Hydrochalcogenation of activated olefines. Synthesis of functionalized dialkylchalcogenides

Article abstract of DOI:10.1016/j.jorganchem.2008.06.014

Alkanethiols, selenols and tellurols are generated in situ by reaction of elemental sulfur, selenium and tellurium with commercial alkyllithiums, followed by reaction with deoxygenated water. The alkanechalcogenols react in situ with activated olefins in a Michael-type addition reaction.

Full text of DOI:10.1016/j.jorganchem.2008.06.014

Journal of Organometallic Chemistry 693 (2008) 2929–2936
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Hydrochalcogenation of activated olefines. Synthesis of functionalized
dialkylchalcogenides
a
a
b
a
João V. Comasseto a, , Rogério A. Gariani , Jefferson L. Princival , Alcindo A. Dos Santos , Fabiano K. Zinn
*
a
´
Instituto de Quımica, Universidade de São Paulo, Av. Prof. Lineu Prestes, 748, 05508-900 São Paulo, SP, Brazil
b Departamento de Qu´ımica, Universidade Federal de São Carlos, 13565-905 São Carlos, SP, Brazil
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 14 May 2008
Received in revised form 9 June 2008
Accepted 9 June 2008
Available online 17 June 2008
Alkanethiols, selenols and tellurols are generated in situ by reaction of elemental sulfur, selenium and tel-
lurium with commercial alkyllithiums, followed by reaction with deoxygenated water. The alkanechalc-
ogenols react in situ with activated olefins in a Michael-type addition reaction.
Ó 2008 Elsevier B.V. All rights reserved.
Keywords:
Alkanethiols
Alkaneselenols
Alkanetellurols
Dialkylsulfides
Dialkylselenides
Dialkyltellurides
1. Introduction
been devoted to develop friendly conditions to generate and use
these reagents in situ, so avoiding their manipulation in the labora-
Organic compounds of sulfur [1], selenium [2] and tellurium [3]
present useful synthetic applications. Notwithstanding their syn-
thetic potential, the organic compounds of these elements, spe-
cially those containing selenium and tellurium, are avoided by
the synthetic organic chemists. The bad reputation of these ele-
ments many times arises from comments found in the literature
concerning the bad smell of the organic chalcogen compounds. A
long time concern of our laboratory is the development of experi-
mental protocols which avoid the manipulation of bad smelling
organochalcogen compounds [4]. We could conclude that some
of the comments on the bad smell of such compounds are effec-
tively true, but only for the low molecular weight representatives
of specific classes of the organochalcogen compounds. Once incor-
porated into a more complex structure, the bad smell of the organ-
ochalcogen compound varnishes or disappears, giving rise to
products which present smell not more unpleasant than most of
the chemicals found in an organic synthesis laboratory. Among
the very bad smelling organochalcogen compounds of large
synthetic use are the alkanethiols and selenols and low weight
non-functionalized dialkylditellurides, precursors of metal alkane-
tellurolates and alkanetellurols. In the last years our laboratory has
tory atmosphere. We found that most of the products resulting
from the interaction of alkanethiols, –selenols and –tellurols
(tellurolates) with organic substrates are easily isolated as non-
bad smelling synthetic intermediates. In this paper we give a full
account of the scope and limitations of the in situ generation and
use of low molecular weight alkanethiols, –selenols and –tellurols
in Michael-type addition reactions to electron-deficient olefins.
2. Results and discussion
The reaction of elemental sulfur with alkyllithiums is a long
known method to prepare thiols [5]. However, nowadays this reac-
tion is rarely used to prepare this class of organosulfur compounds.
In this work we observed that elemental sulfur suspended in THF
reacts rapidly with nbutyllithium giving initially an orange solu-
tion, which becomes limpid and colorless after reaction with stoi-
chiometric amount of nbutyllithium. The initially observed orange
color is probably due to the initial formation of lithium alkylpoly-
sulfides [6], which are transformed into the desired colorless lith-
ium alkanethiolate by addition of the stoichiometric amount of
nbutyllithium. Addition of 2-cyclohexen-1-one (1) to this solution
leads to the formation of 3-(butylthio)cyclohexanone (2) in 50%
isolated yield. However, if deoxygenated water, obtained by
bubbling deoxygenated nitrogen under sonication, is added to
* Corresponding author. Tel.: +55 11 3091 2176; fax: +55 11 3815 5579.
E-mail address: jvcomass@iq.usp.br (J.V. Comasseto).
0022-328X/$ - see front matter Ó 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2008.06.014

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J.V. Comasseto et al. / Journal of Organometallic Chemistry 693 (2008) 2929–2936
the lithium nbutanethiolate solution prior to the addition of 1, the
yield of 2 rises to 98% isolated yield. We can presume that in the
presence of water an equilibrium is established leading to an
alkanethiol in the reaction medium, which reacts with the enone
fins leading to the Michael-type addition products in good yields
(Scheme 2 and Table 1).
When the nbutyllithium solution is added to a suspension of
gray elemental selenium in tetrahydrofuran the reaction mixture
becomes red. After the addition of the stoichiometric amount of
the nbutyllithium the red color fades giving rise to a pale yellow
solution. The initially observed red color probably is due to the for-
mation of alkanepolyselenide anions [11] and the final pale yellow
color corresponds to the lithium alkaneselenolate. Addition of
deoxygenated water to the lithium alkaneselenolate leads to an
equilibration responsible for the presence of the alkaneselenol in
the reaction mixture (Scheme 2).
to give a Michael-type addition reaction to the
system (Scheme 1).
a,b-unsaturated
In this way, it was demonstrated that the presence of water
in the reaction medium is mandatory for the success of the 1,4-
addition reaction. To determine the scope and limitations of the
methodology, other
a,b-unsaturated compounds were allowed to
react with the nBuSLi/ H2O system. The results are summarized
in Table 1.
As can be observed, unhindered enones give excellent yields of
the Michael adducts (Table 1, entries 4, 21 and 24). Enones with
some degree of steric hindrance give less satisfactory yields (Table
1, entries 26 and 27). The yields are however, still comparable with
those obtained for similar compounds prepared by Michael-type
reactions of alkanethiols using other sulfenilation methods [7].
Unsaturated nitrile (Table 1, entry 7) and ester (Table 1, entry
12) also gave good yields of the Michael adduct. Unsaturated alde-
hydes (Table 1, entries 1 and 3) also reacted, but the product had to
be reduced in situ with sodium borohydride in view of the instabil-
ity of the resulting 3-butylthioaldehyde. The resulting alcohols
were isolated in 50% yield. Finally, the sulfenilation of ethyl propi-
olate (Table 1, entry 28) gave the corresponding Z-vinylic sulfide in
80% yield.
It is worth mentioning that during all the operations described
above, the peculiar bad smell of nbutanethiol was not detected. An-
other fact to be mentioned is that no additive was necessary to pro-
mote this Michael-type addition. In recent years a number of
papers were published on the addition of alkanethiols to elec-
tron-deficient olefins [7]. In all cases, the alkanethiols were used
in combination with other agents, which in some cases are expen-
sive or present acidic or basic character. In all papers published on
this subject, the isolated alkanethiol was used as the nucleophilic
starting material. As far as we know, there is just one recent paper
on the in situ generation of the lithium butanethiolate from butyl-
lithium and sulfur in a subsequent step [5b,8].
By using the present method, the 1,4-addition products were
obtained in good yields (Table 1) with no need to manipulate the
bad smelling alkaneselenol and, as in the case of the nbutanethiol
1,4-addition described before, no bad smell was detected during
the addition reaction of the nbutaneselenol to the
system.
a,b-unsaturated
Organotellurols are too unstable to be isolated [12]. It is pre-
sumed that these compounds are formed in situ by reduction of
diorganoditellurides with sodium borohydride. However, no evi-
dences for the formation of such species were presented to date
[12]. Some time ago, the reaction of alkyllithiums with elemental
tellurium to generate alkanetellurolates has been synthetically ex-
plored [3b,13]. We applied this procedure to perform the hydro-
telluration of alkynes under non-reducing conditions [14]. This
method avoids the use of the bad smelling dibutylditelluride as
starting material. In this work, a number of activated olefins were
submitted to the hydrotelluration reaction giving functionalized
alkanetellurides in good yields. nButyl, sbutyl and tbutyllithium
were used to generate the lithium alkanetellurolates (Scheme 3).
We found that both deoxygenated water or ethanol can be used
as the proton source in these 1,4-addition reactions. As in the pre-
ceding cases the chalcogen is rapidly consumed by addition of the
alkyllithium to the suspension of elemental tellurium in THF at
0 °C. Initially a purple solution is formed. The purple color probably
arises from the lithium alkanepolytellurides [11] initially present,
which equilibrate with the alkyllithium leading to the lithium
alkanetellurolate. The color fades as the stoichiometric amount of
the added alkyllithium is reached. Addition of the proton source
followed by the activated olefin gives the 1,4-addition product in
good yield (Table 1). It is worth to mention that the water or
ethanol used as the proton source must be carefully deoxygenated
by sonication while a stream of deoxygenated nitrogen is bubbled
into the vial containing the solvent. The optimal amount of water
was found to be 2.5 times the amount of the lithium alkylchalco-
genate employed. Larger amounts lead to a decrease in the reaction
yield. As in the preceding cases, no bad smell associated with low
molecular weight dialkylditellurides was detected during the reac-
tion or the work-up.
Contrary to the scarcity of synthetic methods involving the
reaction of an alkyllithium and sulfur, the reaction of alkyllithiums
with selenium is widely used to generate lithium alkaneselenolates
which are used in further reactions [9]. However, when alkanesel-
enols are needed, the isolated compounds are used, which are in-
deed very unpleasant compounds to work with [10]. In this work
we employed the same reaction sequence shown in Scheme 1 to
generate alkaneselenols in situ, which reacted with activated ole-
nBuLi /hexane
H2O
O
[nBuSLi]
50%
[nBuSH]
98%
S8
The obtained products constitute a scarcely studied class of or-
ganic tellurium compounds, in view of the comments on the bad
smell, and the light and air instability of dialkyltellurides found
in the literature. In view of this, a more complete study on the
1,4-addition of alkanetellurolates to enones was performed as a
method to prepare functionalized dialkyltellurides (Scheme 3 and
Table 1).
°
THF, C
1
As in the case of the sulfides, surprisingly we observed that
none of the prepared tellurides presented bad smell when in the
pure form. When some of the prepared functionalized tellurides,
O
s
t
specially those bearing a Bu or Bu group, were stored for some
time, a bad smell resembling that of the corresponding dibutyldi-
tellurides was detected. We concluded that the reported bad smell-
ing character of the samples of functionalized tellurides does not
arise from the original by prepared tellurides, but rather from
small amounts of dialkylditellurides resulting from the slow
S
2
Scheme 1. Hydrosulfenylation of activated olefins.

J.V. Comasseto et al. / Journal of Organometallic Chemistry 693 (2008) 2929–2936
2931
Table 1
Dialkylchalcogenides prepared
Entry
1
Electrophile
Product
Yield (%)
50
H
O
a
O
nBuS
H
2a
a
O
2
3
85
50
nBuTe
nBuS
H
4a
H
a
O
O
O
H
2b
4
5
93
86
85
90
97
98
83
nBuS
O
2c
O
nBuTe
4b
O
6
sBuTe
nBuS
5a
CN
7
CN
2d
CN
CN
CN
nBuSe
nBuTe
sBuTe
8
3a
9
4c
5a
10
CN
tBuTe
11
12
13
14
15
16
83
78
79
96
95
6a
O
OEt
nBuS
OEt
O
2e
O
nBuSe
nBuTe
sBuTe
nBuSe
OEt
OEt
OEt
OMe
3b
O
O
O
4d
5b
OMe
82
O
(continued on next page)
3c

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J.V. Comasseto et al. / Journal of Organometallic Chemistry 693 (2008) 2929–2936
Table 1 (continued)
Entry
17
Electrophile
Product
Yield (%)
82
O
nBuTe
nBuTe
OMe
4e
O
O
O
OEt
18
82
OEt
OEt
OEt
O
4f
O
nBuSe
19
20
81
90
OEt
3d
4g
nBuTe
O
O
21
22
97
82
SnBu
2f
O
SenBu
3g
O
23
24
89
96
TenBu
SnBu
4h
O
O
2g
O
25
62
TenBu
4i
26
O
O
66
O
O
SnBu
2h
SnBu
27
28
64
80
2i
O
nBuS
OEt
O
OEt
2j
a2a, 2b and 4a were reduced in situ and the yields refer to the isolated alcohols 7a, 7b and 8.

J.V. Comasseto et al. / Journal of Organometallic Chemistry 693 (2008) 2929–2936
2933
considered, d = 0.0 ppm, 25 °C) as external standard. Infrared spec-
tra were recorded on a Bomem MB-100 spectrophotometer. Low
resolution mass spectra were obtained on a Finnigan 4021 spec-
trometer or on a GC–MS Hewlett Packard 5988-8/5890 spectrom-
eter, both operating at 70 eV. Elemental analyses were performed
in a Perkin–Elmer CHNO analyzer and high resolution mass spectra
were obtained on a Bruker Daltonics Micro TOF with time of flight
analyzer. Column chromatography was carried out with Merck sil-
ica gel (230–400 mesh). Thin layer chromatographies (TLC) were
performed on silica gel F-254 on aluminum. All solvents used were
previously dried and distilled according to the usual methods. Tet-
rahydrofuran and diethyl ether were distilled from sodium/benzo-
phenone under N2, immediately before use. Elemental sulfur,
selenium and tellurium (200 mesh) were purchased from Aldrich.
The remaining chemicals were obtained from commercial sources.
All operations were carried out in dried glassware, under an inert
atmosphere of dry and deoxygenated N2. The IUPAC names were
obtained using the ACD/Lab web service, version 3.5, at http://
www.acdlabs.com/ilab and ChemDraw 9.0.
O
O
nBuLi
THF,
H2O
[nBuSeH]
Se0
[nBuSeLi]
°
C
BuSe
3
Scheme 2. Hydroselenation of activated olefins.
O
O
H2O
RLi
Te0
[RTeH]
[RTeLi]
RTe
4, R = nBu
5, R = sBu
6, R = tBu
4.2. General procedures for the hydrochalcogenations reactions
Scheme 3. Hydrotelluration of activated olefins.
4.2.1. General procedure for the hydrosulfenylation reaction [25]
A 50-mL, two-necked, round-bottomed flask was equipped with
a magnetic stir bar, rubber septa and a glass adapter for a nitrogen
inlet. This reaction flask was flame-dried twice under a positive
nitrogen stream and cooled down to room temperature. Elemental
sulfur (Aldrich, 0.20 g, 6.0 mmol) was added to the reaction flask
followed by freshly distilled THF (10 mL). nButyllithium (5.47 mL
of a 1.17 mol/L solution in hexanes, 6.4 mmol) was added dropwise
to the vigorously stirred S8/THF mixture at 0 °C under nitrogen
atmosphere. After the addition of the first drops of nbutyllithium,
the mixture turned into orange and by the end of the addition of
the stoichiometric amount of nbutyllithium, the powder was com-
pletely consumed and a pale yellow solution had been formed.
Deoxygenated water (0.27 mL, 15.0 mmol) was then slowly added
into the lithium butanethiolate solution. The resulting colorless
solution was stirred for 10 min and the appropriate activated olefin
or alkyne (6.0 mmol) was added in a portion and the solution was
stirred for additional 30 min. After the reaction was complete, the
mixture was quenched with 3 mL of water. The product was ex-
tracted 3 times with ethyl acetate. The combined organic layers
were dried over magnesium sulfate and concentrated under re-
duced pressure. Column chromatography (20:1 hexane/ethyl ace-
tate) of the crude oil on silica gel afforded a colorless oil.
decomposition of the functionalized dialkyltellurides. In this way,
it is advisable to prepare the functionalized dialkyltellurides and
use them immediately for further synthetic transformations.
b-Tellurocarbonyl compounds constitute a rather unexplored
class of organotellurium compounds [15,16]. In view of this fact,
we undertook a systematic investigation on their reactivity and
found that b-telluroketones can be converted to the corresponding
ketals [16,17] and telluroaldehydes, ketones and esters can be re-
duced to corresponding hydroxytellurides [18], which were re-
solved into enantiomers by enzymatic kinetic resolution [19]. All
these tellurium containing compounds can be transformed into
reactive organometallics, by Te/Li exchange [20], followed by
transmetallation [18,21]. The resulting reactive organometallics
were employed in the construction of useful carbon frameworks
[17] and in the synthesis of insect pheromones [22,23].
3. Conclusion
b-Thio- [7] and b-selenocarbonyl [24] compounds are long
known synthetic intermediates which are prepared by Michael-
type addition reactions on a,b-unsaturated compounds with orga-
nothio- or organoselenium nucleophiles. b-Tellurocarbonyl com-
pounds were only recently described [16] and synthetically
explored, showing promising synthetic applications. The method
described in this paper to prepare these classes of compounds is
advantageous over the existing methods in view of its practicabil-
ity and friendly experimental conditions employed.
4.2.2. General procedure for the hydroselenation of olefins [26]
In a two-necked 50 mL equipped as described above, was placed
elemental selenium (0.315 g, 4 mmol) in dry THF (5 mL). To this
suspension at room temperature was added n-butyllithium
(3.08 mL of a 1.3 mol/L solution in hexane, 4 mmol). A deep red
solution was formed as the initial drops of nbutyllithium were
added. By the end of the addition the reaction mixture became pale
yellow. To this solution it was added water (0.18 mL, 10 mmol)
previously deoxygenated under a N2 flow and sonication. Then
the appropriate olefin (4 mmol) was added at room temperature.
The mixture was maintained under stirring for 1 h. The organic
phase was washed with NH4Cl solution (3 Â 15 mL) and brine
(3 Â 15 mL) and then dried with magnesium sulfate. The solution
was filtered and the solvent was evaporated. The residue was puri-
fied by silica gel column chromatography eluting first with hexane,
and then with hexane/ethyl acetate (10:1).
4. Experimental
4.1. General considerations
The 1H and 13C spectra were recorded on either a Bruker DPX-
300, Bruker DRX-500 or a Bruker AC-200 spectrometers using as
internal standard tetramethylsilane and the central peak of CDCl3
(77 ppm), respectively. The 125Te NMR spectra were obtained in a
Bruker DRX-500 spectrometer operating at 157.79 MHz using
CDCl3 as the solvent. The 125Te chemical shifts refer to diphenyldi-
telluride (d = 420 ppm, 25 °C if dimethyltelluride is considered,
d = 0.0 ppm, 25 °C) as external standard. The 77Se NMR spectra
were obtained in a Bruker DRX-500 spectrometer operating at
95.338 MHz using CDCl3 as the solvent. The 77Se chemical shifts re-
fer to diphenyldiselenide (d = 463 ppm, 25 °C if dimethylselenide is
4.2.3. General procedure for the hydrotelluration of olefins [26]
In a two-necked 50 mL flask equipped as described in this sec-
tion. It was placed elemental tellurium (0.511 g, 4.0 mmol) in dry

2934
J.V. Comasseto et al. / Journal of Organometallic Chemistry 693 (2008) 2929–2936
THF (5 mL). To this suspension at room temperature it was added
n, s or t-butyllithium (4.0 mmol, 1.0 equiv.). A deep purple solution
was formed as the initial drops of the alkyllithium were added. By
the end of the addition of the alkyllithium the reaction mixture be-
came pale yellow. To this solution it was added water (0.18 mL,
10 mmol) previously deoxygenated under a N2 flow and sonica-
tion. Then the appropriate olefin or alkyne (4.0 mmol) was added
at room temperature. The mixture was maintained under stirring
at room temperature for 1 h. The organic phase was washed with
NH4Cl solution (3 Â 15 mL) and brine (3 Â 15 mL) and then dried
with MgSO4. The solution was filtered and the solvent was evapo-
rated. The residue was purified by silica gel column chromatogra-
phy eluting first with hexane and then with hexane/ethyl acetate
(10:1).
J = 7.3 Hz, 3H), 1.68–1.76 (dqt, J = 7.3 Hz, J = 6.9 Hz, 2H), 2.77–
2.82 (m, 2H), 2.86–2.92 (m, 2H), 3.32 (sx, J = 6.9 Hz, 1H). 13C
NMR (75 MHz, CDCl3, ppm) d 120.0, 32.9, 24.2, 22.2, 21.5, 13.8,
À7.1. 125Te RMN (157 MHz, CDCl3, ppm, (PhTe)2) d 465.9. LRMS:
m/z (70 eV, relative intensity, %): 241 (5, M+), 185 (11), 183 (10),
156 (9), 57 (65), 41 (100). IR (ZnSe, cmÀ1): 2960, 2923, 2870,
2247, 1455, 1420, 1376, 1250, 1186, 1164, 1133. Anal. Calc.: C,
35.21; H, 5.49; N, 5.87. Found: C, 35.28; H, 5.35; N, 5.84%.
3-(tert-Butyltellanyl)propanenitrile (6a): Yield, 0.79 g (83%). 1H
NMR: (300 MHz, CDCl3, ppm) d 1.66 (s, 9H), 2.89 (m, 4H). 13C NMR
(75 MHz, CDCl3, ppm) d 120.0, 67.8, 35.7, 21.1, À5.4. 125Te RMN
(157 MHz, CDCl3, ppm, (PhTe)2) d 684.7. LRMS: m/z (70 eV, relative
intensity, %): 241 (2, M+), 239 (2), 58 (5), 57 (100), 41 (48). IR (ZnSe,
cmÀ1): 2949, 2857, 2247, 1461, 1420, 1365, 1146, 1018, 907, 879.
Anal. Calc.: C, 35.21; H, 5.49; N, 5.87. Found: C, 35.20; H, 5.17; N,
5.77%.
Ethyl 3-(butylthio)propanoate (2e): (Registry Number: 68298-
26-0), Yield, 0.89 g (78%). 1H NMR (500 MHz, CDCl3, ppm) d 0.91
(t, 7.5 Hz, 3H), 1.27 (t, 7.5 Hz, 3H), 1.40 (sx, J = 7.5 Hz, 2H), 1.57
(qt, J = 7.5 Hz, 2H), 2.53 (t, 7.5 Hz, 2H), 2.59 (t, 7.5 Hz, 2H), 2.78
(t, 7.5 Hz, 2H), 4.15 (q, J = 7.5 Hz, 2H). 13C NMR (125 MHz, CDCl3,
ppm) d 171.7, 60.3, 34.7, 31.6, 31.4, 26.8, 21.7, 14.0, 13.4.
Ethyl 3-(butylselanyl)propanoate (3b): (Registry Number:
444145-05-5), Yield, 0.75 g (79%). 1H NMR: (300 MHz, CDCl3,
ppm) d 0.92 (t, J = 7.3 Hz, 3H), 1.26 (t, J = 7.2 Hz, 3H), 1.40 (sext,
J = 7.3 Hz, 2H), 1.65 (quint, J = 7.3 Hz, 2H), 2.59 (t, J = 7.4 Hz, 2H),
4-(Butylthio)butan-2-one (2c): (Registry Number: 69688-97-7),
Yield, 0.89 g (93%). 1H NMR (500 MHz, CDCl3, ppm) d 0.91 (t,
7.5 Hz, 3H), 1.41 (sx, J = 7.5 Hz, 2H), 1.56 (qt, J = 7.5 Hz, 2H), 2.17
(s, 3H), 2.52 (t, J = 7.5 Hz, 2H), 2.73 (s, 4H). 13C NMR (125 MHz,
CDCl3, ppm) d 206.9, 43.7, 32.1, 31.6, 30.0, 25.8, 21.9, 13.6.
4-(Butyltellanyl)butan-2-one (4b): (Registry Number: 444144-
98-3), Yield, 0.88 g (86%). 1H NMR: (300 MHz, CDCl3, ppm) d 0.92
(t, J = 7.4 Hz, 3H), 1.38 (sext, J = 7.4 Hz, 2H), 1.73 (q, J = 7.4 Hz,
2H), 2.15 (s, 3H), 2,69 (m, 4H), 3.03 (t, J = 7.4 Hz, 2H). 13C NMR
(75 MHz, CDCl3, ppm) d 207.8, 46.4, 34.3, 29.8, 25.0, 13.3, 3.4,
À7,0. 125Te RMN (157 MHz, CDCl3, ppm, (PhSe)2) d 279.6. LRMS:
m/z (70 eV, relative intensity, %): 258 (7, M+), 71 (40), 57 (24), 55
(26), 43 (100). IR (ZnSe, cmÀ1): 2955, 2925, 2865, 1715. Anal. Calc.:
C, 37.56; H, 6.30. Found: C, 37.32; H, 6.02%.
2.72 (A2B2,
Dm/J 1,5 Hz, J = 1.2 Hz, 4H), 4.14 (q, J = 7.2 Hz, 2H).
13C NMR (75 MHz, CDCl3, ppm) d 171.7, 60.1, 35.4, 32.2, 23.5,
22.5, 16.9, 13.8, 13.1. 77Se RMN (95 MHz, CDCl3, ppm, (PhSe)2) d
180.1. LRMS: m/z (70 eV, relative intensity, %): 238 (27, M+), 236
(13), 182 (30), 180 (15), 165 (11), 137 (11), 135 (60), 55 (100). IR
(ZnSe, cmÀ1): 2959, 2930, 2870, 1736, 1372, 1341, 1222, 1163,
1134, 1038. Anal. Calc.: C, 45.53; H, 7.58. Found: C, 45.38; H, 7.39%.
Ethyl 3-(butyltellanyl)propanoate (4d): (Registry Number:
444144-91-6), Yield, 1.10 g (96%). 1H NMR: (300 MHz, CDCl3,
ppm) d 0.92 (t, J = 7.4 Hz, 3H), 1.27 (t, J = 7.1 Hz, 3H), 1.38 (sext,
J = 7.4 Hz, 2H), 1.74 (quint, J = 7.4 Hz, 2H), 2.68 (t, J = 7.4 Hz, 2H),
4-(sec-Butyltellanyl)butan-2-one (5a): Yield, 0.87 g (85%). 1H
NMR: (300 MHz, CDCl3, ppm) d 0.97 (t, J = 7.2 Hz, 3H), 1.63 (d,
J = 7.2 Hz, 3H), 1.67 (quint, J = 7.2 Hz, 2H), 2.15 (s, 3H), 2,73 (tap
,
J = 7.2 Hz, 2H), 3.03 (t, J = 7.2 Hz, 2H), 3.20 (sext, J = 7.2 Hz, 1H).
13C NMR (75 MHz, CDCl3, ppm) d 207.9, 46.5, 33.0, 29.8, 24.3,
21.0, 13.9, 7.3. 125Te RMN (157 MHz, CDCl3, ppm, (PhSe)2) d
432.8. LRMS: m/z (70 eV, relative intensity, %): 258 (10, M+), 71
(42), 57 (36), 55 (21), 43 (100). IR (ZnSe, cmÀ1): 2960, 2926,
2913, 2870, 1718, 1452, 1375, 1180, 1138, 1127, 996. Anal. Calc.:
C, 37.55; H, 6.25. Found: C, 37.28; H, 6.41%.
2.83 (A2B2,
Dm
/J 1,1 Hz, 4H), 4.15 (q, J = 7.1 Hz, 2H). 13C NMR
3-(Butylthio)propanenitrile (2d): (Registry Number: 26901-99-
5), Yield, 0.77 g (90%). 1H NMR (300 MHz, CDCl3, ppm) d 0.92 (t,
J = 4.3 Hz, 3H), 1.42 (sx, J = 4.3 Hz, 2H), 1.58 (qt, J = 4.23 Hz, 2H),
2.58–2.61 (m, 2H), 2.64 (t, J = 4.3 Hz, 2H), 2.78–2.81 (m, 2H). 13C
NMR (75 MHz, CDCl3, ppm) d 118.4, 31.9, 31.5, 27.6, 21.8, 18.9,
13.6. IR (cmÀ1) 2959, 2930, 2869, 2249, 1461, 1423.
(75 MHz, CDCl3, ppm) d 173.1, 60.6, 37.5, 34.3, 25.1, 14.3, 13.4,
3.3, À5.8. 125Te RMN (157 MHz, CDCl3, ppm, (PhTe)2) d 279.2.
LRMS: m/z (70 eV, relative intensity, %): 288 (35), 286 (30, M+),
231 (28), 229 (26), 186 (29), 184 (28), 57 (94), 55 (100). IR (ZnSe,
cmÀ1): 2958, 2928, 2870, 1735. Anal. Calc.: C, 37.82; H, 6.35.
Found: C, 37.69; H, 6.35%.
3-(Butylselanyl)propionitrile (3a): (Registry Number: 1017904-
13-0), Yield, 0.74 g (97%). 1H NMR: (500 MHz, CDCl3, ppm) d 0.93
(t, J = 7.3 Hz, 3H), 1.41 (sext, J = 7.3 Hz, 2H), 1.66 (quint, J = 7.3 Hz,
2H), 2.68 (t, J = 7.3 Hz, 2H), 2.71–2.74 (m, 4H). 13C NMR
(125 MHz, CDCl3, ppm) d 118.8, 32.4, 24.5, 22.8, 19.7, 17.1, 13.5.
77Se RMN (95 MHz, CDCl3, ppm, (PhSe)2) d 19.7. LRMS: m/z
(70 eV, relative intensity, %): 191 (26, M+), 189 (13), 57 (79), 41
(100). IR (ZnSe, cmÀ1): 2959, 2930, 2868, 2249, 1461, 1421,
1263, 1200. Anal. Calc.: C, 44.22; H, 6.89; N, 7.37. Found: C,
44.35; H, 6.72; N, 7.38%.
Ethyl 3-(sec-butyltellanyl)propanoate (5b): (Registry Number:
444144-04-4), Yield, 1.08 g (95%). 1H NMR: (300 MHz, CDCl3,
ppm) d 0.98 (t, J = 7.3 Hz, 3H), 1.27 (t, J = 7.1 Hz, 3H), 1.64 (d,
J = 7.3 Hz, 3H), 1.68 (quint, J = 7.3 Hz, 2H), 2.77–2.90 (m, 4H),
3.20 (sext, J = 7.3 Hz, 1H), 4.15 (q, J = 7.1 Hz, 2H). 13C NMR
(75 MHz, CDCl3, ppm) d 173.0, 60.5, 37.5, 32.9, 24.3, 20.8, 14.1,
13.8, À6.1. 125Te RMN (157 MHz, CDCl3, ppm, (PhTe)2) d 433.3.
LRMS: m/z (70 eV, relative intensity, %): 288 (16, M+), 286 (15),
232 (17), 230 (16), 186 (33), 184 (31), 158 (26), 156 (24), 57
(96), 55 (60), 41 (100). IR (ZnSe, cmÀ1): 2961, 1735, 1454, 1372,
1200, 1133, 1038. Anal. Calc.: C, 37.82; H, 6.35. Found: C, 38.09;
H, 6.27%.
3-(Butyltellanyl)propanenitrile
(4c):
(Registry
Number:
444145-02-2), Yield, 0.93 g (98%). 1H NMR: (500 MHz, CDCl3,
ppm) d 0.93 (t, J = 7.4 Hz, 3H), 1.39 (sext, J = 7.4 Hz, 2H), 1.76
(quint, J = 7.4 Hz, 2H), 2.79 (t, J = 7.4 Hz, 2H), 2.80 (t, J = 7.2 Hz,
2H), 2.90 (t, J = 7.2 Hz, 2H). 13C NMR (75 MHz, CDCl3, ppm) d
120.0, 34.1, 24.9, 21.4, 13.3, 4.2, À6.8. 125Te RMN (157 MHz, CDCl3,
ppm, (PhTe)2) d 317.2. LRMS: m/z (70 eV, relative intensity, %): 241
(5, M+), 239 (4), 149 (15), 57 (33), 32 (100). IR (ZnSe, cmÀ1): 2957,
2927, 2870, 2247, 1461, 1421, 1248, 1160. Anal. Calc.: C, 32.21; H,
5.49; N, 5.87. Found: C, 35.39; H, 5.37; N, 5.74%.
Methyl 3-(butylselanyl)butanoate (3c): Yield, 0.78 g (82%). 1H
NMR: (300 MHz, CDCl3, ppm) d 0.89 (t, J = 7.2 Hz, 3H), 1.38 (sext,
J = 7.2 Hz, 2H), 1.44 (d, J = 7.2 Hz, 3H), 1.63 (quint, J = 7.2 Hz, 2H),
2.53–2.73 (abx, Jax = 6.6 Hz, Jbx = 8.2 Hz, Jab = 15.4 Hz, 4H), 3.30
(sext, J = 7.2 Hz, 1H), 3.67 (s, 3H). 13C NMR (75 MHz, CDCl3, ppm)
d 172.3, 51.8, 43.5, 32.9, 29.3, 23.3, 23.2, 22.8, 13.8. 77Se RMN
(95 MHz, CDCl3, ppm, (PhSe)2) d 285.3. LRMS: m/z (70 eV, relative
intensity, %): 238 (15, M+), 236 (8), 101 (31), 69 (19), 59 (100),
57 (20), 55 (25). IR (ZnSe, cmÀ1): 2957, 2928, 2868, 1740, 1210,
774. Anal. Calc.: C, 45.57; H, 7.65; Found: C, 45.58; H, 7.51%.
3-(sec-Butyltellanyl)propanenitrile (5a): Yield, 0.79 g (83%). 1H
NMR: (300 MHz, CDCl3, ppm) d 0.97 (t, J = 7.3 Hz, 3H), 1.64 (d,

J.V. Comasseto et al. / Journal of Organometallic Chemistry 693 (2008) 2929–2936
2935
Methyl 3-(butyltellanyl)butanoate (4e): (Registry Number:
444144-94-9), Yield, 0.94 g (82%). 1H NMR: (500 MHz, CDCl3,
ppm) d 0.92 (t, J = 7.4 Hz, 3H), 1.39 (sext, J = 7.4 Hz, 2H), 1.66 (d,
J = 7.2 Hz, 3H), 1.76 (q, J = 7.5 Hz, 2H), 2.71 (dt, J = 7.8 Hz,
J = 15 Hz, 2H), 2.80 (abx, Jax = 6.8 Hz, Jbx = 7.8 Hz, Jab = 15.0 Hz,
2H), 3.49 (sext, J = 7.2 Hz, 1H), 3.69 (s, 3H). 13C NMR (125 MHz,
CDCl3, ppm) d 172.6, 51.6, 45.4, 34.4, 25.2, 24.9, 13.4, 9.2, 3.2.
125Te RMN (157 MHz, CDCl3, ppm, (PhTe)2) d 456.3. LRMS: m/z
(70 eV, relative intensity, %): 288 (7, M+), 286 (7), 101 (23), 69
(14), 59 (100), 57 (37), 55 (15). IR (ZnSe, cmÀ1): 2956, 2926,
2870, 1738, 1203, 722. Anal. Calc.: C, 37.82; H, 6.35. Found: C,
37.73; H, 6.39%.
3-(Butyltellanyl)cyclohexanone (4h): (Registry Number:
444144-99-4), Yield, 1.00 g (89%). 1H NMR: (300 MHz, CDCl3,
ppm) d 0.92 (t, J = 7.3 Hz, 3H), 1.38 (sext, J = 7.3 Hz, 2H), 1.77
(quint, J = 7.4 Hz, 2H), 1.77 (m, 1H), 1.93 (m, 1H), 2.07 (m, 1H),
2.29 (m, 1H), 2.39 (m, 1H), 2.63 (dd, J = 1.6 Hz, J = 2.6 Hz, 1H),
2.71 (t, J = 7.4 Hz, 2H), 2.90 (dt, J = 1.6 Hz, 1H), 3.46 (tt, J = 3.4 Hz,
1H). 13C NMR (75 MHz, CDCl3, ppm) d 208.9, 51.3, 41.0, 34.7,
34.3, 27.7, 25.1, 16.1, 13.3, 3.3. 125Te RMN (157 MHz, CDCl3, ppm,
(PhSe)2) d 441.7. LRMS: m/z (70 eV, relative intensity, %): 284 (1,
M+), 97 (13), 96 (16), 69 (33), 68 (72), 57 (52), 55 (36), 41 (100).
IR (ZnSe, cmÀ1): 2955, 2926, 2869, 2258, 1710. Anal. Calc.: C,
42.61; H, 6.44. Found: C, 42.32; H, 6.51%.
Ethyl 3-(butyltellanyl)butanoate (4f): (Registry Number:
444145-03-3), Yield, 0.98 g (82%). 1H NMR: (300 MHz, CDCl3,
ppm) d 0.92 (t, J = 7.4 Hz, 3H), 1.27 (t, J = 7.1 Hz, 3H), 1.39 (sext,
J = 7.3 Hz, 2H), 1.66 (d, J = 7.2 Hz, 3H), 1.76 (q, J = 7.4 Hz, 2H),
2.71 (dt, J = 7.5 Hz, J = 2.7 Hz, 2H), 2.78 (abx, Jax = 7.0 Hz,
Jbx = 8.0 Hz, Jab = 16.0 Hz, 2H), 3.49 (sext, J = 7.1 Hz, 1H), 4.15 (q,
J = 7.1 Hz, 2H). 13C NMR (75 MHz, CDCl3, ppm) d 172.1, 60.5, 45.6,
34.4, 25.2, 24.9, 14.2, 13.4, 9.3, 3.1. 125Te RMN (157 MHz, CDCl3,
ppm, (PhTe)2) d 455.6. LRMS: m/z (70 eV, relative intensity, %):
302 (11, M+), 166 (11), 148 (67), 114 (16), 87 (43), 83 (18), 73
(56), 57 (100). IR (ZnSe, cmÀ1): 2957, 2926, 2870, 1735, 1461,
1196, 1030. Anal. Calc.: C, 40.05; H, 6.72. Found: C, 40.12; H, 6.50%.
Ethyl 3-(butylselanyl)-2-methylpropanoate (3d): Yield, 0.81 g
(81%). 1H NMR: (300 MHz, CDCl3, ppm) d 0.91 (t, J = 7.3 Hz, 3H),
1.25 (d, J = 6.7 Hz, 3H), 1.27 (t, J = 7.1 Hz, 3H), 1.39 (sext,
J = 7.3 Hz, 2H), 1.64 (quint, J = 7.4 Hz, 2H), 2.60 (m, 3H), 2.70 (sext,
J = 6.7 Hz, 1H), 2.84 (dd, J = 6.7 Hz, 1H), 4.15 (q, J = 7.1 Hz, 2H). 13C
NMR (75 MHz, CDCl3, ppm) d 175.2, 60.4, 40.9, 32.6, 26.7, 24.4,
22.9, 17.6, 14.1, 13.5. 77Se RMN (95 MHz, CDCl3, ppm, (PhSe)2) d
153.3. LRMS: m/z (70 eV, relative intensity, %): 252 (18, M+), 250
(9), 196 (8), 168 (11), 150 (21), 148 (11), 122 (24), 115 (23), 87
(33), 41 (100). IR (ZnSe, cmÀ1): 2964, 2930, 2870, 1734. Anal. Calc.:
C, 47.76; H, 7.96. Found: C, 47.97; H, 7.94%.
Ethyl 3-(butyltellanyl)-2-methylpropanoate (4g): (Registry
Number: 444145-03-3), Yield, 1.08 g (90%). 1H NMR: (300 MHz,
CDCl3, ppm) d 0.92 (t, J = 7.3 Hz, 3H), 1.26 (dt, J = 7.2 Hz, 6H),
1.37 (sext, J = 7.2 Hz, 2H), 1.72 (quint, J = 7.4 Hz, 2H), 2.70 (m,
4H), 2.89 (m, 1H), 4.15 (q, J = 7.2 Hz, 2 H). 13C NMR (75 MHz, CDCl3,
ppm) d 175.3, 60.4, 41.8, 34.1, 24.9, 19.2, 14.1, 13.3, 5.4, 3.5. 125Te
RMN (157 MHz, CDCl3, ppm, (PhSe)2) d 221.1. LRMS: m/z (70 eV,
relative intensity, %): 302 (19, M+), 245 (20), 172 (19), 168 (11),
115 (16), 87 (33), 57 (70), 55 (47), 43 (22), 41 (100). IR (ZnSe,
cmÀ1): 2963, 2928, 1732, 1456, 1374, 1252, 1192, 1152, 1045,
1023. Anal. Calc.: C, 40.05; H, 6.67. Found: C, 39.89; H, 6.46%.
3-(Butylthio)cyclohexanone (2f): (Registry Number: 505062-
31-7), Yield, 1.08 g (97%). 1H NMR (500 MHz, CDCl3, ppm) d 0.91
(t, J = 7.0 Hz, 3H), 1.40 (sext, J = 7.5 Hz, 2H), 1.56 (qt, J = 7.5 Hz,
2H), 1.69–1.75 (m, 2H), 2.10–2.17 (m, 2H), 2.28–2.40 (m, 3H),
2.55 (t, J = 7.5 Hz, 2H), 2.68–2.73 (m, 1H), 3.03–3.08 (m, 1H). 13C
NMR (125 MHz, CDCl3, ppm) d 208.8, 48.1, 42.6, 40.8, 31.6, 31.5,
30.1, 24.1, 21.9, 13.5.
3-(Butylthio)-4,4-dimethylcyclohexanone (2g): (Registry Num-
ber: 50987-48-9), Yield, 1.23 g (96%). 1H NMR (500 MHz, CDCl3,
ppm) d 0.90 (t, J = 7.0 Hz, 3H), 1.12 (s, 3H), 1.20 (s, 3H), 1.40 (dsx,
J = 7.0 Hz, 3.0 Hz, 2H), 1.51–1.64 (m, 3H), 1.86 (ddd, J = 14 Hz,
6 Hz, 4 Hz, 1H), 2.27–2.32 (m, 1H) 2.40–2.47 (m, 1H) 2.50–2.56
(m, 3H), 2.67–2.71 (m, 2H). 13C NMR: (125 MHz, CDCl3, ppm) d
208.8, 53.2, 45.6, 38.4, 37.5, 34.2, 31.6, 31.5, 28.6, 21.6, 20.3, 13.3.
3-(Butyltellanyl)-4,4-dimethylcyclohexanone (4i): (Registry
Number: 444145-00-0), Yield, 0.77 g (62%). 1H NMR: (300 MHz,
CDCl3, ppm) d 0.91 (t, J = 7.3 Hz, 3H), 1.17 (s, 2H), 1.20 (s, 3H),
1.37 (sext, J = 7.3 Hz, 2H), 1.72 (quint, J = 7.3 Hz, 2H), 1.77 (m,
1H), 1.97–2.05 (m, 1H), 2.30–2.39 (m, 1H), 2.43–2.56 (m, 1H),
2.66 (td, J = 1.7 Hz, J = 7.3 Hz, 2H), 2.80–2.97 (m, 2H), 3.23 (dd,
J = 5.2 Hz, J = 12.3 Hz, 1H). 13C NMR (75 MHz, CDCl3, ppm) d
209.8, 49.2, 38.2, 38.0, 35.2, 34.5, 34.1, 31.7, 25.4, 23.5, 13.6, 4.2.
125Te RMN (157 MHz, CDCl3, ppm, (PhSe)2) d 361.3. LRMS: m/z
(70 eV, relative intensity, %): 312 (6, M+), 125 (34), 96 (11), 83
(39), 69 (44), 57 (25), 55 (100), 41 (61). IR (ZnSe, cmÀ1): 2956,
2924, 2864, 1713. Anal. Calc.: C, 46.51; H, 7.16. Found: C, 46.49;
H, 7.21%.
(5R)-2-(2-(Butylthio)propan-2-yl)-5-methylcyclohexanone (2h):
(Registry Number: 1017904-05-0), Yield, 0.96 g (66%). 1H NMR
(300 MHz, CDCl3, ppm) d 0.86–0.96 (m, 3H), 0.98–1.02 (m, 3H),
1.32–1.59 (m, 10H), 1.77–2.08 (m, 5H), 2.26–2.32 (m, 1H), 2.40–
2.60 (m, 4H). 13C NMR (75 MHz, CDCl3, ppm) d 210.4, 57.8, 52.2,
46.6, 36.5, 34.5, 31.3, 29.4, 27.7, 27.1, 23.7, 22.1, 22.0, 13.5. IR
(cmÀ1) 1121, 1456, 1711, 2871, 2928, 2957. HRMS calc. for
[C14H26OS+Na]+: 247.1132. Found: 247.1128%.
3-(Butylthio)-1,3-diphenylpronan-1-one (2i): (Registry Num-
ber: 21205-11-8), Yield, 1.14 g (64%). 1H NMR (300 MHz, CDCl3,
ppm) d 0.81 (t, J = 7.2 Hz, 3H), 1.25–1.35 (m, 2H), 1.42–1.52 (m,
2H), 2.24–2.41 (m, 2H), 3.52 (d, J = 7.2Hz, 2H), 4.55 (t, J = 7.2 Hz,
1H), 7.15–7.52 (m, 8H), 7.87–7.90 (m, 2H). 13C NMR (75 MHz,
CDCl3, ppm) d 196.7, 142.0, 136.7, 132.9, 128.4, 128.3, 127.9,
127.7, 127.0, 45.3, 44.2, 31.1, 31.0, 21.7, 13.4. IR (cmÀ1) 2952,
2922, 1961, 1890, 1815, 1769, 1678, 1229.
(Z)-ethyl-3-(butylthio)acrylate (2j):(Registry Number: 875822-
74-5), Yield, 0.90 g (80%). 1H NMR (500 MHz, CDCl3, ppm) d 0.93
(t, J = 7.5 Hz, 3H), 1.28 (t, J = 7.0 Hz, 3H), 1.44 (sx, J = 7.5 Hz, 2H),
1.66 (quint, J = 7.5 Hz, 2H), 2.76 (t, J = 7.5 Hz, 2H), 4.19 (qt,
J = 7.5 Hz, 2H), 5.83 (d, J = 10 Hz, 1H), 7.10 ( d, J = 10 Hz, 1H). 13C
NMR (125 M Hz, CDCl3, ppm) d 166.4, 150.2, 112.6, 59.7, 35.5,
32.1, 21.3, 14.1, 13.3. IR (cmÀ1) 2959, 2931, 2873, 1698, 1569,
1373, 1211, 1105, 1034, 799.
3-(Butylselanyl)cyclohexanone
(3g): (Registry Number:
444145-06-6), Yield, 0.76g (82%). 1H NMR: (300 MHz, CDCl3,
ppm) d 0.91 (t, J = 7.2 Hz, 3H), 1.39 (sext, J = 7.2 Hz, 2H), 1.64
(quint, J = 7.2 Hz, 2H), 1.71–1.88 (m, 2H), 2.07–2.26 (m, 2H),
2.32–2.40 (m, 2H), 2.49 (ddd, J = 1.1 Hz, J = 10.7 Hz, J = 14.3 Hz,
1H), 2.61 (m, 2H), 2.79 (ddt, J = 1.3 Hz, J = 4.6 Hz, J = 14.3 Hz, 1H),
3.16–3.38 (m, 1H). 13C NMR (75 MHz, CDCl3, ppm) d 208.8, 49.3,
40.9, 35.7, 32.7, 32.5, 25.4, 23.1, 23.0, 13.5. 77Se RMN (95 MHz,
CDCl3, ppm, (PhSe)2) d 276.5. LRMS: m/z (70 eV, relative intensity,
%): 234 (12, M+), 97 (58), 96 (6), 69 (100), 68 (13), 57 (10), 55 (65),
41 (99). IR (ZnSe, cmÀ1): 2957, 2931, 2868, 1713, 1448, 1421,
1312, 1276, 1220. Anal. Calc.: C, 51.50; H, 7.78. Found: C, 51.32;
H, 7.60%.
4.3. Hydrochalcogenation followed by reduction
4.3.1. Hydrosulfenilation followed by reduction
The lithium nbutanethiolate solution was prepared from ele-
mental sulfur (0.20 g, 6.0 mmol) as described in Section 4.2.1.
Deoxygenated water (0.27 mL, 15.0 mmol) was slowly added to
the lithium nbutanethiolate solution. The resulting colorless solu-
tion was stirred for 10 min and then the
a,b-unsaturated aldehyde
(6.0 mmol) was added in one portion and the solution was stirred

2936
J.V. Comasseto et al. / Journal of Organometallic Chemistry 693 (2008) 2929–2936
for additional 30 min. After the reaction was complete, the alde-
hyde was reduced in situ with excess of sodium borohydride in eth-
anol. The product was extracted with ethyl acetate (3 Â 20 mL).
The combined organic layers were dried over magnesium sulfate
and concentrated under reduced pressure. Column chromatogra-
phy (4:1 hexane/ethyl acetate) of the crude oil on silica gel affor-
ded a colorless oil.
3-(Butylthio)propan-1-ol (7a): (Registry Number: 26901-99-5),
Yield, 0.44 g (50%). 1H NMR (200 MHz, CDCl3, ppm) d 0.92 (t,
J = 7.0 Hz, 3H), 1.31–1.65 (m, 4H), 1.84 (qt, J = 7.0 Hz, 2H), 2.53 (t,
J = 7.0 Hz, 2H), 2.63 (t, J = 7.0 Hz, 2H), 3.01 (s, 1H), 3.75 (t,
J = 7.0 Hz, 2H). 13C NMR (50 MHz, CDCl3, ppm) d 61.6, 31.7, 31.6,
31.5, 28.6, 21.9, 13.5. IR (cmÀ1) 3362, 2956, 2930, 28721741,
1721, 1650, 1462, 1059.
3-(Butylthio)-3-phenylpropan-1-ol (7b): (Registry Number:
1017904-13-0), Yield: 0.63 g (50%). 1H NMR (500 MHz, CDCl3,
ppm) d 0.82 (t, 7.2 Hz, 3H), 1.22–1.50 (m, 4H), 1.99–2.15 (m, 2H),
2.22–2.36 (m, 2H), 3.51–3.74 (m,2H), 3.95 (t, 7.5 Hz, 1H), 7.18–
7.33 (m, 5H). 13C NMR (125 MHz, CDCl3, ppm) d 142.5, 128.3,
127.6, 126.9, 60.4, 46.3, 39.0, 31.2, 30.5, 21.8, 13.4.
34.2, 34.6, 63.9. 125Te NMR (157.79 MHz, CDCl3, 25°C Ph2Te2,
ppm) d 244.45. LRMS: m/z (70 eV, relative intensity, %): 246 (M+2
,
26%), 244 (M+, 24%), 242 (15%), 240 (3%), 188 (6%), 186 (7%), 172
(23%), 170 (23%), 168 (13%), 144 (4%), 142 (2%), 130 (6%), 126
(4%), 57 (100%), 41 (86%).
Acknowledgements
The authors thank FAPESP, CNPq and CAPES for support.
References
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(b) T.G. Back, Organoselenium Chemistry:
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4.4. Hydrotelluration followed by reduction
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4.4.1. Hydrotelluration of acrolein followed by reduction of
3-(butyltellanyl)propanal (4a)
A solution of lithium nbutyltellurolate was prepared from 1.28 g
(10 mmol) of elemental tellurium as described in Section 4.2.3. To
the yellow solution it was added deoxygenated water (0.43 mL,
24 mmol). The mixture was stirred for 5 min and then acrolein
(0.67 mL, 10 mmol) was added in one portion. The resulting red
mixture was stirred for 30 min and then NaBH4 (0.38 g, 10 mmol)
was added in one portion followed by addition of LiCl (42 mg,
1 mmol). The progress of the reaction was monitored by TLC and
then it was quenched with water (20 mL) and a mixture of ethyl
acetate/hexane (1:1, 50 mL). The phases were separated and the
aqueous phase was washed with a mixture of ethyl acetate/hexane
(1:1.2, 50 mL). The organic phases were combined, dried with mag-
nesium sulfate, filtered and the solvents were removed under re-
duced pressure. The residue was purified by silica gel
chromatography eluting with a mixture of hexane/ethyl acetate
(4:1). Yield of 8: 2.09 g (85%).
[5] (a) J.V. Comasseto, A.S. Guarezemini, Product class 6: acyclic alkanethiolates of
group 1, 2, and 13–15 metals, in: Science of Synthesis, Houben-Weyl, Methods
of Molecular Transformations, Thieme, Stuttgart, 2008, p. 413;
(b) J.V. Comasseto, A.S. Guarezemini, Product class 5: alkanethiols, in: Science
of Synthesis, Houben-Weyl, Methods of Molecular Transformations, Thieme,
Stuttgart, 2008, p. 391.
[6] J.F. Boscato, J.M. Catala, E. Franta, J. Brossas, Tetrahedron Lett. 21 (1980) 1519.
[7] (a) A.T. Khan, S. Ghosh, L.H. Choudhury, Eur. J. Org. Chem. (2006) 2226;
(b) See for example: B.C. Ranu, T. Mandal, Can. J. Chem. 84 (2006) 762;
(c) F.M. Moghaddam, G.R. Bardajee, R.O.C. Veranlou, Synth. Commun. 35
(2005) 2427;
(d) B.C. Ranu, S.S. Dey, Tetrahedron 60 (2004) 4183;
(e) B.C. Ranu, S.S. Dey, A. Hajra, Tetrahedron 59 (2003) 2417;
(f) N. Srivastava, B.K. Banik, J. Org. Chem. 68 (2003) 2109.
[8] X. Huang, Z.C. Xiong, Tetrahedron Lett. 44 (2003) 5913.
[9] J.V. Comasseto, A.S. Guarezemini, Product class 19: acyclic alkaneselenolates of
group 1, 2, and 13–15 metals, in: Science of Synthesis, Houben-Weyl, Methods
of Molecular Transformations, Thieme, Stuttgart, 2008, p. 947.
[10] J.V. Comasseto, A.S. Guarezemini, Product class 18: alkaneselenols, in: Science
of Synthesis, Houben-Weyl, Methods of Molecular Transformations, Thieme,
Stuttgart, 2008, p. 941.
[11] C. Köllemann, D. Obendorf, F. Sladky, Phosphorus Sulfur 38 (1988) 69.
[12] J.V. Comasseto, A.S. Guarezemini, Product class 31: alkanetellurols, in: Science
of Synthesis, Houben-Weyl, Methods of Molecular Transformations, Thieme,
Stuttgart, 2008, p. 1137.
[13] J.V. Comasseto, A.S. Guarezemini, Product class 32: acyclic alkanetellurolates
of group 1, 2, and 13–15 metals, in: Science of Synthesis, Houben-Weyl,
Methods of Molecular Transformations, Thieme, Stuttgart, 2008, p. 1139.
[14] (a) M.L. Vieira, F.K. Zinn, J.V. Comasseto, J. Braz. Chem. Soc. 12 (2001) 586;
(b) G. Zeni, H.B. Formiga, J.V. Comasseto, Tetrahedron Lett. 41 (2000) 1311.
[15] K. Ohe, H. Takahashi, S. Uemura, N. Sugita, Nippon Kagaku Kaishi (1987) 1469.
[16] F.K. Zinn, V.E. Righi, S.C. Luque, H.B. Formiga, J.V. Comasseto, Tetrahedron Lett.
43 (2002) 1625.
[17] J.V. Comasseto, A.A. Dos Santos, Phosphorus Sulfur Silicon 183 (2008) 939.
[18] A.A. Dos Santos, J.L. Princival, J.V. Comasseto, S.M.G. de Barros, J.E. Brainer
Neto, Tetrahedron 63 (2007) 5167.
[19] A.A. Dos Santos, C.E. Da Costa, J.L. Princival, J.V. Comasseto, Tetrahedron:
Asymm. 17 (2006) 2252.
[20] J.L. Princival, S.M.G. Barros, J.V. Comasseto, A.A. Dos Santos, Tetrahedron Lett.
46 (2005) 4423.
[21] A.A. Dos Santos, J.L. Princival, J.V. Comasseto, unpublished results.
[22] A.A. Dos Santos, R.S. Ferrarini, J.L. Princival, J.V. Comasseto, Tetrahedron Lett.
47 (2006) 8933.
[23] A.A. Dos Santos, R.S. Ferrarini, J.L. Princival, J.V. Comasseto, J. Braz. Chem. Soc.
000 (2008).
[24] (a) See for example: P.A. Grieco, M. Miyashita, Tetrahedron Lett. (1974) 1869;
(b) K.B. Sharpless, M.W. Young, R.F. Lauer, Tetrahedron Lett. (1973) 1979.
4.4.2. Hydrotelluration of ethyl acrylate followed by reduction of
3-butyltelanylpropionic acid ethyl ester (4d)
A solution of lithium nbutyltellurolate was prepared from 0.64 g
(5 mmol) of elemental tellurium as described in Section 4.2.3. To
the yellow solution it was added deoxygenated water (0.22 mL,
12 mmol). The mixture was stirred for 5 min and then ethyl acry-
late (0.54 mL, 5 mmol) was added in one portion. The resulting red
mixture was stirred for 30 min and then LiAlH4 (0.57 g, 15 mmol)
was added in three portions. The progress of reaction was moni-
tored by TLC and then it was quenched with water (20 mL) and a
mixture of ethyl acetate/hexane (1:1, 50 mL). The phases were sep-
arated and the aqueous phase was washed with a mixture of ethyl
acetate/hexane (1:1.2, 50 mL). The organic phases were combined,
dried with magnesium sulfate, filtered and the solvents were re-
moved under reduced pressure. The residue was purified by silica
gel chromatography eluting with a mixture of hexane/ethyl acetate
(4:1). Yield of 8: 1.92 g (78%).
3-(Butyltellanyl)propan-1-ol (8): 1H RMN: (Registry Number:
943643-06-9), (300 MHz, CDCl3, ppm) d 0.89 (t, J3 = 7.2 Hz, 3H),
1.36 (sext, J3 = 7.2 Hz, 2H), 1.70 (quint, J3 = 7.5 Hz, 2H), 1.91–2.00
(m, 3H), 2.63 (t, J3 = 7.5 Hz), 2.66 (t, J3 = 7.5 Hz), 3.66 (t,
J3 = 6.3 Hz). 13C RMN (75 MHz, CDCl3, ppm) d 2.1, 2.8, 13.3, 25.0,
[25] For
a preliminary communication see: R.A. Gariani, A.A. Dos Santos, J.V.
Comasseto, Synth. Commun. 38 (2008) 789.
[26] For a preliminary communication see Ref. [16].