An alternative approach for the synthesis of aryl-alkyl tellurides: Reaction of aryl iodides with metal alkyltellurolates promoted by CuI

Article abstract of DOI:10.1016/j.tet.2011.09.014

Aryl iodides react with metal organotellurolates in tetrahydrofuran/ dimethylformamide in the presence of CuI (5 mol %) or CuI (5 mol %) and 1,10-phenanthroline (10 mol %) to afford the corresponding aryl-alkyl tellurides in good yields.

Full text of DOI:10.1016/j.tet.2011.09.014

Tetrahedron 67 (2011) 8763e8768
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journal homepage: www.elsevier.com/locate/tet
An alternative approach for the synthesis of arylealkyl tellurides: reaction of aryl
iodides with metal alkyltellurolates promoted by CuI
*
ꢀ
~
Marcio S. Silva , Joao V. Comasseto
~
~
Instituto de Química, Universidade de Sao Paulo, Av. Prof. Lineu Prestes, 748, Caixa Postal 26077, 05508-000 Sao Paulo, SP, Brazil
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 24 July 2011
Received in revised form 1 September 2011
Accepted 6 September 2011
Available online 10 September 2011
Aryl iodides react with metal organotellurolates in tetrahydrofuran/dimethylformamide in the presence
of CuI (5 mol %) or CuI (5 mol %) and 1,10-phenanthroline (10 mol %) to afford the corresponding
arylealkyl tellurides in good yields.
Ó 2011 Elsevier Ltd. All rights reserved.
Keywords:
Organotellurolate
Coupling reaction
Arylealkyl telluride
Copper iodide
Aryl iodide
1. Introduction
transformations to yield organotellurides are scarce.8 Indeed, to the
best of our knowledge, CuI-promoted reactions of metal organo-
The organic chemistry of tellurium is currently well developed,
and several classes of organotellurides have found application as
synthetic reagents,1,2 particularly in the preparation of biologically
active compounds.3 Systematic investigations of the biological ac-
tivities of organic derivatives of tellurium in different oxidation
states have revealed interesting results.4 For example, organo-
tellurium (IV) compounds are potent inhibitors of cysteine pro-
teases,5 while organotellurium (II) compounds have been shown to
be glutathione peroxidase mimetics.4b Moreover, a recent publi-
cation has claimed, with full justification, that the organic chem-
istry of tellurium must be considered an emerging area with great
potential in the search for new and more potent drugs.6 In the light
of these comments, practical methods for the synthesis of orga-
notellurium compounds are apposite, particularly those that avoid
the manipulation of low molecular weight dialkylditellurides in the
preparation of nucleophilic species of tellurium.
tellurolates with aryl halides have yet to be described.9 The aim of
the present study was, therefore, to explore the reactions of aryl
iodides with metal organotellurolates in order to establish a novel
and general route to arylealkyl tellurides.
Classical methods for the preparation of arylealkyl tellurides1
involve the production of aryltellurolate anions through the in-
sertion of elemental tellurium into an aryl organometallic, or by
reduction of a diarylditelluride and reaction of the metal aryltel-
lurolate with an alkylating agent (Scheme 1, route 1).1c Both of
these methods are incompatible with aryl rings bearing functional
groups that are sensitive to reducing agents or to organometallics.
In the present study, an inverse approach is adopted in which the
alkyl moiety forms part of the metal organotellurolate generated
under non-reducing conditions that are inert to a number of
functional groups (Scheme 1, route 2).
In recent years, the use of CuI in catalytic amounts to promote
the coupling of aryl halides with substrates bearing different types
of functional groups has been explored7 and applied in the syn-
thesis of structurally complex molecules.7b However, while CuI-
promoted reactions that generate organosulfides and organo-
selenides are known, details concerning the analogous
Scheme 1. General approaches to the synthesis of arylealkyl tellurides.
In this paper, we describe the preparation of arylealkyl tellu-
rides in good yields by reaction of aryl iodides with lithium alkyl-
tellurolates in dimethylformamide (DMF) and tetrahydrofuran
* Corresponding author. Tel.: þ55 11 3091 2176; fax: þ55 11 3815 5579; e-mail
addresses: marciosasi@usp.br (M.S. Silva), jvcomass@iq.usp.br (J.V. Comasseto).
0040-4020/$ e see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2011.09.014

8764
M.S. Silva, J.V. Comasseto / Tetrahedron 67 (2011) 8763e8768
Table 2
(THF) in the presence of 10 mol % 1,10-phenanthroline and/or
5 mol % CuI (Scheme 2).
Influence of aryl halide 1 and alkyl tellurium 2 on the course of the reaction
TenBu
X
CuI (5 mol%) / DMF
THF / 80 ºC
nBuTeY
+
1
2
3a
Entry
1
AreX
(1)
nBuTeY
(2)
Timea (h)
Yield of 3ab
(%)
I
nBuTeMgBr
2b
6
82
1a
1b
1c
Scheme 2. Synthesis of arylealkyl tellurides by reaction of aryl iodides and lithium
alkyltellurolates in the presence of CuI or CuI and 1,10-phenanthroline.
Br
nBuTeLi
2a
2
3
24
24
24
n.r.
n.r.
29
2. Results and discussion
Cl
I
nBuTeLi
2a
Lithium organotellurolate 2 was prepared by the addition of the
appropriate alkyl lithium to a suspension of elemental tellurium in
THF at room temperature. The lithium organotellurolate (obtained
as a clear yellow solution) was transferred via a cannula to a solu-
tion of the appropriate aryl iodide 1 and CuI (5 mol %) at room
temperature. The yields of products 3 obtained after heating the
reaction mixture at 80 ꢀC (oil bath temperature) for the indicated
times are presented in Tables 1e4. Yields were calculated on the
basis of the quantity of product obtained after purification by col-
umn chromatography (CC) over silica gel, taking into account the
amount of aryl iodide consumed during the reaction.
(nBuTe)2
2c
4
1a
a
Reaction was monitored by TLC and GC.
Isolated yield, after CC over silica gel, based upon phenyl iodide (1a) consumed.
b
Table 3
Influence of the lithium organotellurolate 2 on the course of the reaction
Table 1
I
TeR
Optimization of the reaction conditions
CuI (5 mol%) / DMF
THF / 80 ºC
+
RTeLi
TenBu
I
[Cu] (5 mol%) / Co-solvent
nBuTeLi
+
1a
2
3
THF / 80 ºC
Entry
1
RTeLi
Product
Time (h)
Yield of 3a
(%)
1a
2a
3a
(2)
(3)
MeTeLi
8
80
Entry
[Cu]
Co-solvent
Timea (h)
Yield of 3ab
TeMe
2d
(%)
1
2
3
4
5
6
7
8
d
d
24
24
6
24
24
6
6
6
12
6
6
25
48
40
59
68
85
56
75
52
94
82
38
3b
CuI
CuI
d
d
2
3
4
5
sBuTeLi
2e
6
6
84
75
d
TesBu
DMSO
DMF
DMSO
Dioxane
CH3CN
Toluene
DMF
DMF
DMF
d
CuI
CuI
CuI
CuI
CuI
CuBr
CuCl
3c
tBuTeLi
2f
TetBu
9
10
11
12
3d
PhTeLi
2g
12
12
51b
37b
12
Te
)
2
a
Reaction was monitored by TLC and GC.
Isolated yield, after CC over silica gel, based upon phenyl iodide (1a) consumed.
b
3e
pMeOPhTeLi
2h
Te
)
2
Initially, control reactions were performed with THF, THF/
MeO
dimethylsulfoxide (DMSO) or THF/DMF as solvent but in the ab-
sence of CuI (Table 1, entries 1,4 and 5), and in each case relatively
low yields of 3a were obtained after 24 h at 80 ꢀC. Addition of
5 mol % of CuI to the reaction mixture improved the yields con-
siderably irrespective of the solvent employed, thus showing that
the presence of CuI is beneficial for yield enhancement. With the
system CuI/DMF (Table 1, entry 10), the isolated yield of 3a was 94%
after 6 h at 80 ꢀC. For comparison purposes, reactions involving the
systems CuI/THF and CuI/DMSO were quenched after 6 h at 80 ꢀC
and the yields of 3a obtained were 40 and 85%, respectively. These
3f
a
Isolated yield, after CC over silica gel, based upon phenyl iodide (1a) consumed.
The phenyl iodide 1a was recovered.
b
reactions were monitored by TLC and GC, and in each case,
unreacted phenyl iodide could be detected after 6 h at 80 ꢀC. All of
the reactions were performed in triplicate and the yields did not
change significantly (ꢁ5%) from run to run. Solvents other than THF,
DMSO and DMF were tested together with different copper salts,

M.S. Silva, J.V. Comasseto / Tetrahedron 67 (2011) 8763e8768
8765
Table 4
Reaction of aryl iodides with lithium n-butyltellurolate using the system CuI/DMFa
TenBu
I
CuI (5 mol %) / DMF
THF / 80 ºC
nBuTeLi
+
R'
R'
2a
3
1
Entry
1
ArI
(1)
Product
(3)
Time(h)
6
Yield of 3b
(%)
TenBu
I
90
1d
3g
TenBu
TenBu
I
2
3
4
5
6
12
12
15
88
68
55
47
MeO
1e
MeO
Cl
3h
I
Cl
F
3i
1f
TenBu
I
F
1g
3j
TenBu
I
CF3
CF3
3k
1h
TenBu
I
6
7
6
7
85
77
H2N
O
H2N
O
1i
3l
TenBu
I
N
N
H
H
1j
3m
TenBu
I
O
O
S
O
8
9
7
6
75
83
S
O
N
H
N
H
1k
3n
TenBu
I
OH
1l
OH
3o
TenBu
I
10
11
24
n.r.
O
1m
O
3p
I
TenBu
6
84
1n
3q
TenBu
N
I
N
12
10
56c
1o
3r
a
Reaction conditions: aryl iodide 1 (1 mmol), lithium n-butyltellurolate (2a) (2 mmol), CuI (5 mol %) and DMF (1 mL) in THF (5 mL) at 80 ꢀC under nitrogen.
Isolated yields.
b
c
A non-catalyzed substitution reaction of 2-iodopyridine (1o) with nBuTeLi (2a) has been reported previously.10

8766
M.S. Silva, J.V. Comasseto / Tetrahedron 67 (2011) 8763e8768
Table 6
but in all cases inferior yields of 3a were obtained as shown in
Table 1.
Reaction of aryl iodides 1 with lithium n-butyltellurolate (2a) using the system CuI/
1,10-phenanthroline/DMF
In view of its efficiency, the CuI/DMF system was adopted as
standard in order to investigate the effects of the structures of the
aryl halide 1 and the organotellurium 2 on products and yields. As
shown in Table 2, reaction of nBuTeMgBr (2b) with phenyl iodide
(1a) gave a yield of 3a that was slightly lower than that observed in
the reaction with nBuTeLi (2a) (cf. Table 1, entry 10 and Table 2,
entry 1). The reaction of phenyl iodide (1a) with dibutylditelluride
(2c) under the same conditions gave 3a in only 29% yield based
upon consumption of 1a (Table 2, entry 4). In contrast, the reaction
of nBuTeLi (2a) with phenyl bromide (1b) or phenyl chloride (1c)
(Table 2, entries 2 and 3, respectively) did not afford the desired
product 3a.
Table 3 shows the influence of the nature of lithium orga-
notellurolate 2 on products and yields. Use of lithium methyl-,
sec-butyl and tert-butyltellurolate under the standard condi-
tions afforded products in good yields (Table 3, entries 1e3).
Lithium aryltellurolates (2g and h) did not react with phenyl
iodide (1a) (Table 3, entries 4 and 5), but rather the product
comprised the diaryltelluride (3e and f) corresponding to the
lithium aryltellurolate and was contaminated with the
diarylditelluride.
Finally, the influence of the nature of the aryl iodide 1 on
product yield was investigated. The results obtained by reaction of
lithium n-butyltellurolate (2a) with aryl iodides 1 bearing different
functional groups are shown in Table 4, from which it can be ob-
served that the reaction is compatible with several functionalities
and affords good yields in most cases (Table 4, entries 1, 2 and
6e11). However, the presence of electron withdrawing groups
seems to be detrimental to the success of the reaction, and for p-
iodoacetophenone (1m) (Table 4, entry 10) no product was
observed.
It is well known that the presence of additives in the medium
can improve the yield of coupling reactions that are promoted by
CuI.7 On this basis, the CuI-promoted reaction between lithium n-
butyltellurolate (2a) and p-iodoacetophenone (1m) was repeated
in the presence of diverse additives. The desired product, p-butyl-
telluroacetophenone (3p), was formed in variable yields but the
highest was afforded with 1,10-phenanthroline (Table 5, entry 2). In
view of these results, the reactions with p-chloroiodobenzene (3i)
(Table 6, entry 1), p-fluoroiodobenzene (3j) (Table 6, entry 2)
and m-CF3-iodobenzene (3k) (Table 6, entry 3) were performed
in the presence of 1,10-phenanthroline, generating the products
and yields shown in Table 6. In all cases yields were improved
in comparison with those observed in the absence of additives
(cf. Table 4, entries 3, 4 and 5, respectively).
Entry
1
ArI
Product
Timea (h)
Yield of 3b
(%)
TenBu
I
I
12
84
69
58
62
Cl
Cl
F
1
f
3i
TenBu
2
3
12
24
12
F
1g
3j
TenBu
I
CF3
1h
CF3
3k
TenBu
I
4
O
O
1m
3p
a
Reaction was monitored by TLC and GC.
Isolated yield after CC over silica gel.
b
3. Conclusions
A mild and practical method has been developed by which to
prepare functionalized arylealkyl tellurides under conditions that
are compatible with a number of functionalities. It is of interest to
note that the prepared compounds did not emit unpleasant odours
and, when free of solvent, could be handled safely in the presence
of light and air. Moreover, the compounds, when stored under re-
frigeration, remained stable for several months with no perceptible
decomposition.
4. Experimental
4.1. General experimental methods
Reactions between metal organotellurolates and aryl iodides
were carried out using dry solvents in anhydrous conditions under
nitrogen. Standard syringe techniques were applied in the transfer
of dry solvents, and some air-sensitive reagents were introduced
into reaction vessels through rubber septa. THF was distilled from
sodium benzophenone prior to use. DMF was distilled from CaH2
Table 5
Influence of the presence of ligands on reaction yields
ꢁ
CuI (5 mol%) / DMF
Ligand (10 mol%)
and stored under 4 A molecular sieves.
TenBu
I
nBuTeLi
Reactions were monitored by TLC analysis on layers of silica gel
60 F254 (Merck) eluted with hexane/ethyl acetate (9:1) and visu-
alized under UV light and/or by treatment with 5% p-anisaldehyde
in 10% H2SO4 and heat. GC analyses were performed using a Shi-
madzu model 2014 instrument (column DB1 30ꢂ0.32 mm
+
THF / 80 ºC
O
O
1m
2a
3p
Entry
Ligand (10 mol %)
None
Timea (h)
24
12
12
24
15
Yield of 3pb
(%)
idꢂdf¼0.25
mm, flame ionization detector and chromatographic
conditions: 60e230 ꢀCdinjector 240 ꢀCdsample volume
Ldpressure 44.0 kPa). Flash CC was carried out over silica gel
1
2
3
4
5
0
62
56
28
45
1
m
1,10-Phenanthroline
-Proline
with particle size 230e400 mesh (Merck). IR spectra were mea-
sured using a Bomem MB 100/FT-IR spectrophotometer with
samples dissolved in CHCl3 solution: wavenumbers are reported
in cmꢃ1. NMR spectra were recorded on Varian INOVA 200
(200 MHz) or 300 (300 MHz) instruments with samples dissolved
L
Glycol
Pyridine
a
Reaction was monitored by TLC and GC.
Isolated yield after CC over silica gel.
b

M.S. Silva, J.V. Comasseto / Tetrahedron 67 (2011) 8763e8768
8767
in CDCl3. Chemical shifts are reported in
d
(ppm) relative to TMS
7.16 (d, J¼8.6 Hz, 2H), 2.89 (t, J¼7.4 Hz, 2H),1.76 (quin, J¼7.2 Hz, 2H),
1.38 (app sext, J¼7.6 Hz, 2H), 0.90 (t, J¼7.4 Hz, 3H); 13C NMR
standard for 1H and to CDCl3 for 13C NMR: coupling constants (J)
are reported in hertz. Mass spectra (MS) were determined using
a Shimadzu model CG-17A/QP5050A mass spectrometer and high
(50 MHz, CDCl3) (d, ppm): 139.7, 134.0, 129.3, 109.2, 33.8, 25.0, 13.3,
8.9; CAS No 874148-10-4.11
resolution (HR) MS were recorded on
MicroTOF.
a Bruker Daltonics
4.3.5. n-Butyl(4-fluorophenyl)tellane (3j). Yellow oil; yield 0.155 g
(55%); 1H NMR (200 MHz, CDCl3) (
d
, ppm): 7.69 (dd, J¼8.6 and
4.2. Preparation of lithium organotellurolates
5.6 Hz, 1H), 6.90 (t, J¼9.0 Hz, 3H), 2.87 (t, J¼7.4 Hz, 2H), 1.75 (quin,
J¼7.0 Hz, 2H),1.37 (app sext, J¼7.4 Hz, 2H), 0.89 (t, J¼7.0 Hz, 3H); 13C
The appropriate organolithium reagent (2.0 mmol) in hexane
was added dropwise to a suspension of elemental tellurium
(0.255 g, 2 mmol) in 5 mL of dry THF maintained under nitrogen in
a two necked 50 mL round bottomed flask equipped with a mag-
netic stirrer and rubber septa. A clear solution was formed after
5 min of stirring at room temperature.
NMR (50 MHz, CDCl3) (
d
, ppm): 162.3 (1J¼246.05 Hz), 140.8
(3J¼7.45 Hz), 116.4 (2J¼20.65 Hz), 105.1 (4J¼3.55 Hz), 33.8, 25.0,
13.4, 8.9; HRMS (ESI) m/z: calcd for C10H13FTe: 282.0063; found:
283.0094 (þH); CAS No 1159428-50-8.12
4.3.6. n-Butyl(3-(trifluoromethyl)phenyl)tellane (3k). Yellow oil;
yield 0.156 g (47%); 1H NMR (200 MHz, CDCl3) (
d, ppm): 7.85e7.93
4.3. General procedure for the reaction of lithium
organotellurolates with aryl iodides promoted by CuI or CuI
plus ligand
(m, 2H), 7.49e7.53 (m, 1H), 7.29 (t, J¼7.6 Hz, 1H), 2.96 (t, J¼7.4 Hz,
2H), 1.80 (quin, J¼7.2 Hz, 2H), 1.42 (app sext, J¼7.4 Hz, 2H), 0.91 (t,
J¼7.2 Hz, 3H); CAS No 113556-16-4.13
Lithium organotellurolate 2 (2 mmol; prepared as in Section 4.2)
in 5 mL of dry THF was added to aryl iodide 1 (1.0 mmol), CuI (0.01g,
5 mol %) and dry DMF (1 mL) maintained under nitrogen in a two
necked 50 mL round bottomed flask equipped with a magnetic
stirrer, a reflux condenser and a rubber septum. The reaction
mixture was heated at 80 ꢀC (water bath temperature) and the
progress of the reaction was monitored by TLC and GC. When
consumption of 1 had ceased, the reaction mixture was quenched
at room temperature by addition of saturated aqueous NH4Cl so-
lution (10 mL) and subsequently extracted with EtOAc (3ꢂ10 mL).
The combined organic layers were washed with aqueous NaCl
(10 mL), dried over MgSO4 and concentrated under reduced pres-
sure. The residue was purified by CC over silica gel eluting with
hexane/EtOAc mixtures with a gradual increase in polarity to afford
products 3 with yields shown in Tables 1e4.
4.3.7. 4-(Butyltellanyl)benzenamine (3l). Yellow oil; yield 0.237 g
(85%); IR (CHCl3 solution) (nmax, cmꢃ1): 3352, 2956, 1488, 616; 1H
NMR (200 MHz, CDCl3) (
d
, ppm): 7.55 (d, J¼8.4 Hz, 2H), 6.54 (d,
J¼8.6 Hz, 2H), 3.7 (br s, 2H), 2.78 (t, J¼7.4 Hz, 2H), 1.72 (quin,
J¼7.0 Hz, 2H),1.36 (app sext, J¼7.4 Hz, 2H), 0.88 (t, J¼7.2 Hz, 3H); 13C
NMR (50 MHz, CDCl3) (d, ppm): 146.3, 141.1, 116.0, 97.4, 33.8, 24.9,
13.4, 8.7; GC/MS m/z (relative intensity): 279 (23) [Mþ], 222 (35), 93
(100), 57 (24), 41 (37); HRMS (ESI) m/z: calcd for C10H15NTe:
279.02667; found: 280.0349 (þH).
4.3.8. N-(4-(Butyltellanyl)phenyl)acetamide (3m). Yellow oil; yield
0.247 g (77%); IR (CHCl3 solution) (nmax, cmꢃ1): 3299, 2956, 1668,
821, 510; 1H NMR (200 MHz, CDCl3) (
d, ppm): 7.96 (br s, 1H), 7.64 (d,
J¼8.4 Hz, 2H), 7.36 (d, J¼8.6 Hz, 2H), 2.86 (t, J¼7.6 Hz, 2H), 2.16 (s,
3H), 1.75 (quin, J¼7.0 Hz, 2H), 1.37 (app sext, J¼7.6 Hz, 2H), 0.88 (t,
Reactions promoted by CuI plus ligand were carried out using an
identical procedure but with the addition of 10 mol % of the ap-
propriate ligand to the reaction mixture. The yields of products 3
are shown in Tables 5 and 6.
J¼7.4 Hz, 3H); 13C NMR (50 MHz, CDCl3) (
d, ppm): 168.7, 139.4,
137.6, 120.6, 105.7, 33.8, 24.9, 24.4, 13.3, 8.7; GC/MS m/z (relative
intensity): 321 (7) [Mþ], 222 (11), 93 (54), 57 (39), 41 (100); HRMS
(ESI) m/z: calcd for C12H17NOTe: 321.0372; found: 344.0270 (þNa).
4.3.1. n-Butyl(phenyl)tellane (3a). Yellow oil; yield 0.248 g (94%);
4.3.9. N-(4-(Butyltellanyl)phenyl)-4-benzenesulfonamide(3n).
Yellow oil; yield 0.325 g (75%); IR (CHCl3 solution) (nmax, cmꢃ1):
1H NMR (300 MHz, CDCl3) (
d, ppm): 7.78e7.81 (m, 2H), 7.25e7.37
(m, 3H), 2.99 (t, J¼7.5 Hz, 2H), 1.87 (quin, J¼7.2 Hz, 2H), 1.48 (app
3256, 2922, 1159, 665; 1H NMR (200 MHz, CDCl3) (
d, ppm): 7.70
sext, J¼7.5 Hz, 2H), 0.98 (t, J¼7.2 Hz, 3H); 13C NMR (75 MHz, CDCl3)
(d, J¼8.2 Hz, 2H), 7.54 (d, J¼8.6 Hz, 2H), 7.21 (d, J¼8.0 Hz, 2H),
6.93 (d, J¼8.6 Hz, 2H), 2.82 (t, J¼7.4 Hz, 2H), 2.36 (s, 3H), 1.71
(quin, J¼7.0 Hz, 2H), 1.34 (app sext, J¼7.4 Hz, 2H), 0.86 (t,
(d, ppm): 138.4, 129.3, 127.6, 112.1, 34.2, 25.3, 13.6, 8.7; GC/MS m/z
(relative intensity): 264 (43) [Mþ], 208 (32), 77 (100), 57 (59), 41
(62), 43 (69); CAS No 32343-98-9.11
J¼7.2 Hz, 3H); 13C NMR (50 MHz, CDCl3) (
d, ppm): 143.9, 139.4,
136.2, 135.8, 129.7, 127.2, 121.7, 107.1, 33.7, 24.9, 21.5, 13.3, 8.7;
GC/MS m/z (relative intensity): 278 (38) [MþꢃTosyl], 91 (100), 57
(42), 41 (58); HRMS (ESI) m/z: calcd for C17H21NO2Ste: 433.0355;
found: 456.0247 (þNa).
4.3.2. n-Butyl(o-tolyl)tellane (3g). Yellow oil; yield 0.250 g (90%);
1H NMR (300 MHz, CDCl3) (
d, ppm): 7.65e7.68 (m, 1H), 7.17e7.27
(m, 2H), 7.02e7.08 (m, 1H), 2.93 (t, J¼7.5 Hz, 2H), 2.47 (s, 3H), 1.83
(quin, J¼7.2 Hz, 2H), 1.46 (app sext, J¼7.2 Hz, 2H), 0.96 (t, J¼7.5 Hz,
3H); 13C NMR (75 MHz, CDCl3) (
d
, ppm): 142.3, 136.7, 129.1, 127.5,
4.3.10. 4-(Butyltellanyl)phenol (3o). Yellow oil; yield 0.232 g (83%);
IR (CHCl3 solution) (ymax, cmꢃ1): 3375, 2957, 1575, 854; 1H NMR
126.5, 116.6, 33.7, 26.5, 25.3, 13.5, 7.6; CG/MS m/z (relative in-
tensity): 278 (29) [Mþ], 91 (100), 57 (29), 41 (35); CAS No 874147-
99-6.11
(200 MHz, CDCl3) (
d
, ppm): 7.12e7.20 (m, 2H), 6.29 (tap, J¼7.8 Hz,
1H), 6.64e6.69 (m, 1H), 4.88 (brs, 1H), 2.84 (t, J¼7.4 Hz, 2H), 1.72
(quin, J¼7.0 Hz, 2H), 1.32 (app sext, J¼7.4 Hz, 2H), 0.83 (t, J¼7.4 Hz,
4.3.3. n-Butyl(4-methoxyphenyl)tellane (3h). Yellow oil; yield
3H); 13C NMR (50 MHz, CDCl3) (
d, ppm): 155.5, 130.4, 130.1, 124.6,
0.259 g (88%); 1H NMR (300 MHz, CDCl3) (
d
, ppm): 7.67 (d,
114.6, 112.8, 33.9, 25.1, 13.4, 8.5; GC/MS m/z (relative intensity): 278
(23) [Mþ], 94 (100), 57 (30), 41 (26); HRMS (ESI) m/z: calcd for
C10H14OTe: 280.01069; found: 303.0041 (þNa).
J¼13.2 Hz, 2H), 6.75 (d, J¼13.2 Hz, 2H), 2.82 (t, J¼11.1 Hz, 2H), 1.73
(quin, J¼10.5 Hz, 2H), 1.39 (app sext, J¼11.1 Hz, 2H), 0.88 (t,
J¼10.8 Hz, 2H); 13C NMR (75 MHz, CDCl3) (
d, ppm): 159.6, 140.8,
115.0, 100.5, 55.1, 33.8, 24.9, 13.4, 8.7; CAS No 32343-98-9.11
4.3.11. 1-(4-(Butyltellany)phenyl)ethanone (3p). Yellow oil; yield
0.190 g (62%); 1H NMR (200 MHz, CDCl3) (
d, ppm): 7.67e7.61 (m,
4.3.4. n-Butyl(4-chlorophenyl)tellane (3i). Yellow oil; yield 0.202 g
4H), 2.88 (t, J¼7.2 Hz, 2H), 2.48 (s, 3H), 1.73 (q, J¼8.1 Hz, 2H), 1.33
(68%); 1H NMR (200 MHz, CDCl3) (
d
, ppm): 7.62 (d, J¼8.6 Hz, 2H),
(app sext, J¼7.6 Hz, 2H), 0.83 (t, J¼7.5 Hz, 3H); 13C NMR (50 MHz,

8768
M.S. Silva, J.V. Comasseto / Tetrahedron 67 (2011) 8763e8768
CDCl3) (
d
, ppm): 197.7,136.7,135.9,128.6,121.0, 33.8, 26.7, 25.2,13.5,
Acknowledgements
8.8; CAS No 874148-02-4.11
The authors wish to thank FAPESP, CNPq and CAPES for financial
4.3.12. Butyl(naphthalen-2-yl)tellane (3q). Yellow oil; yield 0.264 g
support.
(84%); 1H NMR (200 MHz, CDCl3) (
d, ppm): 8.20 (br s, 1H), 7.61e7.81
(m, 4H), 7.40e7.50 (m, 2H), 2.97 (t, J¼7.6 Hz, 2H), 1.80 (quin,
Supplementary data
J¼7.2 Hz, 2H),1.39 (app sext, J¼7.4 Hz,1H), 0.89 (t, J¼7.2 Hz, 3H); 13C
NMR (50 MHz, CDCl3) (d, ppm): 137.6, 135.0, 134.1, 132.4, 128.1,
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.tet.2011.09.014.
127.7, 127.1, 126.2, 126.1, 109.2, 33.9, 25.0, 13.4, 8.6; CAS No 95849-
65-3.14
References and notes
4.3.13. 2-(Butyltellanyl)pyridine (3r). Yellow oil; yield 0.148
(56%); 1H NMR (200 MHz, CDCl3) (
g
d
, ppm): 8.48 (dq, J¼5.0 and
1. (a) Irgolic, K. C. Organotellurium compounds In. Houben-weyl Methods of
Organic Chemistry; Klaman, R., Ed.; Georg Thieme: Stuttgart, 1990; Vol. E12b;
(b) Comasseto, J. V.; Clososki, G. C.; Cunha, R. L. O. R. Tellurium In. Compre-
hensive Organometallic Chemistry III; Crabtree, R. H., Mingos, D. M. P., Eds.;
Elsevier: Amsterdam, 2007; Vol. 9, pp 587e648; (c) Petragnani, N.; Stefani, H. A.
Tellurium in Organic Synthesis, Second Edition; Academic: London, 2007.
2. For reviews see: (a) Comasseto, J. V.; Barrientos-Astigarraga, R. R. Aldrichimica
1.0 Hz, 1H), 7.48 (dt, J¼7.8 and 1.0 Hz, 1H), 7.32 (dt, J¼7.4 and 2.0 Hz,
1H), 7.01 (ddd, J¼7.4, 6.2 and 1.4 Hz, 1H), 3.14 (t, J¼7.4 Hz, 2H), 1.90
(quin, J¼7.2 Hz, 2H), 1.43 (app sext, J¼7.4 Hz, 2H), 0.93 (t, J¼7.2 Hz,
3H); 13C NMR (50 MHz, CDCl3) (
d, ppm): 150.7, 141.2, 135.3, 131.6,
120.9, 33.9, 25.2, 13.4, 9.3; CAS No 181647-39-2.10
€
Acta 2000, 33, 66e78; (b) Zeni, G.; Ludtke, D. S.; Panatieri, R. B.; Braga, A. L.
Chem. Rev. 2006, 106, 1032e1076.
3. For reviews see: (a) Wendler, E. P.; Dos Santos, A. A. Synlett 2009, 1034e1040;
(b) Princival, J. L.; Dos Santos, A. A.; Comasseto, J. V. J. Braz. Chem. Soc. 2010, 21,
2042e2054; (c) For a recent example see: Ferrarini, R. S.; Dos Santos, A. A.;
Comasseto, J. V. Tetrahedron Lett. 2010, 51, 6843e6846.
4. For reviews see: (a) Nogueira, C. W.; Zeni, G.; Rocha, J. B. T. Chem. Rev. 2004, 104,
6255e6285; (b) Cunha, R. L. O. R.; Gouvea, I. E.; Juliano, L. An. Acad. Bras. Cienc.
2009, 81, 393e407; (c) Alberto, E. E.; Nascimento, V.; Braga, A. L. J. Braz. Chem.
Soc. 2010, 21, 2032e2041.
4.3.14. Methyl(phenyl)tellane (3b). Yellow oil; yield 0.178 g (80%);
1H NMR (200 MHz, CDCl3) (
d
, ppm): 7.05e7.59 (m, 2H), 7.27e7.40
(m, 1H), 7.11e7.17 (m, 2H), 2.12 (s, 3H); 13C NMR (50 MHz, CDCl3) (
d
,
ppm): 136.7, 129.1, 128.7, 127.1, ꢃ16.6; GC/MS m/z (relative in-
tensity): 222 (59) [Mþ], 207 (52), 77 (100), 51 (57); CAS No 161063-
16-7.15
5. (a) Albeck, A.; Weitman, H.; Sredni, B.; Albeck, M. J. Inorg. Chem. 1998, 37,
1704e1712; (b) Cunha, R. L. O. R.; Urano, M. E.; Chagas, J. R.; Almeida, P. C.;
Bincoletto, C.; Tersariol, I. L. S.; Comasseto, J. V. Bioorg. Med. Chem. Lett. 2005, 15,
755e760.
4.3.15. sec-Butyl(phenyl)tellane (3c). Yellow oil; yield 0.222
g
(84%); 1H NMR (200 MHz, CDCl3) (
d
, ppm): 7.78e7.81 (m, 2H),
7.17e7.34 (m, 3H), 3.40 (app sext, J¼7.0 Hz,1H),1.69 (quin, J¼9.0 Hz,
€
6. Ba, L. A.; Doring, M.; Jamier, V.; Jacob, C. Org. Biomol. Chem. 2010, 8, 4203e4216.
2H), 1.61 (d, J¼7.2 Hz, 3H), 0.98 (t, J¼7.2 Hz, 3H); 13C NMR (50 MHz,
7. For reviews see: (a) Ma, D.; Cai, Q. Acc. Chem. Res. 2008, 41, 1450e1460; (b)
Evano, G.; Blanchard, N.; Toumi, M. Chem. Rev. 2008, 108, 3054e3131; (c) For
a recent example see: Huang, Y.-B.; Yang, C.-T.; Yi, J.; Deng, X.-J.; Fu, Y.; Liu, L. J.
Org. Chem. 2011, 76, 800e810; (d) Niu, L.-F.; Cai, Y.; Liang, C.; Hui, X.-P.; Xu, P.-F.
Tetrahedron 2011, 67, 2878e2881.
CDCl3) (d, ppm): 140.3, 129.1, 127.9, 111.6, 32.6, 26.1, 24.1, 14.1; GC/
MS m/z (relative intensity): 264 (36) [Mþ], 208 (68), 77 (100), 57
(71), 41 (46); CAS No 83817-37-2.16
8. For a review see: Beletskaya, I. P.; Ananikov, V. P. Chem. Rev. 2011, 111,1596e1636.
9. Suzuki, H.; Abe, H.; Ohmasa, N.; Osuka, A. Chem. Lett. 1981, 1115e1116 This
paper describes the formation of diaryltellurides by heating a mixture of nitro-
iodoarenes and sodium benzenetellurolate (prepared by reduction of diphe-
nylditelluride with NaBH4 in hexamethylphosphoramide) at 90 ꢀC in the
presence of stoichiometric amounts of CuI. In most cases the yields obtained
were only moderate (65e53%), and when DMF or DMSO were used as solvents,
the expected products were not formed.
10. Kondo, Y.; Shilai, M.; Ushiyama, M.; Sakamoto, T. J. Chem. Soc., Perkin Trans. 1
1996, 1781e1782.
11. Cella, R.; Cunha, R. L. O. R.; Reis, A. E. S.; Pimenta, D. C.; Klitzke, C. F.; Stefani, H.
A. J. Org. Chem. 2006, 71, 244e250.
12. Singh, F. V.; Milagre, H. M. S.; Eberlin, M. N.; Stefani, H. A. Tetrahedron Lett. 2009,
50, 2312e2316.
13. Comasseto, J. V.; Lang, E. S.; Ferreira, J. T. B.; Simonelli, F.; Correia, V. R. J. Or-
ganomet. Chem. 1987, 364, 329e340.
14. Cunha, R. L. O. R.; Omori, A. T.; Castelani, P.; Toledo, F. T.; Comasseto, J. V. J.
Organomet. Chem. 2004, 683, 3631e3636.
4.3.16. tert-Butyl(phenyl)tellane (3d). Yellow oil; yield 0.198
(75%); 1H NMR (200 MHz, CDCl3) (
, ppm): 7.88e7.92 (m, 2H),
7.22e7.42 (m, 3H), 1.59 (s, 9H); 13C NMR (50 MHz, CDCl3) (
, ppm):
142.1, 128.9, 128.4, 112.8, 35.5, 29.1; GC/MS m/z (relative intensity):
264 (20) [Mþ], 208 (33), 77 (71), 57 (100), 41 (39); HRMS (ESI) m/z:
calcd for C10H14Te: 264.01577; found: 265,0160 (þH); CAS No
83817-38-3.17
g
d
d
4.3.17. Diphenyltellane (3e). Yellow oil; yield 0.158 g (56%); 1H NMR
(300 MHz, CDCl3) (d, ppm): 7.73e7.77 (m, 4H), 7.23e7.35 (m, 6H);
13C NMR (75 MHz, CDCl3) (
298680-10-0.18
d, ppm): 138.1, 129.6, 127.9,114.8; CAS No
15. Khurana, J. M.; Sharma, V.; Chack, S. A. Tetrahedron 2007, 63, 966e969.
16. Cougnon, F.; Feray, L.; Bazin, S.; Bertrand, M. Tetrahedron 2007, 63, 11959e11964.
17. Tamago, S.; Iida, K.; Yoshida, J. Tetrahedron Lett. 2001, 42, 5061e5064.
18. Taniguchi, N. J. Org. Chem. 2007, 72, 1241e1245.
19. Alves, D.; Pena, J. M.; Vieira, A. S.; Botteselle, G. V.; Guadagnin, R. C.; Stefani, H.
A. J. Braz. Chem. Soc. 2009, 20, 988e992.
4.3.18. Bis(4-methoxyphenyl)tellane (3f). Yellow oil; yield 0.151 g
(44%); 1H NMR (200 MHz, CDCl3) (
d
, ppm): 7.62 (d, J¼6.6 Hz, 4H),
6.75 (d, J¼6.6 Hz, 4H), 3.76 (s, 6H); 13C NMR (50 MHz, CDCl3) (
d,
ppm): 159.6, 139.7, 115.4, 104.3, 55.2; CAS No 4456-34-2.19