The coupling of butylvinyltellurides with organometallic reagents catalysed by nickel complexes

Article abstract of DOI:10.1016/j.tet.2007.06.057

Vinylic tellurides couple efficiently with sp, sp² and sp³ hybridised organometallic compounds (Li, MgX and Zn species) in the presence of dichloro-bis(triphenylphosphine)nickel(II) as catalyst.

Full text of DOI:10.1016/j.tet.2007.06.057

Tetrahedron 63 (2007) 8801–8809
The coupling of butylvinyltellurides with organometallic
reagents catalysed by nickel complexes
a
Cristiano Raminelli, Joao Gargalaka, Jr., Claudio C. Silveira and Joao V. Comasseto
a
b
a,
*
~
ꢀ
~
aInstituto de Quꢀımica, Universidade de Sa~o Paulo, Av. Prof. Lineu Prestes, 748, 05508-900 Sa~o Paulo, SP, Brasil
bDepartamento de Quꢀımica, Universidade Federal de Santa Maria, 97105-900 Santa Maria, RS, Brasil
Received 23 March 2007; revised 7 June 2007; accepted 12 June 2007
Available online 22 June 2007
Abstract—Vinylic tellurides couple efficiently with sp, sp2 and sp3 hybridised organometallic compounds (Li, MgX and Zn species) in the
presence of dichloro-bis(triphenylphosphine)nickel(II) as catalyst.
Ó 2007 Elsevier Ltd. All rights reserved.
1. Introduction
1999,10 and its use in the assembly of several unsaturated
systems has been reported.11 The mechanism of the reaction
has recently been investigated.12
Over the last two decades, organic tellurium compounds
have been the focus of intensive study and a number have
proven to be valuable synthetic intermediates.1 A full inves-
tigation into the toxicity of these compounds has been car-
ried out,2 and the allegation that they possess somewhat
unpleasant odours and are generally unstable to light and
air has been shown not to be totally correct.3 In this context,
dialkyl tellurides, which have long been considered unsuit-
able for synthetic purposes, have recently been prepared as
stable, non-noxious compounds presenting significant syn-
thetic potential.4
In view of the high price of palladium compounds, a number
of other elements have been considered as potential catalysts
for the coupling of vinylic tellurides and alkynes. Nickel
compounds are known to be efficient catalysts in coupling
reactions,13 as was aptly demonstrated by the pioneering
work of Uemura et al.14 on the coupling of phenyl-
vinyltellurides with Grignard reagents promoted by Ni(II)
complexes (Scheme 1). More recently, Silveira et al.15
reported that dichloro-bis(triphenylphosphine)nickel(II)
(Ni(PPh3)2Cl2) (2) and CuI catalyse the reaction of bis-
vinylic tellurides 1 with monosubstituted alkynes in the
presence of pyrrolidine to give enynes in good yield and
with retention of the Z double bond geometry (Scheme 2).
The vinylic tellurides constitute a class of organic tellurium
compounds that is most often employed in organic synthe-
sis.1 The method of choice for the preparation of the vinylic
tellurides is by hydrotelluration of an alkyne,1,5 a unique
anti-hydrometallation reaction that proceeds via a free radi-
cal process leading to the exclusive formation of product
with the Z-configuration.6 In view of this stereoselectivity,
various vinylic tellurides have already been employed
successfully in the synthesis of biologically active com-
pounds.4,7 Some of these synthetic routes4a,7b,d have utilised
the most explored property of the vinylic tellurides, namely,
their transformation into reactive organometallic com-
pounds by a tellurium/metal exchange reaction,8 whilst
others involved coupling of vinylic tellurides with cupra-
tes7a,9 or with monosubstituted alkynes promoted by palla-
dium(II) chloride.7c This latter reaction has been
developed considerably since it was first described in
R1
H
Ph
H
PhTe
H
Ph
H
Ph
H
Ni (II)
+
R1MgBr
+
+
Ph
R
R1
H
Scheme 1.
R
Ni(dppe)Cl2 (2, 5 mol%)
R1
H
+
R
R
Te
1
CuI (5 mol%)
pyrrolidine
R1
Scheme 2.
In the present work, the coupling of vinylic tellurides with
sp, sp2 and sp3 hybridised organometallic compounds in
the presence of dichloro-bis(triphenylphosphine)nickel(II)
(Ni(PPh3)2Cl2) or dichloro-(1,2-bis(diphenylphosphino)-
ethane)nickel(II) (Ni(dppe)Cl2) as catalyst has been studied.
Keywords: Coupling reaction; Tellurides; Nickel complexes; Catalysis;
Organometallic reagents.
* Corresponding author. Tel.: +55 11 3091 2176; fax: +55 11 3091 1180;
e-mail: jvcomass@iq.usp.br
0040–4020/$ - see front matter Ó 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2007.06.057

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C. Raminelli et al. / Tetrahedron 63 (2007) 8801–8809
2. Results and discussion
With the aim of synthesising functionalised enynes, vinylic
telluride 3f was submitted to the coupling reaction under
the established conditions. The product of this reaction
was, however, compound 6 derived from the coupling of
3f with the lithium alkynoate and subsequent addition of
lithium alkynoate to the ester group (Scheme 4). In order
to overcome this problem, the lithium alkynoate 4a was
transformed into the zinc alkynoate 7 by reaction with
ZnCl2. Coupling of 3f with 7 gave the desired product 5j
but as a mixture of Z and E enynes in which the E isomer
was the major component (Scheme 4).
As an extension to our previous studies,15 the aim of the
present work was to prepare Z-enediynes, which are struc-
tural moieties that are present in various important bioactive
natural products.16 However, bis-enynic tellurides are not
available through the hydrotelluration of diynes since, under
the conditions used to prepare bis-vinylic tellurides,8e diyne
substrates yield tellurophenes instead.17 For this reason, bu-
tyltelluroenynes, which are readily prepared by hydrotellu-
ration of diynes with di-n-butylditelluride/NaBH4,5,8c were
employed as vinylic tellurides in the coupling reaction. Sur-
prisingly, these compounds did not couple with monosubsti-
tuted alkynes under the conditions shown in Scheme 2.
The above strategy was applied to the coupling of telluride
3g, in which the double bond cannot isomerise, and this
gave rise to the formation of coupling products 5k and 5l
in good yields (Scheme 5). This result demonstrates that
the methodology can be applied successfully to functional-
ised substrates provided that the double bond of the coupling
product cannot undergo inversion of configuration.
As an alternative procedure, alkynoates were employed as
substrates instead of alkynes in the coupling reaction. It
was anticipated that in the case of the butylvinyltellurides
3, the by-products observed by Uemura et al.14 (Scheme 1)
would not be formed, since only the sp2 carbon is expected
to react18 (Scheme 3). A preliminary study was performed in
order to determine the most appropriate conditions for the
chosen coupling reaction,19 and the results are summarised
in Table 1. The highest yield of product was obtained
when 2.5 equiv of the lithium acetylide 4 and 5 mol % of
Ni(dppe)Cl2 (2) were employed (Table 1, entry 3).
In order to extend the coupling methodology to sp2 hybri-
dised carbanions, vinylic tellurides 3a and 3c were treated,
respectively, with 2-furfurylzinc (8a) and 2-thienylzinc
(8b) according to Scheme 6. The coupling products 9a and
9b were formed in good yields, but whilst 9a was obtained
as a 95:5 diastereomeric mixture of the Z and E olefins, 9b
was present as a single isomer.
R
Te
R
Te
We have recently demonstrated that arylbutyltellurides can
be transformed into arylcuprates20 and aryllithium com-
pounds,21 respectively, through tellurium/copper and tellu-
rium/lithium exchange reactions. Using the latter exchange
reaction, 4-methoxyphenyllithium 1021 was prepared, di-
ethyl zinc or ZnCl2 added in order to form the expected or-
ganometallic species 11–14 (Scheme 7),22 which were then
reacted with vinylic telluride 3a. In the case of the zinc com-
pound 11, a 35% yield of the olefin 15 was formed after 24 h
reflux. Under similar reaction conditions, the zincate 12 re-
acted with 3a to form a complex mixture of unidentified
products. When the diorganozinc 13 was reacted with 3a,
a complex mixture of products was also formed, but in this
case compound 15 and 1-phenyl-1-hexene could be identi-
fied. Finally, the coupling products 15 and 16 were obtained
in good yields when the diarylzinc 14 was reacted with 3a
(Scheme 8).
one site for coupling
two sites for coupling
Scheme 3.
In order to establish the range and limitations of the coupling
procedure, a number of vinylic tellurides and alkynes were
subjected to the reaction conditions shown in Table 1 (entry
3), and the results are presented in Table 2. In all cases, the
formation of dibutylditelluride and the diyne resulting from
the homocoupling of the starting lithium acetylide was ob-
served. The vinylic tellurides 3a, 3c, 3d and 3e gave good
yields of coupling products (Table 2, entries 1, 2, and 5–
9), whilst 3b gave only traces of product. This suggests
that steric effects can influence the course of the reaction
since the carbinol carbon of 3b bears a large substituent. Ad-
ditionally, the protecting group of telluride 3e was lost dur-
ing the coupling reaction and the deprotected alcohol 5i was
formed in quantitative yield (Table 2, entry 9).
The formation of 1-phenyl-1-hexene when telluride 3a was
allowed to react with the organozinc 13, led us to investigate
Table 1. Optimisation of the conditions for the coupling reaction
Te
3
nickel catalyst
M
(1 mmol)
, THF (10 mL)
4
N2, reflux
Entry
M¼metal (mmol)
Nickel catalyst (mol%)
Temperature
Time (h)
Isolated yield (%)
1
2
3
4
5
6
MgBr (2.5)
Li (2.5)
Li (2.5)
Li (1.5)
Li (1.5)
Li (2.5)
Ni(PPh3)2Cl2 (5.0)
Ni(PPh3)2Cl2 (5.0)
Ni(dppe)Cl2 (5.0)
Ni(dppe)Cl2 (5.0)
Ni(dppe)Cl2 (1.0)
Ni(dppe)Cl2 (5.0)
Reflux
Reflux
Reflux
Reflux
Reflux
Room temperature
4
3
3
3
24
72
70
90
100
87
Traces
Traces

C. Raminelli et al. / Tetrahedron 63 (2007) 8801–8809
8803
Table 2. Coupling reaction of Z-vinylic tellurides and lithium acetylides with Ni(dppe)Cl2 catalyst
Ni(dppe)Cl2 (2, 5 mol%)
R
R
Te
3
R1
5
(4, 2.5 mmol)
Li
R1
THF (10 mL), N2, reflux
Entry
1
R
R1
Product
Reaction time (h)
Isolated yield (%)
100
Ph
Ph 3a
n-C5H11 4a
3
n-C5H11
5a
Ph
2
3
4
5
6
7
Ph 3a
Ph 4b
12
12
12
7
93
Ph
5b
n-C5H11 4a
Traces
Traces
100
Si O
5c
Si O
n-C5H11
3b
Ph 4b
Si O
Si O
Ph
3b
5d
O
O
N
O
O
N
n-C5H11 4a
Me3Si 4c
n-C5H11 4a
n-C5H11
3c
5e
N
N
4
64
SiMe3
3c
5f
n-H9C4
3d
5
97
n-C5H11
n-C4H9
a
5g
n-H9C4
3d
8
5
75
n-
C5H11
5h
4d
9
n-C5H11 4a
12
100
Si
O
HO
n-
C5H11
5i
3e
a
Configuration determined by IR.
n-
C5H11
Ni(dppe)Cl2 (2, 5 mol%)
THF (10 mL), N2, reflux, 3 h
OH
O
TeBu
)
2
n-H11C5
(2.5 mmol)
Li
n-C5H11
O
3f
6
4a
(1-3 mmol)
ZnCl2
O
ClZn
n-C5H
11 (7, 7.5 mmol)
O
Ni(dppe)Cl2 (5 mol%)
THF (30 mL), N2, reflux, 3 h
5j
n-
C5H11
(E : Z / 95 : 5)
78%
Scheme 4.
the coupling reaction of dialkylzinc compounds with the vi-
nylic tellurides 3a, 3c and 3g. When vinylic telluride 3a was
reacted for 3 h under reflux with bis(n-butyl)zinc in the
presence of Ni(dppe)Cl2, a mixture of the Z and E isomers
of the olefin 17 was formed. It is worth mentioning that no
change in the isomeric ratio of 17 was observed after 24 h

8804
C. Raminelli et al. / Tetrahedron 63 (2007) 8801–8809
O
O
detellurated products that could be detected and identified
in the crude reaction mixture by GC–MS analysis.
Ni(dppe)Cl2 (2, 5 mol%)
(2.5 mmol)
R1
ZnCl
THF (10 mL), N2, reflux, 18 h
TeBu
3g
R1
R1 = n-C5H11 (5k, 91%)
1 = Ph (5l, 90%)
(1 mmol)
3. Conclusion
R
The coupling reaction of vinylic tellurides with organome-
tallic compounds promoted by Ni(dppe)Cl2 provides a viable
alternative to the similar coupling reaction employing the
more expensive palladium compounds as catalyst.
Scheme 5.
reflux in THF. After 3 h under reflux, vinylic telluride 3c re-
acted with bis(n-butyl)zinc in the presence of Ni(dppe)Cl2 to
give the coupling product 18 as a single stereoisomer in 60%
yield. Reaction of diethyl zinc with the telluroenone 3g gave
51% of the coupling product 19 after 3 h under reflux
(Scheme 9). The lower yields of the coupling reaction with
alkylzinc compounds can be attributed to a tellurium/zinc
exchange23 leading, after work up, to the corresponding
4. Experimental
4.1. Materials and general procedures
Tellurium powder (ꢀ200 mesh) and standard chemicals
were obtained from commercial sources. All reagents and
TeBu
O
9a
3a
Ni(dppe)Cl2 (2, 5 mol%)
THF (10 mL), N2, reflux, 48 h
Z : E = 95 : 5
(1 mmol)
82%
O
N
O
N
TeBu
ZnCl
(2.5 mmol)
X = O (8a) or S (8b)
X
S
3c
9b
(1 mmol)
81%
ZnCl2, N2, -35oC
-35 °
C
r.t., 15 min.
°
n-BuLi, THF, N2, -70 C
Li
°
-35 °C, 30 min.
-70 C
X
X
Scheme 6.
ZnCl2, N2, -70 °C
r.t., 15 min.
O
TeBu
O
O
ZnCl
Zn
-70 °C
11
n-BuLi, THF, N2, -70 °C
Et2Zn, N2, -70 °C
r.t., 30 min.
15 min
Li
-70 °C
12
13
O
Li
ZnCl2, N2, -70 °C
r.t., 30 min.
r.t., 30 min.
10
O
O
Zn
Zn
n-BuLi, N2, -70 °C
1/2 ZnCl2, N2, -70 °C
r.t., 30 min.
-70 °C
2
14
Scheme 7.
TeBu
15
3a
O
81%
(0.5 mmol)
O
Ni(dppe)Cl2 (2, 5-10 mol%)
O
THF (5 mL), N2, reflux, 24 h
O
Zn
TeBu
2
3g
16
O
(14, 1.25 mmol)
(0.5 mmol)
92%
Scheme 8.

C. Raminelli et al. / Tetrahedron 63 (2007) 8801–8809
8805
TeBu
17
Z : E = 9 : 1
3a
(1 mmol)
60%
Ni(dppe)Cl2 (2, 10 mol%)
THF (10-30 mL), N2, reflux, 3 h
O
N
O
N
TeBu
(alkyl)2Zn
(2.5-7.5 mmol)
18
3c
(1 mmol)
O
60%
O
TeBu
19
3g
51%
(3 mmol)
Scheme 9.
solvents were purified and dried prior to use according to
the published methods.24 THF was distilled from sodium/
benzophenone under N2 immediately before use,24 whilst
n-BuLi was titrated using 1,10-phenanthroline.25 Nitrogen
gas used in the reactions was deoxygenated and dried as
described in the literature,8b,24 and all operations were
carried out in flame-dried glassware. The following reagents
were prepared according to the literature procedures:
Ni(PPh3)2Cl2,26 Ni(dppe)Cl2,27 butyl(Z-(styryl))tellane
(3a),8b ((Z)-4-(butyltellanyl)but-3-en-2-yloxy)(tert-butyl)-
dimethylsilane (3b),12 4-((Z)-3-(butyltellanyl)allyl)mor-
pholine (3c),8b butyl((Z)-oct-1-en-3-ynyl)tellane (3d),28
((2E,4Z)-5-(butyltellanyl)penta-2,4-dienyloxy)trimethylsilane
(3e),29 (Z)-ethyl 3-(butyltellanyl)acrylate (3f),30 3-(butyl-
tellanyl)-5,5-dimethylcyclohex-2-enone (3g)31 and butyl-
(4-methoxyphenyl)tellane.21 All the organic tellurium
compounds presented analytical data that were in agreement
with those reported in the literature. Column chromatograph-
ic separations were carried out using Merck silica gel 60
(0.063–0.200 mm). IUPAC names wereverified using Chem-
Draw Ultra (version 8.0) software.
stirrer/hot plate and silicone oil bath, and containing ethyl-
magnesium bromide (2.5 mL of a 1 mol Lꢀ1 solution in
THF, 2.5 mmol) at 50 ꢁC under an atmosphere of N2. The re-
action mixture was stirred for 1 h at 50 ꢁC following which
the magnesium reagent was ready for use.
4.3.2. Preparation of lithium acetylides.32 The appropriate
alkyne (2.75 mmol) and THF (2.5 mL) were added by sy-
ringe to a 15 mL two-necked round-bottomed flask, equip-
ped with a rubber septum and magnetic stirrer, and
maintained under a N2 atmosphere at ꢀ70 ꢁC. n-BuLi
(1.92 mL of a 1.3 mol Lꢀ1 solution in hexane, 2.5 mmol)
was added dropwise at ꢀ70 ꢁC, and the reaction mixture
stirred at this temperature for 10 min after which the lithium
reagent was ready for use.
4.3.3. Preparation of alkynylzinc chloride.33 ZnCl2
(2.5 mL of a 1.0 mol Lꢀ1 solution in THF, 2.5 mmol) was
added in a single portion to the appropriate lithium acetylide
(2.5 mmol; prepared as described above) maintained at
ꢀ70 ꢁC under a N2 atmosphere. The reaction mixture was
warmed to room temperature and then stirred for 20 min
following which the zinc reagent was ready for use.
4.2. Instrumentation
1H and 13C NMR spectra were obtained using a Bruker AC-
200 (1H, 200 MHz; 13C, 50 MHz) or a Varian INOVA 300
(1H, 300 MHz; 13C, 75 MHz) spectrometer. All spectra
were measured in CDCl3 with tetramethylsilane (TMS) as
internal standard. Low resolution mass spectra were re-
corded on a Shimadzu CG-17A/CGMS-QP5050A spec-
trometer, whilst high resolution spectra were measured on
a VG Autospec instrument. Near-IR spectra were deter-
mined on Bomem MB-100 or MB-Series spectrometers.
4.3.4. Coupling reaction. The nickel complex (0.05 mmol),
appropriate telluride (1 mmol), THF (10 mL) and the appro-
priate metal alkynoate (2.5 mmol, prepared as described
above) were added by syringe to a 50 mL two-necked
round-bottomed flask equipped with a reflux condenser, rub-
ber septum, magnetic stirrer/hot plate and silicone oil bath.
The reaction mixture was refluxed under an atmosphere of
N2 for the time indicated in Tables 1 and 2 or in Schemes
4 and 5. The reaction was quenched with brine (50 mL)
and the resulting mixture extracted with ethyl acetate
(3ꢂ50 mL). The extracts were dried over MgSO4, filtered,
the solvent evaporated under reduced pressure and the resi-
due purified by column chromatography over silica gel using
an appropriate eluent.
€
Melting points were measured using a Buchi B-545 appara-
tus. Elemental analyses were performed on a Perkin Elmer
2400 CNH analyser at the Microanalytical Laboratory of
~
the Institute of Chemistry, University of Sao Paulo, SP,
Brazil.
4.3. Coupling reaction between tellurides and metal
acetylides using nickel complexes as catalysts
4.3.5. 1-((Z)-Non-1-en-3-ynyl)benzene (5a) [CAS Regis-
try Number 172368-35-3]. Product eluted with pentane,
quantitative yield 0.198 g (100%). The spectral data agreed
with those from the literature.10
4.3.1. Preparation of hept-1-ynylmagnesium bromide.32
Hept-1-yne (0.240 g, 2.5 mmol) was added dropwise by sy-
ringe to a 15 mL two-necked round-bottomed flask, equip-
ped with a reflux condenser, rubber septum, magnetic
4.3.6. (Z)-1,4-Diphenylbut-1-en-3-yne (5b) [CAS Regis-
try Number 13343-78-7]. Product eluted with hexane, yield

8806
C. Raminelli et al. / Tetrahedron 63 (2007) 8801–8809
0.190 g (93%). The spectral data agreed with those from the
literature.15
51 (29.4%). Mass Calcd for C13H16: 172.1252. Found:
172.1232.
4.3.7. 4-((Z)-Dec-2-en-4-ynyl)morpholine (5e). Product
eluted with ethyl acetate, quantitative yield 0.221 g
(100%); H NMR (200 MHz, CDCl3) d 5.89 (dt, J¼11.0,
4.3.11. (2E,4Z)-Dodeca-2,4-dien-6-yn-1-ol (5i) [CAS Reg-
istry Number 157554-21-7]. Product eluted with hexane/
ethyl acetate (8:2), quantitative yield 0.178 g (100%). The
spectral data agreed with those from the literature.34
1
7.0 Hz, 1H), 5.63 (d, J¼11.0 Hz, 1H), 3.72 (t, J¼4.8 Hz,
4H), 3.25 (dd, J¼6.8, 1.1 Hz, 2H), 2.49 (t, J¼4.8 Hz, 4H),
2.34 (td, J¼6.8, 1.9 Hz, 2H), 1.55 (quint, J¼7.0 Hz, 2H),
1.44–1.25 (m, 4H), 0.91 (t, J¼7.0 Hz, 3H); 13C NMR
(50 MHz, CDCl3) d 136.9, 112.9, 96.1, 76.6, 66.8, 57.5,
53.4, 30.9, 28.3, 22.0, 19.3, 13.8; near-IR (film) cmꢀ1
3027 (w), 2958 (s), 2932 (s), 2857 (s), 2800 (m), 2215
(w), 1619 (w), 1454 (m), 1326 (m), 1291 (m), 1119 (s);
LRMS m/z (relative intensity) 221 [M+] (1.7%), 206
(3.8%), 192 (12.6%), 178 (18.3%), 164 (100.0%), 150
(27.4%), 134 (25.4%), 120 (82.5%), 106 (35.6%), 91
(49.2%), 77 (73.9%), 56 (63.3%). Anal. Calcd for
C14H23NO: C, 75.97; H, 10.47; N, 6.33. Found: C, 75.62;
H, 10.48; N, 6.10.
4.3.12. (Z)-8-(Hept-1-ynyl)heptadeca-9-en-6,11-diyn-8-ol
(6). Yield 73% (by GC); analyses of crude material—1H
NMR (200 MHz, CDCl3) d 6.81 (d, J¼10.1 Hz, 1H), 6.53
(d, J¼10.5 Hz, 1H); near-IR (film) cmꢀ1 3399 (m, broad),
3056 (w), 2957 (s), 2930 (s), 2859 (s), 2228 (m), 1462
(m), 1378 (m), 1180 (m), 728 (m); LRMS m/z (relative inten-
sity) 340 [M+] (0.5%), 244 (27.3%), 229 (2.6%), 215 (7.5%),
201 (100.0%), 188 (5.9%), 173 (22.3%), 159 (15.1%), 145
(47.6%), 131 (96.6%), 115 (42.9%), 105 (21.1%), 91
(40.3%), 77 (36.2%), 55 (49.5%).
4.3.13. Ethyl dec-2-en-4-ynoate (5j). Reaction scale
3 mmol, product eluted with hexane followed by ethyl ace-
tate, yield (after horizontal distillation) 0.455 g (78%). GC
analysis of the purified product showed it to be a 95:5 mix-
ture of the E and Z isomers of 5j, respectively. (E)-5j [CAS
Registry Number 66901-42-6]: The spectral data agreed
with those from the literature.35 (Z)-5j: Identified in the
mixture by LRMS m/z (relative intensity) 194 [M+]
(1.9%), 179 (0.7%), 166 (35.9%), 149 (22.2%), 137
(13.3%), 123 (47.0%), 109 (100.0%), 91 (20.6%), 81
(69.6%), 65 (28.8%), 55 (48.9%), and by a low intensity
doublet at d 6.01 with J¼11.4 Hz in the 1H NMR
(200 MHz, CDCl3).
4.3.8. 4-((Z)-5-(Trimethylsilyl)pent-2-en-4-ynyl)morpho-
line (5f). Product eluted with ethyl acetate/hexane (8:2),
yield 0.142 g (64%); H NMR (200 MHz, CDCl3) d 6.04
1
(dt, J¼11.0, 7.0 Hz, 1H), 5.68 (dt, J¼11.0, 1.3 Hz, 1H),
3.73 (t, J¼4.8 Hz, 4H), 3.29 (dd, J¼7.0, 1.3 Hz, 2H), 2.52
(t, J¼4.6 Hz, 4H), 0.20 (s, 9H); 13C NMR (50 MHz,
CDCl3) d 139.7, 112.8, 101.1, 100.6, 66.8, 57.6, 53.5,
ꢀ0.1; near-IR (film) cmꢀ1 3028 (w), 2960 (s), 2897 (m),
2855 (m), 2810 (m), 2148 (m), 1453 (m), 1326 (m), 1251
(s), 1119 (s), 846 (s); LRMS m/z (relative intensity) 223
[M+] (0.4%), 208 (2.8%), 194 (8.3%), 180 (5.9%), 167
(19.8%), 150 (24.1%), 135 (4.2%), 123 (15.7%), 109
(9.3%), 86 (12.8%), 73 (100.0%), 59 (38.7%). Anal. Calcd
for C12H21NOSi: C, 64.52; H, 9.48; N, 6.27. Found: C,
64.47; H, 9.42; N, 6.53.
4.3.14. 3-(Hept-1-ynyl)-5,5-dimethylcyclohex-2-enone
(5k). Product eluted with hexane/ethyl acetate (9:1), yield
0.198 g (91%); 1H NMR (200 MHz, CDCl3) d 6.14 (s,
1H), 2.39 (t, J¼6.8 Hz, 2H), 2.30 (d, J¼1.8 Hz, 2H), 2.24
(s, 2H), 1.57 (quint, J¼6.9 Hz, 2H), 1.45–1.25 (m, 4H),
1.05 (s, 6H), 0.91 (t, J¼7.0 Hz, 3H); 13C NMR (50 MHz,
CDCl3) d 198.8, 142.1, 130.3, 101.7, 80.4, 60.0, 50.8,
44.5, 33.3, 30.8, 27.8, 27.8, 21.9, 19.1, 13.7; near-IR (film)
cmꢀ1 3048 (w), 2958 (s), 2934 (s), 2869 (s), 2218 (s),
1667 (s), 1596 (s), 1465 (m), 1355 (s), 1277 (s); LRMS
m/z (relative intensity) 218 [M+] (21.5%), 203 (14.5%),
189 (5.8%), 175 (18.2%), 162 (34.2%), 147 (34.1%), 134
(37.0%), 119 (100.0%), 106 (47.2%), 91 (68.8%), 77
(44.0%), 65 (21.2%), 55 (37.3%). Anal. Calcd for
C15H22O: C, 82.52; H, 10.16. Found: C, 82.29; H, 10.15.
4.3.9. (Z)-Pentadeca-7-en-5,9-diyne (5g). Product eluted
with hexane, yield 0.196 g (97%); 1H NMR (200 MHz,
CDCl3) d 5.65 (s, 2H), 2.32 (t, J¼6.4 Hz, 4H), 1.50–1.18
(m, 10H), 0.89–0.80 (m, 6H); 13C NMR (50 MHz, CDCl3)
d 118.8, 97.7, 97.6, 78.3, 78.3, 31.0, 30.7, 28.3, 22.2, 21.8,
19.7, 19.4, 13.8, 13.5; near-IR (film) cmꢀ1 3026 (w), 2958
(s), 2932 (s), 2861 (m), 2216 (w), 1577 (w), 1463 (w),
1326 (w), 745 (m); LRMS m/z (relative intensity) 202
(42.4%), 187 (2.2%), 173 (3.5%), 159 (6.5%), 145
(26.8%), 131 (65.8%), 117 (77.5%), 105 (44.1%), 91
(100.0%), 77 (44.0%), 63 (22.5%), 51 (25.8%). Mass Calcd
for C15H22: 202.1692. Found: 202.1721.
4.3.15. 5,5-Dimethyl-3-(2-phenylethynyl)cyclohex-2-
enone (5l). Product eluted with hexane/ethyl acetate (9:1),
yield 0.201 g (90%); H NMR (200 MHz, CDCl3) d 7.51–
4.3.10. (Z)-2-Methyldodeca-1,5-dien-3,7-diyne (5h).
Product eluted with hexane, yield 0.129 g (75%); H NMR
1
1
(200 MHz, CDCl3) d 5.86 (d, J¼10.5 Hz, 1H), 5.79 (dt,
J¼10.5, 1.7 Hz, 1H), 5.35 (d, J¼0.9 Hz, 1H), 5.28 (quintap,
J¼1.7 Hz, 1H), 2.42 (td, J¼7.0, 1.7 Hz, 2H), 1.95 (d, J¼
1.3 Hz, 3H), 1.64–1.38 (m, 4H), 0.92 (t, J¼7.0 Hz, 3H);
13C NMR (50 MHz, CDCl3) d 126.9, 122.3, 120.1, 118.1,
99.2, 97.3, 86.2, 78.3, 30.7, 23.3, 21.9, 19.5, 13.5; near-IR
(film) cmꢀ1 3097 (w), 3025 (w), 2959 (s), 2931 (s), 2868
(s), 2219 (w), 2191 (w), 1679 (w), 1610 (w), 1458 (m),
1399 (w), 897 (s), 745 (s); LRMS m/z (relative intensity)
172 (81.3%), 157 (4.6%), 142 (31.1%), 128 (100.0%), 115
(74.9%), 102 (8.2%), 91 (28.4%), 77 (32.4%), 63 (24.0%),
7.45 (m, 2H), 7.40–7.32 (m, 3H), 6.30 (t, J¼1.7 Hz, 1H),
2.43 (d, J¼1.3 Hz, 2H), 2.29 (s, 2H), 1.09 (s, 6H); 13C
NMR (50 MHz, CDCl3) d 198.9, 141.2, 132.0, 131.4,
129.5, 128.5, 122.1, 99.4, 88.7, 51.1, 44.4, 33.8, 28.1;
near-IR (film) cmꢀ1 3058 (w), 2958 (s), 2872 (m), 2823
(w), 2199 (m), 1665 (s), 1593 (s), 1359 (s), 1277 (s), 759
(s), 691 (s); LRMS m/z (relative intensity) 224 [M+]
(63.1%), 209 (15.8%), 181 (19.0%), 168 (100.0%), 139
(62.6%), 126 (9.5%), 114 (8.3%), 98 (2.5%), 89 (9.6%),
77 (9.2%), 63 (9.9%), 55 (9.2%). Anal. Calcd for
C16H16O: C, 85.68; H, 7.19. Found: C, 85.39; H, 7.40.

C. Raminelli et al. / Tetrahedron 63 (2007) 8801–8809
8807
4.4. Coupling reaction between vinylic tellurides and
aromatic zinc reagents or zincate catalysed by
Ni(dppe)Cl2
4.4.7. Coupling reaction. Ni(dppe)Cl2 (0.05–0.10 mmol,
see Schemes 6 and 8), the appropriate telluride (0.5–
1 mmol), THF (5–10 mL) and the appropriate zinc reagent
or zincate (1.25–2.5 mmol, prepared as described above)
were added by syringe to a 50 mL two-necked round-
bottomed flask equipped with a reflux condenser, rubber sep-
tum, magnetic stirrer/hot plate and silicone oil bath. The
reaction mixture was refluxed under an atmosphere of N2
for the time indicated in Schemes 6 and 8. The reaction
was quenched with brine (50 mL) and the resulting mixture
extracted with ethyl acetate (3ꢂ50 mL). The extracts were
dried over MgSO4, filtered, the solvent evaporated under re-
duced pressure and the residue purified by column chroma-
tography over silica gel using an appropriate eluent.
4.4.1. Preparation of 2-furanyl (8a) or 2-thienylzinc chlo-
ride (8b).36 Furan or thiophene (2.5 mmol) and THF
(7.5 mL) were added by syringe to a 15 mL two-necked
round-bottomed flask, equipped with a rubber septum and
magnetic stirrer, and maintained under a N2 atmosphere at
ꢀ70 ꢁC. n-BuLi (1.92 mL of a 1.3 mol Lꢀ1 solution in hex-
ane, 2.5 mmol) was added drop-wise at ꢀ70 ꢁC, the reaction
mixture was warmed to ꢀ35ꢁ and stirred for 15 min. ZnCl2
(2.5 mL of a 1.0 mol Lꢀ1 solution in THF, 2.5 mmol) was
added to the mixture, the whole warmed to room tempera-
ture and stirred for 15 min following which the zinc reagent
was ready for use.
4.4.8. 2-Styrylfuran (9a). Reaction scale 1 mmol, product
eluted with hexane, yield 0.140 g (82%). GC analysis of
the purified product showed it to be a 95:5 mixture of the
Z and E isomers of 9a, respectively. (Z)-9a [CAS Registry
Number 18138-87-9]: The spectral data agreed with those
from the literature.36 (E)-9a [CAS Registry Number
21676-00-6]: Identified in the mixture by LRMS m/z (rela-
tive intensity) 170 [M+] (100.0%), 155 (1.4%), 141
(94.3%), 115 (58.8%), 102 (4.7%), 89 (10.3%), 77 (9.2%),
70 (20.2%), 63 (22.1%), 55 (33.7%), 51 (20.9%), 40
(95.7%), and by two low intensity doublets at d 7.05 and
6.89 both with J¼16.2 Hz in the 1H NMR (200 MHz,
CDCl3).
4.4.2. Preparation of 4-methoxyphenyllithium (10).21 Bu-
tyl(4-methoxyphenyl)tellane (1.25–2.5 mmol) and THF
(2.5–5.0 mL) were added by syringe to a 15 mL two-necked
round-bottomed flask, equipped with a rubber septum and
magnetic stirrer, and maintained under a N2 atmosphere at
ꢀ70 ꢁC. n-BuLi (0.92–1.92 mL of a 1.3 mol Lꢀ1 solution
in hexane, 1.25–2.5 mmol) was added in a single portion
at ꢀ70 ꢁC and the reaction mixture stirred for 20 min after
which the lithium reagent was ready for use.
4.4.3. Preparation of 4-methoxyphenylzinc chloride
(11).33 ZnCl2 (1.25 mL of a 1.0 mol Lꢀ1 solution in THF,
1.25 mmol) was added in a single portion to 4-methoxyphe-
nyllithium (1.25 mmol, prepared as described above) main-
tained under a N2 atmosphere at ꢀ70 ꢁC. The reaction
mixture was warmed to room temperature and stirred for
30 min after which the zinc reagent was ready for use.
4.4.9. 4-((Z)-3-(Thiophen-2-yl)allyl)morpholine (9b). Re-
action scale 1 mmol, product eluted with hexane/ethyl ace-
1
tate (7:3), yield 0.169 g (81%), mp 39–41 ꢁC; H NMR
(200 MHz, CDCl3) d 7.29 (d, J¼4.4 Hz, 1H), 7.04–7.00
(m, 2H), 6.67 (d, J¼11.9 Hz, 1H), 5.67 (dt, J¼11.8,
6.1 Hz, 1H), 3.74 (t, J¼4.6 Hz, 4H), 3.37 (dd, J¼6.6,
1.8 Hz, 2H), 2.54 (t, J¼4.4 Hz, 4H); 13C NMR (50 MHz,
CDCl3) d 139.9, 128.0, 126.8, 126.8, 125.8, 123.9, 66.9,
57.1, 53.7; near-IR (KBr) cmꢀ1 3100 (w), 2968 (w), 2936
(w), 2897 (w), 2855 (w), 2786 (w), 2686 (w), 2648 (w),
1629 (w), 1449 (m), 1292 (s), 1112 (s); LRMS m/z (relative
intensity) 209 [M+] (26.4%), 178 (1.3%), 164 (1.8%), 150
(7.9%), 135 (4.8%), 123 (73.5%), 112 (100.0%), 100
(7.7%), 97 (12.6%), 86 (15.8%), 79 (22.5%), 77 (14.1%),
56 (42.3%), 45 (47.7%). Anal. Calcd for C11H15NOS: C,
63.12; H, 7.22; N, 6.69. Found: C, 63.11; H, 6.94; N, 7.21.
4.4.4. Preparation of 4-methoxyphenyldiethyl lithium
zincate (12).23 Et2Zn (1.25 mL of a 1.0 mol Lꢀ1 solution
in THF, 1.25 mmol) was added in a single portion to 4-
methoxyphenyllithium (1.25 mmol, prepared as described
above) maintained under a N2 atmosphere at ꢀ70 ꢁC. The
reaction mixture was warmed to room temperature and
stirred for 30 min following which the zincate was ready
for use.
4.4.5. Preparation of 4-methoxyphenyl-n-butylzinc
(13).37 ZnCl2 (1.25 mL of a 1.0 mol Lꢀ1 solution in THF,
1.25 mmol) was added in a single portion to 4-methoxyphe-
nyllithium (1.25 mmol, prepared as described above) main-
tained under a N2 atmosphere at ꢀ70 ꢁC. The reaction
mixture was warmed to room temperature, stirred for
30 min, cooled again to ꢀ70 ꢁC and n-BuLi (0.96 mL of
a 1.3 mol Lꢀ1 solution in hexane, 1.25 mmol) was added. Fi-
nally, the mixture was warmed to room temperature and
stirred for 30 min after which the zinc reagent was ready
for use.
4.4.10. (Z)-1-Methoxy-4-styrylbenzene (15) [CAS Regis-
try Number 1657-53-0]. Reaction scale 0.5 mmol, product
eluted with hexane, yield 0.085 g (81%). The spectral data
agreed with those from the literature.38
4.4.11. 3-(4-Methoxyphenyl)-5,5-dimethylcyclohex-2-
enone (16) [CAS Registry Number 29339-44-4]. Reaction
scale 0.5 mmol, product eluted with hexane, yield 0.106 g
(92%), mp 43–45 ꢁC. The spectral data agreed with those
from the literature.39
4.4.6. Preparation of bis(4-methoxyphenyl)zinc (14).23
ZnCl2 (1.25 mL of a 1.0 mol Lꢀ1 solution in THF,
1.25 mmol) was added in a single portion to 4-methoxyphe-
nyllithium (2.5 mmol, prepared as described above) main-
tained under a N2 atmosphere at ꢀ70 ꢁC. The reaction
mixture was warmed to room temperature and stirred for
30 min after which the zinc reagent was ready for use.
4.5. Coupling reaction between vinylic tellurides and
bis(alkyl)zinc reagents catalysed by Ni(dppe)Cl2
4.5.1. Preparation of bis(n-butyl)zinc.23 ZnCl2 (2.5 mL of
a 1.0 mol Lꢀ1 solution in THF, 2.5 mmol) was added by
syringe to a 15 mL two-necked round-bottomed flask,

8808
C. Raminelli et al. / Tetrahedron 63 (2007) 8801–8809
Panatieri, R. S.; Braga, A. L. Chem. Rev. 2006, 106, 1032; (c)
Petragnani, N.; Stefani, H. A. Tetrahedron 2005, 61, 1313;
(d) Comasseto, J. V.; Barrientos-Astigarraga, R. E.
Aldrichimica Acta 2000, 33, 66.
equipped with a rubber septum and magnetic stirrer, and
maintained under a N2 atmosphere at ꢀ70 ꢁC. n-BuLi
(3.85 mL of a 1.3 mol Lꢀ1 solution in hexane, 5 mmol)
was added dropwise at ꢀ70 ꢁC, the reaction mixture warmed
to room temperature and stirred for 15 min after which the
zinc reagent was ready for use.
2. Nogueira, C. W.; Zeni, G.; Rocha, J. B. T. Chem. Rev. 2004,
104, 6255.
3. Dos Santos, A. A.; Castelani, P.; Bassora, B. K.; Fogo, J. C.,
Jr.; Costa, C. E.; Comasseto, J. V. Tetrahedron 2005, 61,
9173.
4.5.2. Coupling reaction. Ni(dppe)Cl2 (0.053 g,
0.10 mmol), the appropriate telluride (1 mmol), THF
(10 mL) and the appropriate zinc reagent (2.5 mmol, pre-
pared as described above or purchased from Aldrich Chem-
ical Co.) were added by syringe to a 50 mL two-necked
round-bottomed flask equipped with a reflux condenser, rub-
ber septum, magnetic stirrer/hot plate and silicone oil bath.
The reaction mixture was refluxed under an atmosphere of
N2 for 3 h and quenched with brine (50 mL). The solid resi-
dues were filtered off over Celite and silica gel and washed
several times with ethyl acetate. The aqueous phase was ex-
tracted with ethyl acetate (3ꢂ50 mL) and the bulked extracts
dried over MgSO4, filtered, the solvent evaporated under re-
duced pressure and the residue purified by column chroma-
tography over silica gel using an appropriate eluent.
4. (a) Dos Santos, A. A.; Ferrarini, R. S.; Princival, J. L.;
Comasseto, J. V. Tetrahedron Lett. 2006, 47, 8933; (b) Dos
Santos, A. A.; Da Costa, C. E.; Princival, J. L.; Comasseto,
J. V. Tetrahedron: Asymmetry 2006, 17, 2252; (c) Princival,
J. L.; Barros, S. M. G.; Comasseto, J. V.; Dos Santos, A. A.
Tetrahedron Lett. 2005, 46, 4423; (d) Dos Santos, A. A.;
Comasseto, J. V. J. Braz. Chem. Soc. 2005, 16, 511.
5. For a review see: Vieira, M. L.; Zinn, F. K.; Comasseto, J. V.
J. Braz. Chem. Soc. 2001, 12, 586.
6. Keppler, A. F.; Cerchiaro, G.; Augusto, O.; Miyamoto, S.;
Prado, F.; Di Maschio, P.; Comasseto, J. V. Organometallics
2006, 25, 5059.
7. (a) Diego, D. G.; Cunha, R. L. O. R.; Comasseto, J. V.
Tetrahedron Lett. 2006, 47, 7147; (b) Marino, J. P.; McClure,
M. S.; Holub, D. P.; Comasseto, J. V.; Tucci, F. C. J. Am.
Chem. Soc. 2002, 124, 1664; (c) Zeni, G.; Panatieri, R. B.;
Lissner, E.; Menezes, P. H.; Braga, A. L.; Stefani, H. A. Org.
Lett. 2001, 6, 819; (d) Yang, J.; Cohn, S. T.; Romo, D. Org.
Lett. 2000, 2, 763.
8. (a) Dabdoub, M. J.; Begnini, M. L.; Cassol, T. M.; Guerreiro,
P. G., Jr.; Silveira, C. C. Tetrahedron Lett. 1998, 54, 2371; (b)
Tucci, F. C.; Chieffi, A.; Comasseto, J. V.; Marino, J. P.
J. Org. Chem. 1996, 61, 4975; (c) Dabdoub, M. J.; Dabdoub,
V. B.; Comasseto, J. V. Tetrahedron Lett. 1992, 33, 2261; (d)
Barros, S. M.; Dabdoub, M. J.; Dabdoub, V. B.; Comasseto,
J. V. Organometallics 1989, 8, 1661; (e) Barros, S. M.;
Comasseto, J. V.; Berriel, J. Tetrahedron Lett. 1989, 30,
7353; (f) Miller, J. A.; Leong, W.; Zweifel, G. J. Org. Chem.
1988, 53, 1839; (g) Hiiro, T.; Kambe, N.; Ogawa, A.;
Miyoshi, N.; Murai, S.; Sonoda, N. Angew. Chem., Int. Ed.
Engl. 1987, 26, 1187; (h) Kauffmann, T. Angew. Chem., Int.
Ed. Engl. 1982, 21, 410; (i) Seebach, D.; Beck, A. K. Chem.
Ber. 1975, 108, 314.
9. (a) Chieffi, A.; Comasseto, J. V. Tetrahedron Lett. 1994, 35,
4063; (b) Chieffi, A.; Comasseto, J. V. Synlett 1995, 671.
10. Zeni, G.; Comasseto, J. V. Tetrahedron Lett. 1999, 40, 4619.
11. (a) Hirabayashi, K.; Nara, Y.; Shimizu, T.; Kamigata, N. Chem.
Lett. 2004, 33, 1280; (b) Zeni, G.; Menezes, P. H.; Moro, A. V.;
Braga, A. L.; Silveira, C. C.; Stefani, H. A. Synlett 2001, 1473.
For a review see: Zeni, G.; Braga, A. L.; Stefani, H. A. Acc.
Chem. Res. 2003, 36, 731.
4.5.3. 1-(Hex-1-enyl)benzene (17). The product eluted with
hexane, the residue obtained after column chromatography
was dissolved in ethyl acetate (30 mL) and the extract
washed with 1% aqueous NaClO (30 mL) and H2O
(2ꢂ50 mL), yield 0.096 g (60%). GC analysis of the purified
product showed it to be a 9:1 mixture of the Z and E isomers
of 17, respectively. (Z)-17 [CAS Registry Number 15325-
54-9]: The spectral data agreed with those from the litera-
ture.8b (E)-17 [CAS Registry Number 6111-82-6]: Identified
in the mixture by LRMS m/z (relative intensity) 160 [M+]
(26.6%), 131 (3.1%), 117 (100.0%), 104 (68.7%), 91
(31.8%), 77 (10.0%), 65 (7.3%), 51 (10.2%).40
4.5.4. 4-((Z)-Hept-2-enyl)morpholine (18) [CAS Registry
Number 144758-48-5]. The product eluted with hexane and
then ethyl acetate, yield 0.110 g (60%); 1H NMR (200 MHz,
CDCl3) d 5.58 (dtd, J¼11.0, 7.0, 1.3 Hz, 1H), 5.44 (dtd,
J¼11.0, 7.0, 1.0 Hz, 1H), 3.72 (t, J¼4.8 Hz, 4H), 3.01 (d, J¼
6.6 Hz, 2H), 2.46 (t, J¼4.4 Hz, 4H), 2.07 (quint, J¼6.6 Hz,
2H), 1.37–1.30 (m, 4H), 0.90 (t, J¼6.6 Hz, 3H); 13C NMR
(50 MHz, CDCl3) d 133.6, 125.1, 66.8, 55.3, 53.5, 31.6,
27.1, 22.1, 13.8; near-IR (film) cmꢀ1 3015 (w), 2959 (m),
2929 (m), 2856 (m), 2802 (m), 1456 (m), 1293 (m), 1119
(s); LRMS m/z (relative intensity) 183 [M+] (5.4%), 154
(0.4%), 140 (2.2%), 126 (9.5%), 110 (11.0%), 100
(13.6%), 96 (8.3%), 87 (100.0%), 81 (10.2%), 67 (9.0%),
57 (44.5%), 55 (39.1%).
12. Raminelli, C.; Prechtl, M. H. G.; Santos, L. S.; Eberlin, M. N.;
Comasseto, J. V. Organometallics 2004, 23, 3990.
4.5.5. 3-Ethyl-5,5-dimethylcyclohex-2-enone (19) [CAS
Registry Number 28017-78-9]. Reaction scale 3 mmol,
yield (after horizontal distillation) 0.234 g (51%). The spec-
tral data agreed with those from the literature.41
13. (a) Metal-Catalyzed Cross-Coupling Reactions; Diederich, F.,
Stang, P. J., Eds.; Willey-VCH: Weinheim, 1998; (b) Metal–
Catalyzed Cross–Coupling Reactions; Meijere, A., Diederich,
F., Eds.; Willey-VCH: Weinheim, 2004; Vols. 1 and 2.
14. (a) Uemura, S.; Fukuzawa, S. Tetrahedron Lett. 1982, 23, 1181;
(b) Uemura, S.; Fukuzawa, S.; Patil, S. R. J. Organomet. Chem.
1983, 243, 9.
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