Cesium hydroxide-catalyzed reaction of terminal alkynes with diarylditellurides to synthesize alkynyl tellurides

Article abstract of DOI:10.1080/00397910802026519

In the presence of a catalytic amount of cesium hydroxide under an air atmosphere, the reaction of diarylditellurides (1.0 mmol) with terminal alkynes (2.2 mmol) at room temperature exclusively give alkynyl tellurides in good yields. Copyright Taylor & Fr

Full text of DOI:10.1080/00397910802026519

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Cesium Hydroxide–Catalyzed
Reaction of Terminal Alkynes
with Diarylditellurides to
Synthesize Alkynyl Tellurides
Kang Bing Zou a , Ren Hua Qiu a , Da Wei Fang a , Xin
You Liu a & Xin Hua Xu a
a College of Chemistry and Chemical Engineering,
Hunan University , Changsha, China
Published online: 18 Aug 2008.
To cite this article: Kang Bing Zou , Ren Hua Qiu , Da Wei Fang , Xin You Liu &
Xin Hua Xu (2008) Cesium Hydroxide–Catalyzed Reaction of Terminal Alkynes with
Diarylditellurides to Synthesize Alkynyl Tellurides, Synthetic Communications: An
International Journal for Rapid Communication of Synthetic Organic Chemistry, 38:13,
2237-2242, DOI: 10.1080/00397910802026519
To link to this article: http://dx.doi.org/10.1080/00397910802026519
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Synthetic Communications1, 38: 2237–2242, 2008
Copyright # Taylor & Francis Group, LLC
ISSN: 0039-7911 print/1532-2432 online
DOI: 10.1080/00397910802026519
Cesium Hydroxide–Catalyzed Reaction of
Terminal Alkynes with Diarylditellurides to
Synthesize Alkynyl Tellurides
Kang Bing Zou, Ren Hua Qiu, Da Wei Fang,
Xin You Liu, and Xin Hua Xu
College of Chemistry and Chemical Engineering,
Hunan University, Changsha, China
Abstract: In the presence of a catalytic amount of cesium hydroxide under an
air atmosphere, the reaction of diarylditellurides (1.0 mmol) with terminal alkynes
(2.2 mmol) at room temperature exclusively give alkynyl tellurides in good yields.
Keywords: Alkynyl telluride; Cesium hydroxide; Diarylditelluride; Terminal
alkyne
Cesium base has received increasing interest in the past few years, and
many articles have reported its powerful basicity, offering a new reagent
for the formation of a variety of carbon–heteroatom and carbon–carbon
bonds. Because of its strong basicity, it can efficiently promote many
reactions such as areneselenylation of aryl bromides and iodides;[1]
three-component coupling of aliphatic alcohols, CO2, and alkyl halides;[2]
cross-coupling reaction of arylsilanols with substituted aryl halide;[3]
a
one-pot, two-step synthesis of tetrahydro asterriquinone E;[4] palladium-
catalyzed amination of aryl iodide;[5] O-alkylation of alcohols for the
efficient ether synthesis and mixed alkyl carbonates;[6,7] Se-alkylation of
benzeneselenol and benzeneselenenyl bromide for the highly efficient syn-
thetic unsymmetrical organoselenides;[8] N-alkylation of primary amines
for the efficient preparation of secondary amines;[9] and so on. Cesium
base can react with terminal alkynes to give a nucleophilic alkynide
Received in the USA September 15, 2007
Address correspondance to Xin Hua Xu, College of Chemistry and Chemical
Engineering, Hunan University, Changsha 410082, China. E-mail: xhx1581@
21cn.com
2237

2238
K. B. Zou et al.
Table 1. Synthesis of alkynyl tellurides 3a–g
Entry
R
Ar
Mp (ꢀC)
Yield (%)
3a
3b
3c
3d
3e
3f
CH3OCH2
C6H5OCH2
HOCH2
n-C6H13
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
Oil
Oil
Oil
Oil
89
83
78
86
86
88
90
Oil
70–71[12]
69–70[20]
C6H5
C6H5
p-CH3OC6H4
p-CH3C6H4
3g
anion. Literature reports show that cesium hydroxide catalyzed alkynyla-
tion of aldehyde, ketones, and nitrills[10] and promoted the reaction of
terminal alkynee with benzeneselenenyl bromide.[8] Our group reported
the cesium hydroxide catalyzed a reaction of terminal alkynes with
diaryldiselenides, and the results showed that under an air atmos-
phere and at room temperature, it gave a mixture of (Z)-1,2-bis-
(aryseleno)-1-alkenes and alkynyl selenides. Under an N2 atmosphere
and at room temperature, the reaction gave exclusively (Z)-1,2-bis-
(aryseleno)-1-alkenes.[11] Diarylditelluride is similar to diaryldiselenide
in properties, and this promoted us to investigate the reaction of terminal
alkynes with diarylditellurides in the presence of a catalytic amount of
cesium hydroxide. In this article we report the results.
The experiments showed that in the presence of a catalytic amount
of cesium hydroxide (0.2 mmol), using tetrahydrofuran (THF) as solvent, at
room temperature and under an air atmosphere, terminal alkynes (2.2 mmol)
reacted with diarylditellurides (1.0 mmol) to give exclusively alkynyl tellurides
in good yields (Scheme 1). The results are summarized in Table 1.
The mechanism of the cesium hydroxide–catalyzed reaction is
described in Scheme 2.
The terminal alkynes reacted with cesium hydroxide to give water and
acetylide ion, which reacted with diarylditellurides to give alkynyl tellurides
and cesium aryltelluride. The latter was oxidized by oxygen in the presence
of water and was converted into the starting diarylditelluride. Thus, to
make ArTeTeAr react completely, air is necessary. In the absence of oxy-
gen, the highest yields of alkynyl tellurides are 50% based on telluride atom.
We investigated the case under an N2 atmosphere, and the result
showed it gave only alkynyl telluride. About 50% diarylditelluride was
Scheme 1. Cesium hydroxide catalyzed alkynyl tellurides synthesis.

Synthesis of Alkynyl Tellurides
2239
Scheme 2. The possible mechanism of the reaction.
recovered, and no 1,2-bis(arytelluro)-1-alkene was obtained. This result
indicated that in room temperature and in THF, the ArTeCs cannot
undergo the nucelophilic addition to alkynyl tellurides. Under the same
conditions, ArSeCs could efficiently carry out addition to alkynyl sele-
nides.[11] It is well known that ArTeM is a stronger nucleophile than
ArSeM in the usual nucleophilic substitution reaction. Thus, the differ-
ence in the reaction is because arylselenovinylic anions have higher stab-
ility than the corresponding aryltellurovinylic anions.
The alkynyl tellurides is an important synthetic intermediate.
Some methods to prepare alkynyl tellurides were developed, such as
the reaction of the lithium alkynides with elemental tellurium, followed
by trapping the intermediates lithium tellurolates with alkyl halides or
by the reaction of the corresponding lithium alkynylides with aryl-
tellurium bromides,[12,13] treatment of haloacetylenes with lithium
organotellurolates,[14] reaction of appropriate terminal alkynes with phe-
nyltellurium bromide in the presence of cuprious iodide,[15] reaction of
terminal alkynes with diarylditellurides in DMSO in the presence of
cuprious iodide, treatment of alkynylphenyliodonium tosylates with
sodium arenetellurolates,[16] treatment of arenetellurenyl halides
with Grignard reagents,[17] and the reaction of arenetellurenamides with
terminal alkynes.[18] However, these methods are deficient in some
respects; they are expensive or toxic, use not readily available reagents,
have strict reaction conditions or difficulties with isolation of the pro-
ducts, or have limited scope.
The present method has its own advantages: atom economy based
on tellurium, readily available starting materials, undried and nontoxic
solvent, no inert atmosphere, mild conditions, and simple reaction
and workup procedures. It provides a simple and practical path for the
preparation of alkynyl tellurides.
EXPERIMENTAL
1H NMR and 13C NMR were recorded on an Inova-400 spectrometer
using CDCl3 as the solvent with TMS as an internal standard. MS spectra
were determined on an HP5989A spectrometer.

2240
K. B. Zou et al.
General Procedure for the Preparation of Alkynyl Tellurides
Diaryl ditelluride (1.0 mmol) and cesium hydroxide (30 mg, 0.2 mmol)
were added to a solution of alkynes (2.2 mmol) in THF (10.0 mL). The
reaction mixture was stirred at room temperature for 48 h under an air
atmosphere and monitored by thin-layer chromatography (TLC) until
the diarylditelluride was fully reacted. After removal of THF under vac-
uum, 10 mL of water were added to the residue and extracted with
petroleum ether (3 ꢁ 30 ml). The combined organic phase was dried over
anhydrous Na2SO4 and concentrated under vacuum. The residue was
purified by flash chromatography and eluted with petroleum ether=ethyl
ethyl ether (30:1) to give 3a–g.
Data
1
Compound 3a: IR (film) n=cmꢂ1: 2150; H NMR 3.42 (s, 3H), 4.39
(s, 2H), 7.26–7.28 (m, 3H), 7.69–7.71 (m, 2H); 13C NMR 135.4, 129.7,
128.0, 112.4, 111.0, 61.0, 57.6, 44.8; MS (m=z): 276 (Mþ).
Compound 3b: IR (film) n=cmꢂ1: 2145; 1H NMR 4.93 (s, 2H), 6.96–
6.98 (m, 4H), 7.22–7.31 (m, 4H), 7.62–7.64 (m, 2H), 13C NMR 157.6,
135.5. 129.7, 129.4, 128.0, 121.4, 115.0, 112.3, 109.9, 57.1, 29.7; MS
(m=z): 333 (Mþ).
1
Compound 3c: IR (film) n=cmꢂ1: 2140; H NMR 2.02 (s, 1H), 4.53
(s, 2H), 7.27–7.28 (m, 3H), 7.70–7.72 (m, 2H); MS (m=z): 262 (Mþ).
1
Compound 3d[19]: IR (film) n=cmꢂ1: 2140; H NMR 0.87 (t, 3H),
1.07–1.74 (m, 8H), 2.58 (t, J ¼ 6.9 Hz, 2H), 7.10–7.26 (m, 3H), 7.53–
7.74 (m, 2H); MS (m=z): 316 (Mþ).
Compound 3e: IR (film) n=cmꢂ1: 2135; 1H NMR 7.26–7.30 (m, 1H),
7.33–7.36 (m, 5H), 7.51–7.53 (m, 2H), 7.59–7.62 (m, 2H); MS (m=z): 308
(Mþ).
1
Compound 3f: IR (KBr) n=cmꢂ1: 2140; H NMR 3.70 (s, 3H), 6.79
(d, J ¼ 9.0 Hz, 2H), 7.30 (m, 5H), 7.71 (d, J ¼ 9.0 Hz, 2H); MS (m=z): 338
(Mþ).
1
Compound 3g: IR (KBr) n=cmꢂ1: 2140; H NMR 2.34 (s, 3H), 7.14
(d, 2H, J ¼ 8.0 Hz), 7.31–7.33 (m, 3H), 7.47–7.49 (m, 4H); MS (m=z): 322
(Mþ).
ACKNOWLEDGMENT
Projects 20372020 and 02JJY4053 were supported by the National
Nature Science Foundation of China and Hunan respectively.

Synthesis of Alkynyl Tellurides
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