as
developing agents. Baker silica gel (particle size 0.040–
0.063mm) was used for flash chromatography. Hydrogen
nuclear magnetic resonance spectra (1H NMR) were obtained at
400 MHz on Bruker Avance III HD spectrometer. Spectra were
recorded in CDCl3 solutions. Chemical shifts are reported in
ppm, referenced to tetramethylsilane (TMS) as the external
(4-Chlorophenyl)(phenylethynyl)tellane (3d): Yield: 0.152 g
(89%); white solid; mp 108 - 110 °C. 1H NMR (CDCl3, 400 MHz) δ
(ppm) = 7.63 (d, J = 8.1 Hz, 2H); 7.46-7.21 (m, 7H). 13C NMR
(CDCl3, 100 MHz) δ (ppm) = 136.3 (2C), 134.4, 131.9 (2C), 129.9
(2C), 128.7, 128.2 (2C), 123.1, 114.6, 110.7, 47.1. MS (relative
intensity) m/z: 342 (M+, 12), 212 (100), 176 (20), 151 (6), 101
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(22), 75 (19). HRMS calculated for C14H9ClTe [M]+: 341.9533. 191 (100), 114 (11), 77 (11), 51 (10). HRMS cVaielcwuAlratitceledOnflioner
+
DOI: 10.1039/C9NJ01995B
Found: 341.9461.
C16H15Te [M + H] : 337.0236, Found: 337.0229.
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2-((Phenylethynyl)tellanyl)thiophene (3e): Yield: 0.089 g (62%); [(4-tert-Butyl)phenyl)ethynyl](phenyl)tellane (3k): Yield: 0.133
yellow solid; mp 54 - 56 °C. 1H NMR (CDCl3, 400 MHz) δ (ppm) = g (73%); yellow solid; mp 67 - 69 °C. 1H NMR (CDCl3, 400 MHz) δ
7.52 – 7.50 (m, 2H), 7.41 –7.38 (m, 2H), 7.28 – 7.26 (m, 3H), 7.0 (ppm) = 7.72-7.69 (m, 2H); 7.42-7.39 (m, 2H); 7.35-7.32 (m, 2H);
– 6.98 (m, 1H). 13C NMR (CDCl3, 100 MHz) δ (ppm) = 140.9, 7.26-7.22 (m, 3H); 1.29 (s, 9H). 13C NMR (CDCl3, 100 MHz) δ
134.8, 131.9 (2C), 128.9, 128.6, 128.1 (2C), 123.1, 111.9, 98.2, (ppm) = 151.9, 134.8 (2C), 131.7 (2C), 129.7 (2C), 127.7, 125.2
47.9. MS (relative intensity) m/z: 314 (M+, 9), 185 (14), 184 (2C), 120.3, 114.4, 113.3, 46.3, 34.7, 31.1 (3C). MS (relative
(100), 152 (11), 139 (13), 101 (16). HRMS calculated for C12H9STe intensity) m/z: 364 (M+, 14), 291 (13), 234 (34), 219 (100), 141
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[M + H]+: 314.9487. Found: 314.9490.
(9), 77 (9). HRMS calculated for C18H18Te [M]+: 364.0471, Found:
364.0464.
Butyl(phenylethynyl)tellane (3f): Yield: 0.058 g (40%); orange
oil. 1H NMR (CDCl3, 400 MHz) δ (ppm) = 7.42-7.39 (m, 2H); 7.31- [(4-Chlorophenyl)ethynyl](phenyl)tellane (3l): Yield: 0.147 g
1
7.26 (m, 3H); 2.88 (t, J = 7.4 Hz, 2H); 1.91 (quint. J = 7.4 Hz, 2H); (86%); yellow solid. mp 94 – 96 °C. H NMR (CDCl3, 400 MHz) δ
1.45 (sex. J = 7.4 Hz, 2H); 0.95 (t, J = 7.4 Hz, 3H). 13C NMR (CDCl3, (ppm) = 7.73 (d, J = 7.0 Hz, 2H), 7.44 – 7.11 (m, 7H). 13C NMR
100 MHz) δ (ppm) = 131.6 (2C), 128.1 (3C), 123.7, 111.3, 44.5, (CDCl3, 100 MHz) δ (ppm) = 135.3 (2C), 134.6, 133.0 (2C), 129.8
33.6, 24.6, 13.3, 9.9. MS (relative intensity) m/z: 288 (M+, 22), (2C), 128.5 (2C), 128.0, 121.8, 112.9, 112.8, 49.0. MS (relative
286 (21), 232 (20), 143 (9), 129 (11), 102 (100), 75 (19), 57 (26), intensity) m/z: 342 (M+, 11), 212 (100), 176 (21), 100 (8), 77 (12),
41 (31). HRMS calculated for C12H14Te [M]+: 288.0158. Found: 51 (17). HRMS calculated for C14H9ClTe [M]+: 341.9455. Found:
288.0175.
341.9450.
[(2-Methoxyphenyl)ethynyl](phenyl)tellane (3g): Yield: 0.150 g (Naphthalen-2-ylethynyl)(phenyl)tellane (3m): Yield: 0.159 g
1
(89%); yellow oil. 1H NMR (CDCl3, 400 MHz) δ (ppm) = 7.76-7.71 (89%); yellow solid; mp 60 - 62 °C. H NMR (CDCl3, 400 MHz) δ
(m, 2H); 7.42-7.39 (m, 1H); 7.25-7.21 (m, 4H); 6.88 (td, J = 7.5 (ppm) = 7.95 (s, 1H); 7.77-7.73 (m, 5H); 7.50-7.41 (m, 3H); 7.27-
Hz, 1H); 6.86-6.81 (m, 1H); 3.84 (s, 3H). 13C NMR (CDCl3, 100 7.23 (m, 3H). 13C NMR (CDCl3, 100 MHz) δ (ppm) = 135.1 (2C),
MHz) δ (ppm) = 160.2, 134.5 (2C), 133.5, 129.9, 129.5 (2C), 132.8, 132.7, 131.8, 129.7 (2C), 128.4, 127.8, 127.6, 126.8,
127.5, 120.2, 113.6, 112.4, 110.6, 110.4, 55.6, 51.2. MS (relative 126.5, 120.5, 114.6, 113.1, 48.0. MS (relative intensity) m/z: 358
intensity) m/z: 338 (M+, 19), 208 (100), 178 (11), 165 (27), 131 (M+, 6), 228 (100), 151 (22), 77 (21), 51 (15). HRMS calculated
(51), 88 (15), 77 (37), 44 (22). HRMS calculated for C15H13OTe for C18H13Te [M + H]+: 359.0079, Found: 359.0065.
[M+H]+: 339.0029. Found: 339.0018.
(Cyclohex-1-en-1-ylethynyl)(phenyl)tellane (3n): Yield: 0.098 g
Phenyl(m-tolylethynyl)tellane (3h): Yield: 0.130 g (81%); yellow (63%); yellow oil. 1H NMR (CDCl3, 400 MHz) δ (ppm) = 7.75-7.68
oil. 1H NMR (CDCl3, 400 MHz) δ (ppm) = 7.82-7.79 (m, 2H); 7.37- (m, 2H); 7.30-7.27 (m, 3H); 6.20 (m, 1H); 2.23-2.18 (m, 4H); 1.72-
7.32 (m, 5H); 7.30-7.26 (m, 1H); 7.20-7.17 (m, 1H); 2.38 (s, 3H). 1.59 (m, 4H). 13C NMR (CDCl3, 100 MHz) δ (ppm) = 136.3, 134.6
13C NMR (CDCl3, 100 MHz) δ (ppm) = 137.9, 135.0 (2C), 132.4, (2C), 129.6 (2C), 127.6, 121.1, 116.5, 113.5, 43.4, 29.2, 25.5,
129.7 (2C), 129.5, 128.9, 128.1, 127.8, 123.1, 114.4, 113.2, 46.9, 22.2, 21.3. MS (relative intensity) m/z: 312 (M+, 35), 308 (19),
21.2. MS (relative intensity) m/z: 322 (M+, 12), 192 (100), 165 165 (86), 153 (49), 103 (21), 77 (100), 51 (51). HRMS calculated
(8), 115 (20), 77 (10), 51 (11). HRMS calculated for C15H13Te for C14H14Te [M]+: 312.0158. Found: 312.0154.
[M+H]+: 323.0079. Found: 323.0065.
Hept-1-yn-1-yl(phenyl)tellane (3o): Yield: 0.107 g (71%); orange
Phenyl(p-tolylethynyl)tellane (3i): Yield: 0.145 g (90%); yellow oil. 1H NMR (CDCl3, 400 MHz) δ (ppm) = 7.69-7.64 (m, 2H); 7.25-
1
solid; mp 60 - 62 °C. H NMR (CDCl3, 400 MHz) δ (ppm) = 7.72- 7.22 (m, 3H); 2.56 (t, J = 7.1 Hz, 2H); 1.57 (quint. J = 6.9 Hz, 2H);
7.69 (m, 2H); 7.35 (d, J = 7.9 Hz, 2H); 7.24-7.22 (m, 3H); 7.10 (d, J 1.43-1.28 (m, 4H); 0.90 (t, J = 7.1 Hz, 3H). 13C NMR (CDCl3, 100
= 7.9 Hz, 2H); 2.33 (s, 3H). 13C NMR (CDCl3, 100 MHz) δ (ppm) = MHz) δ (ppm) = 134.6 (2C), 129.5 (2C), 127.5, 116.1, 113.2, 34.7,
138.8, 134.9 (2C), 131.8 (2C), 129.6 (2C), 128.9 (2C), 127.7, 31.0, 28.6, 22.1, 21.0, 13.9. MS (relative intensity) m/z: 302 (M+,
120.3, 114.3, 113.3, 46.3, 21.4. MS (relative intensity) m/z: 322 23), 143 (42), 129 (23), 115 (100), 95 (30), 77 (41), 55 (19), 41
(M+, 11), 207 (178), 192 (100), 115 (26), 77(13), 44 (22). HRMS (17). HRMS calculated for C13H16Te [M]+: 302.0314, Found:
calculated for C15H13Te [M + H]+: 323.0079. Found: 323.0079.
302.0314.
[(4-Ethylphenyl)ethynyl](phenyl)tellane (3j): Yield: 0.144 g (3,3-Dimethylbut-1-yn-1-yl)(phenyl)tellane (3p): Yield: 0.043 g
1
(86%); yellow solid; mp 46 - 48 °C. H NMR (CDCl3, 400 MHz) δ (30%); yellow oil. 1H NMR (CDCl3, 400 MHz) δ (ppm) = 7.70-7.64
(ppm) = 7.72-7.69 (m, 2H); 7.40-7.37 (m, 2H); 7.25-7.21 (m, 3H); (m, 2H); 7.31-7.23 (m, 3H); 1.34 (s, 9H). 13C NMR (CDCl3, 100
7.14-7.11 (m, 2H); 2.62 (q, J = 7.6 Hz, 2H); 1.20 (t, J = 7.6 Hz, 3H). MHz) δ (ppm) = 134.0 (2C), 129.5 (2C), 127.4, 124.4, 113.5, 33.5,
13C NMR (CDCl3, 100 MHz) δ (ppm) = 145.1, 134.8 (2C), 131.9 31.1 (3C), 29.7. MS (relative intensity) m/z: 288 (M+, 19), 207
(2C), 129.6 (2C), 127.7 (2C), 127.7, 120.5, 114.4, 113.3, 46.3, (13), 143 (100), 128 (30), 77 (28), 53 (11), 41 (19). HRMS
28.7, 15.3. MS (relative intensity) m/z: 336 (M+, 16), 206 (90), calculated for C12H14Te [M]+: 288.0158. Found: 288.0173.
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Braga, H. A. Stefani, C. W. Nogueira, Tetrahedron Lett. 2004, 45,
Ethyl 3-(phenyltellanyl)propiolate (3q): Yield: 0.122 g (80%);
orange oil. H NMR (CDCl3, 400 MHz) δ (ppm) = 7.77-7.74 (m,
View Article Online
4823.
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DOI: 10.1039/C9NJ01995B
2H); 7.38-7.28 (m, 3H); 4.25 (q, J = 7.1 Hz, 2H); 1.32 (t, J = 7.2 Hz,
3H). 13C NMR (CDCl3, 100 MHz) δ (ppm) = 152.0, 136.3 (2C),
129.9 (2C), 128.7, 110.8, 107.2, 61.8, 55.4, 13.9. MS (relative
intensity) m/z: 304 (M+, 21), 232 (12) 129 (91), 102 (100), 77
(62), 51 (74), 44 (8). HRMS calculated for C11H11O2Te [M + H]+:
304.9821. Found: 304.9811.
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Nogueira, G. Zeni, Tetrahedron Lett. 2005, 46, 8761. (c) J. P.
Marino, M. S. McClure, D. P. Holub, J. V. Comasseto, F. C. Tucci,
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3-(Phenyltellanyl)prop-2-yn-1-ol (3r): Yield: 0.084 g (64%);
1
yellow oil. H NMR (CDCl3, 400 MHz) δ (ppm) = 7.71-7.67 (m,
2H); 7.29-7.21 (m, 3H); 4.48 (s, 2H); 2.74 (s, 1H). 13C NMR (CDCl3,
100 MHz) δ (ppm) = 135.4 (2C), 129.6 (2C), 128.0, 113.2, 112.3,
52.0, 44.5. MS (relative intensity) m/z: 262 (M+, 11), 115 (72), 77
(86), 55 (23), 44 (100). HRMS calculated for C9H8OTe [M]+:
261.9637. Found: 261.9633.
2-Methyl-4-(phenyltellanyl)but-3-yn-2-ol (3s): Yield: 0.078 g
(54%); yellow oil. 1H NMR (CDCl3, 400 MHz) δ (ppm) = 7.67-7.64
(m, 2H); 7.28-7.22 (m, 3H); 2.34 (s, 1H); 1.57 (s, 6H). 13C NMR
(CDCl3, 100 MHz) δ (ppm) = 134.8 (2C), 129.7 (2C), 127.8, 119.7,
112.7, 66.3, 40.0, 31.4. MS (relative intensity) m/z: 290 (10), 272
(11), 141 (100), 102 (26). HRMS calcd. for C11H12OTe [M]+:
289.9945. Found: 289.9945.
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Souza, L. S. Madureira, J. Zukerman-Schpector, M. N. Eberlin, M.
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Conflicts of interest
There are no conflicts to declare.
Acknowledgements
We are grateful for the financial support and scholarships
from the Brazilian agencies CNPq and FAPERGS (PRONEM
16/2551-0000240-1). CNPq is also acknowledged for the
fellowship for G.P. and D.A. This study was financed in party by
the Coordenação de Aperfeiçoamento de Pessoal de Nivel
Superior - Brasil (CAPES) - Finance Code 001.
Notes and references
[1] (a) N. Petragnani, H. A. Stefani, in: Tellurium in Organic
Synthesis: Second, Updated and Enlarged Edition, London, 2007.
(b) E. E. Alberto, A. L. Braga, In Selenium and Tellurium
Chemistry
- From Small Molecules to Biomolecules and
Materials; Derek, W. J.; Risto, L., Eds.; Springer: Berlin
Heidelberg, 2011. (c) N. Petragnani, H. A. Stefani, Tetrahedron
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Res. 2003, 36, 731. (e) G. Zeni, D. S. Ludtke, R. B. Panatieri, A. L.
Braga, Chem. Rev. 2006, 106, 1032. (f) H. A. Stefani, J. M. Pena,
F. Manarin, R. A. Ando, D. M. Leal, N. Petragnani, Tetrahedron
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Gariani, J. V. Comasseto, A. A. dos Santos, Tetrahedron Lett.,
2007, 48, 1485. (h) S. Zhang, L. Kolluru, S. K. Vedula, D. Whippie,
J. Jin, Tetrahedron Lett. 2017, 58, 3594. (i) G. Zeni, D. Alves, A. L.
[14] C. Liu, T. Hyugano, A. Ouchi, Org. Lett. 2009, 11, 4870.
[15] S. W. Kwok, J. R. Fotsing, R. J. Fraser, V. O. Rodionov, V. V.
Fokin, Org. Lett. 2010, 12, 4217.
[16] M. Schmidt, W. Siebert, The Chemistry of Sulphur, Selenium,
Tellurium
and
Polonium.
Pergamon
Press,
1973
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Table of contents
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Metal-free
TeR1
K3PO
4 (5 mol%)
R1TeTeR1
R = R1 = aryl, alkyl
+
H
R
DMSO
, 25 °C
open flask
R
9
30-93%
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The reaction of diorganyl ditellurides with terminal alkynes is described using K3PO4 as a
catalyst.