Addition of Z-vinylic higher order cyanocuprates to enones followed by O-functionalization

Article abstract of DOI:10.1016/S0040-4020(00)00254-4

Transmetalation reaction between Z-vinylic tellurides and higher order cyanocuprates generated the corresponding Z-vinylic cyanocuprates. Conjugate addition of these cuprates to enones followed by O-functionalization led to silyl enol ethers, vinyl phosphates and vinyl triflates. The vinyl triflates were transformed into highly unsaturated systems by coupling with alkynes or with Z-vinyl zinc chlorides under Pd (0) catalysis. (C) 2000 Elsevier Science Ltd.

Full text of DOI:10.1016/S0040-4020(00)00254-4

TETRAHEDRON
Pergamon
Tetrahedron 56 (2000) 3327±3337
Addition of Z-Vinylic Higher Order Cyanocuprates to Enones
Followed by O-Functionalization
*
D. N. Moraes, R. E. Barrientos-Astigarraga, P. Castelani and J. V. Comasseto
Â
Instituto de Quõmica, Universidade de SaÄo Paulo, Av. Prof. Lineu Prestes, 748-05508-900, Cx. P. 26077,
CEP 05599-070, SaÄo Paulo, Brazil
Received 19 January 2000; accepted 23 March 2000
AbstractÐTransmetalation reaction between Z-vinylic tellurides and higher order cyanocuprates generated the corresponding Z-vinylic
cyanocuprates. Conjugate addition of these cuprates to enones followed by O-functionalization led to silyl enol ethers, vinyl phosphates and
vinyl tri¯ates. The vinyl tri¯ates were transformed into highly unsaturated systems by coupling with alkynes or with Z-vinyl zinc chlorides
under Pd (0) catalysis. q 2000 Elsevier Science Ltd. All rights reserved.
Introduction
development of practical methods to prepare alkyl vinyl
tellurides with high regio- and stereoselectivity led us1,2b,4
and others2c,5 to explore synthetically the pioneering obser-
vation made by Kauffmann. The early efforts in this area
used aryl vinyl tellurides 1 as precursors of Z-vinyl lithiums
2.5a However, we found that depending on the reaction time
and conditions, mixtures of vinyl and aryl lithiums 3 can be
formed,4 as both species have the metallic counter ion asso-
ciated to sp2 carbanionic species, presenting similar
stability. Therefore, we decided to use alkyl vinyl 4 or bis
vinyl tellurides 5 for this purpose,2b since these precursors of
vinyl organometallics do not present such drawback
(Scheme 1).
In the course of recent years our laboratory has devoted
efforts to ®nd synthetic applications to Z-vinylic tellurides,1
since these compounds can be easily prepared by hydro-
telluration of alkynes.1,2 In the majority of the cases the
reaction occurs with high regioselectivity and with the
exclusive formation of the Z isomer, which is sterically
stable. To our knowledge no isomerization of vinylic
tellurides during the isolation and puri®cation processes
was reported. In a seminal paper, Kauffmann,3 in 1982,
reported that phenyl vinyl telluride could be transformed
into vinyl lithium and captured by electrophiles. The
Scheme 1.
Keywords: Z-vinylic tellurides; higher order cyanocuprates; conjugated addition; vinyl tri¯ates; vinyl phosphates; silyl enol ethers.
* Corresponding author. Tel.: 155-11-818-2176; fax: 155-11-815-5579; e-mail: jvcomass@quim.iq.usp.br
0040±4020/00/$ - see front matter q 2000 Elsevier Science Ltd. All rights reserved.
PII: S0040-4020(00)00254-4

3328
D. N. Moraes et al. / Tetrahedron 56 (2000) 3327±3337
Scheme 2.
In view of the easier preparation of the butyl vinyl tellurides
41,6 as compared to the bis vinylic tellurides 5,1,2a,6 we
preferred the ®rst to generate Z-vinylic organometallics.
The preparation of E-vinylic organometallics by transmetal-
ation reactions is a well-established methodology,7 since
most of the precursors of reactive vinyl organometallic
species are obtained by hydrometallation of alkynes,
which gives the E ole®n through a syn addition.8 As a conse-
quence, the preparation of Z-vinyl organometallics (e.g.
vinyl lithium and vinyl copper species) by a transmetalation
reaction is not a trivial synthetic task. The discovery that the
transmetalation of Z-vinylic tellurides occurs with total
retention of the ole®n geometry,1,4,6,9 coupled with the easy
preparation of these organo element intermediates through
hydrotelluration of alkynes,1,2,6 opened the perspective of
using them to assemble more complex carbon skeletons.
As organocopper reagents are widely used organometallics
to form carbon±carbon bonds, we investigated in detail the
transformation of butyl vinyl tellurides 4 and bis vinyl tellu-
rides 5 into higher order vinylcyanocuprates.6,9 In order to
demonstrate the scope and limitations of this methodology,
the higher order vinyl cyanocuprates 6, generated in this
way, were reacted with a variety of electrophiles such as
Scheme 3.

D. N. Moraes et al. / Tetrahedron 56 (2000) 3327±3337
3329
a,b unsaturated ketones 7,6,9a,b,d epoxides 86,9c and halo-
alkynes 9,10 giving rise to unsaturated systems of great
synthetic interest, such as 4-vinylketones 10, homoallylic
alcohols 11, Z-enynes 12 and Z-enediynes 13 (Scheme 2).
In the search for synthetic applications for the vinyl
phosphates obtained 18, we attempted to assemble highly
unsaturated systems by coupling them with Z-vinyl cyano-
cuprates 6 prepared from vinylic tellurides 4 or 5. The
reaction was, however, unsuccessful. Vinyl phosphate 18a
was transformed into the corresponding vinyl iodide by
reaction with TMSCl/NaI in acetonitrile16 in 60% yield.
However, a 1:1 mixture of regioisomers 27a and 27b was
formed (Eq. (1)). Finally, an interesting application for the
vinyl phosphates of the type 18f was found, which consists
in their transformation into functionalized tetrasubstituted
vinylic telluride 28 by reaction with lithium n-butyl tellu-
rolate 29 (Scheme 4).17
Results and Discussion
Among the synthetically useful reactions of organocopper
reagents is the 1,4 addition to enones, followed by reaction
with appropriate electrophiles leading to O-functionali-
zation. In this work, we performed a systematic study of
the 1,4 addition of higher order Z-vinylic cyanocuprates to
enones followed by reaction with trimethylsilylchloride
(14), diethyl-(15a) and diphenylphosphorochloridrate
(15b) and N-phenyltri¯uoromethanesulfonamide (16)
(Scheme 3).
Among the vast spectrum of synthetic transformations
possible to perform on the obtained systems, we mention
the cyclopropanation of silyl enol ethers 17 followed by
annulation to give 22,11 the reduction12 or organometallic
coupling13 of vinyl phosphates 18 leading to unsaturated
systems 23 or 24, respectively. The coupling reactions of
vinyl tri¯ates 19, with organo zinc compounds 2014 and with
terminal alkynes 2114 catalyzed by Pd0, were studied in this
work.
ꢀ1†
Vinyl tri¯ates are among the most synthetically explored
derivatives of O-functionalization of enolate ions.14 Few
reports on the 1,4 addition of cuprates to enones followed
by tri¯ate formation do exist14 and none of them deal with
higher order cuprates. Recently, we demonstrated that our
methodology of Z higher order vinyl cyanocuprate for-
mation can be successfully applied to generate vinyl
tri¯ates.18 In this paper we give a full account of this
reaction. Initially we attempted to use tri¯ic anhydride as
the tri¯ing agent. The yields were however low and did not
exceed 30%. By changing tri¯ic anhydride for tri¯ic
chloride only gummy unidenti®ed products were obtained.
The method of choice to prepare the vinyl tri¯ates consisted
in the preparation of the higher order vinyl cyanocuprate by
addition of the appropriate Z-vinylic telluride 4 (2 mmol) to
a solution of dimethyl cyanocuprate (2 mmol) at room
temperature followed by the addition of the enone 7
(2.2 mmol) at 2758C. To the enolate formed was added
N-phenyltri¯uoromethanesulfonamide (18) (2.6 mmol) and
HMPA (6.0 mmol). Work up and puri®cation by ¯ash silica
gel chromatography gave the vinyl tri¯ates 19a±g with the
yields shown in Table 1. The use of a co-solvent was crucial
for the success of the reaction. In the reaction of telluride 4a
with enone 7a in the absence of a co-solvent after 48 h a
40% yield of vinyl tri¯ate 19a was obtained; with DME and
TMEDA as the co-solvent a 50% yield of 19a was formed
after 36 and 24 h, respectively; by using HMPA as the co-
solvent, 19a was obtained in 60% yield after 4 h. All
compounds obtained were suf®ciently stable to be puri®ed
by column chromatography.
Although the conjugated addition of cuprates to enones
followed by enolate trapping with trialkylsilyl chlorides is
a well known reaction,15 we decided to investigate it using
our reaction conditions, since the obtained silyl enol ethers
17 present a Z double bond strategically positioned to give
substituted cyclohexenes 22 if submitted to the reaction
sequence shown in Scheme 3.11 The reaction was performed
by addition of TMEDA (6 mmol) to a suspension of CuCN
(2 mmol) in THF. To this clear solution cooled to 2758C
was added MeLi (4 mmol) followed by heating to room
temperature and addition of the vinylic telluride 4
(2 mmol) or 5 (1 mmol). After stirring for 45 min, the
mixture was cooled again, to 2758C and the enone 7 was
added. Addition of trimethylsilyl chloride (14), work up and
puri®cation by distillation gave 17a±e in synthetically
useful yields (Table 1).
Although less studied than the formation of silyl enol ethers
17, the generation of vinyl phosphates 18 by conjugate
addition of Gilman cuprates to enones followed by enolate
trapping has been described.15 Notwithstanding, the 1,4
addition of higher order cyanocuprates to enones followed
by capture with phosphorochloridrates 15 has not yet been
reported. As already mentioned (Scheme 3) vinyl phos-
phates are synthetically useful.12,13,16 With this synthetic
utility in mind we explored our vinylic telluride/higher
order vinylic cyanocuprates methodology to prepare vinyl
phosphates. The Z-vinyl cyanocuprate generated from the
corresponding Z-vinylic telluride 4 (2 mmol) or 5 (1 mmol)
was reacted with an enone 7 (2.2 mmol) at 2758C and to the
resulting enolate was added diethyl- (15a) or diphenyl-
phosphorochloridrates (15b) (3.2 mmol) in THF and
TMEDA (6 mmol). The product was puri®ed by silica gel
chromatography to give the vinyl phosphates 18a±f in good
yields (Table 1).
In this case the construction of highly unsaturated con-
jugated systems by elaboration of the product of the 1,4
addition/electrophile capture was successful.
Our vinylic telluride transmetalation methodology proved to
be a valuable method to generate Z-vinyl zinc chlorides.

3330
D. N. Moraes et al. / Tetrahedron 56 (2000) 3327±3337
Table 1. Products of the 1,4-addition of Z-vinylic cuprates to enones followed by O-functionalization
Entry
1
Telluride
Enone
Product
Yield (%)
85
2
5a
7a
7a
85
3
4
60
72
5a
5
6
7
5a
5a
5a
4a
7b
90
70
80
7c
8
9
7c
7a
50
65
10
7a
67

D. N. Moraes et al. / Tetrahedron 56 (2000) 3327±3337
3331
Table 1 (continued)
Entry
Telluride
Enone
Product
Yield (%)
11
12
13
4c
7a
7a
7a
65
67
4d
4d
65
14
15
7a
7a
55
65
16
17
18
4a
4a
4a
70
60
50
7d
Organo zinc chlorides are useful intermediates for a number
of synthetic transformations.19 The Z-vinyl zinc chlorides
were prepared by treating butyl Z-vinylic tellurides 4
(1.2 mmol) in THF with n-butyllithium (1.2 mmol) at
2758C and then adding a solution of ZnCl2 (1.3 mmol) at
the same temperature. The Z-vinyl zinc chlorides 30 formed
in this way were added to a mixture of Pd[P(Ph)3]4
(0.1 mmol) and the enol tri¯ate 19a (1.0 mmol). The
coupled products 25a±c were obtained in good yields
(Scheme 5).
Sonogashira reaction on the obtained vinyl tri¯ate 19a gave
the coupled products 26a±e in good yields (Scheme 6).
In conclusion, the 1,4-addition of Z-vinyl cyanocuprates to
enones followed by O-functionalization can be used to

3332
D. N. Moraes et al. / Tetrahedron 56 (2000) 3327±3337
Scheme 4.
Scheme 5.
Scheme 6.
assemble highly unsaturated systems, in the case of the vinyl
tri¯ates, the vinyl phosphates are precursors of
functionalized tri- and tetrasubstituted Z-vinylic tellurides.
The silyl enol ethers are being used in our laboratory in
carbocyclization reactions.
was purchased from Aldrich and dried overnight in an
oven at 1008C, CuCN was dried under vacuum in an
Abderhalden apparatus over P2O5, at 708C. The following
reagents were prepared according to the literature pro-
cedures: butyl vinyl tellurides,6 bis vinylic tellurides,2a,6
dibutyl ditelluride,6 N-phenyl tri¯uoromethanesulfona-
mide.21 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.
Experimental
1H and 13C NMR spectra were recorded on either a Bruker
DPX-300, Bruker DRX-500 or a Bruker AC-200 spec-
trometers using as internal standard tetramethylsilane and
the central peak of CDCl3 (77 ppm), respectively. Infrared
spectra were recorded on a Perkin±Elmer 1600 spectro-
photometer. Low resolution mass spectra were obtained
on a Finnigan 4021 spectrometer or on a GC/MS-Hewlett±
Packard 5988-8/5890 spectrometer, both operating at 70 eV.
Elemental analysis was performed at the Microanalytical
Laboratory of the Chemistry Institute, University of SaÄo
Paulo. Column chromatography was carried out with
Merck silica gel (230±400 mesh). Thin layer chroma-
tography (TLC) was performed on silica gel F-254 on
aluminum. All solvents used were previously dried and
distilled according to the usual methods.20 THF and diethyl
ether were distilled from sodium/benzophenone under N2,
immediately before use. Elemental tellurium (200 mesh)
General procedure for the 1,4 addition of higher order
mixed cyanocuprates 6 to enones followed by
O-functionalization by chlorotrimethylsilane (14)
Methyl lithium (4.0 mmol, 1.0 M in diethyl ether, 4.0 mL)
was added to a suspension of CuCN (2.0 mmol, 0.18 g) in
THF (10 mL) at 2758C. The reaction mixture was then
stirred until a clear solution was obtained and allowed to
warm to room temperature. The appropriate Z-vinylic
telluride 4 (2.0 mmol) or 5 (1.0 mmol) was added and
stirred for 45 min. The solution was cooled back to
2758C and the corresponding enone (2.2 mmol) was
added. After 20 min, chlorotrimethylsilane 14 (2.6 mmol,

D. N. Moraes et al. / Tetrahedron 56 (2000) 3327±3337
3333
0.60 g) diluted in THF (5 mL) was added. The reaction
mixture was stirred for 1 h, allowed to warm to room
temperature and then treated with 1:1 solution of saturated
aqueous NH4Cl and NH4OH (20 mL), extracted with ethyl
acetate (3£20 mL), dried, evaporated and the residue was
puri®ed by Kugehlror distillation affording the silyl enol
ethers 17.
85 (41), 73 (100), 67 (13), 55 (18). Anal. calcd for
C19H32O3Si: C, 67.66, H, 9.77. Found: C, 67.55, H, 9.75.
Trimethyl({3-[(Z)-1-octen-3-ynyl]-1-cyclohexen-1-yl}oxy)-
silane (17e). Yield: 0.37 g (67%), H NMR (200 MHz,
1
CDCl3) d (ppm) 5.61 (dd, Jˆ10.1, 10.0 Hz, 1H); 5.33 (dt,
Jˆ10.6, 2.1 Hz, 1H); 4.69±4.67 (m, 1H); 3.34±3.24 (m,
1H); 2.30 (td, Jˆ6.9, 2.0 Hz, 2H); 2.01±1.91 (m, 2H);
1.75±1.69 (m, 2H); 1.61±1.59 (m, 1H); 1.50 (quint.,
Jˆ7.1 Hz, 2H); 1.40 (sext., Jˆ7.3 Hz, 2H); 1.22±1.19 (m,
1H); 0.88 (t, Jˆ7.2 Hz, 3H); 0.15 (s, 9H). 13C NMR
(50 MHz, CDCl3) d (ppm) 151.2, 146.6, 108.0, 106.8,
94.5, 77.1, 35.8, 30.9, 29.7, 28.4, 21.9, 21.4, 19.2, 13.5,
0.2. IR (cm21) (neat) 3018, 2959, 2934, 2863, 1719, 1661,
1456, 1367, 1252, 1201, 1188, 907, 847. LRMS m/z (rel.
int.) 276 (5) (M1), 233 (10), 219 (11), 191 (2), 143 (5), 129
(10), 91 (4), 73 (100). HRMS exact mass calcd for
C17H28OSi: 276.19094. Found: 276.19054.
Trimethyl({3-[(Z)-2-phenylethenyl]-1-cyclohexen-1-yl}-
oxy)silane (17a). Yield: 0.46 g (85%), 1H NMR (200 MHz,
CDCl3) d (ppm) 7.45±7.26 (m, 5H); 6.47 (d, Jˆ11.5 Hz,
1H); 5.60 (dd, Jˆ11.2, 10.8 Hz, 1H); 4.89±4.88 (m, 1H);
3.56±3.48 (m, 1H); 2.17±2.10 (m, 2H); 1.93±1.65 (m, 3H);
1.48±1.34 (m, 1H); 0.29 (s, 9H). 13C NMR (50 MHz,
CDCl3) d (ppm) 151.3, 137.5, 137.4, 128.6, 128.1, 127.5,
126.5, 107.3, 33.7, 29.6, 29.4, 21.4, 0.3. IR (cm21) (neat)
3414, 3015, 1594, 1582, 1487, 1449, 1335, 1294, 779, 695,
686, 503. LRMS m/z (rel. int.) 272 (67) (M1), 257 (6), 244
(8), 195 (12), 181 (17), 153 (14), 128 (15), 115 (13), 91 (13),
73 (100). Anal. calcd for C17H24OSi: C, 74.96, H, 9.05.
Found: C, 75.39, H, 9.23.
General procedure for the 1,4 addition of higher order
mixed cyanocuprates 6 to enones followed by
O-functionalization by diethylchlorophosphorochloridrate
(15a)
({4,4-Dimethyl-3-[(Z)-2-phenylethenyl]-1-cyclohexen-1-yl}-
oxy)(trimethyl)silane (17b). Yield: 0.43 g (72%), 1H NMR
(200 MHz, CDCl3) d (ppm) 7.35±7.16 (m, 5H); 6.45 (d,
Jˆ11.6 Hz, 1H); 5.50 (t, Jˆ11.4 Hz, 1H); 4.81±4.79 (m,
1H); 3.15±3.08 (m, 1H); 2.23±2.01 (m, 2H); 1.60±1.48
(m, 1H); 1.42±1.28 (m, 1H); 0.87 (s, 3H); 0.84 (s, 3H);
0.19 (s, 9H). 13C NMR (50 MHz, CDCl3) d (ppm) 150.2,
137.8, 137.8, 128.8, 128.1, 126.4, 106.8, 43.1, 34.9, 31.8,
28.0, 27.7, 27.6, 23.4, 0.4. IR (cm21) (neat) 3012, 2958,
2922, 2896, 1662, 1600, 1449, 1253, 1197, 1167, 918,
884. LRMS m/z (rel. int.) 300 (17) (M1), 244 (100), 229
(10), 181 (2), 153 (58), 128 (14), 91 (14), 73.(88). Anal. for
C19H28OSi: C, 75.94, H, 9.39. Found: C, 76.33, H, 9.35.
Methyllithium (4.0 mmol, 1.0 M in THF/Cumene, 4.0 mL)
was added to a suspension of CuCN (2.0 mmol, 0.18 g) in
THF (10 mL) at 2758C. The reaction mixture was then
stirred until a clear solution was obtained and allowed to
warm to room temperature. The appropriate Z-vinylic
telluride 4 (2.0 mmol) or 5 (1.0 mmol) was added and
stirred for 45 min. The solution was cooled back to
2758C and the corresponding enone (2.2 mmol) was
added. After 20 min, TMEDA (6.0 mmol, 0.70 mL) and
diethylphosphorochloridrate 15a (2.6 mmol, 0.46 g) in
THF (5 mL) were added and the solution was allowed to
warm to 08C. The reaction mixture was stirred for 1 h and
then treated with 1:1 solution of saturated aqueous NH4Cl/
NH4OH (3£20 mL), extracted with ethyl acetate
(3£20 mL), dried, evaporated and the residue was puri®ed
by ¯ash silica gel chromatography using a 3:1 hexane:ethyl
acetate as eluent affording the vinyl phosphates 18.
Trimethyl({3-[(Z)-2-phenylethenyl]-1-cyclopenten-1-yl}-
oxy)silane (17c). Yield: 0.36 g (70%), 1H NMR (200 MHz,
CDCl3) d (ppm) 7.31±7.20 (m, 5H); 6.33 (d, Jˆ11.4 Hz,
1H); 5.55 (t, Jˆ10.8 Hz, 1H); 4.63±4.56 (m, 1H); 3.85±
3.72 (m, 1H); 2.46±2.11 (m, 3H); 1.75±1.54 (m, 1H);
0.22 (s, 9H). 13C NMR (50 MHz, CDCl3) d (ppm) 156.0,
138.1, 137.5, 128.7, 128.4, 128.2, 128.1, 127.1, 126.5,
105.6, 40.4, 33.3, 29.6, 0.1. IR (cm21) (neat) 3061, 3005,
1746, 1643, 1344, 1310, 1253, 1187, 929, 869. LRMS m/z
(rel. int.) 258 (50) (M1), 243 (3), 181 (25), 155 (13), 128
(14), 91 (10), 73 (100). Anal. calcd for C16H22OSi: C, 74.38,
H, 8.52. Found: C, 74.69, H, 8.30.
Diethyl 3-[(Z)-2-phenylethenyl]-1-cyclohexen-1-yl phos-
phate (18a). Yield: 0.57 g (85%), H NMR (300 MHz,
1
CDCl3) d (ppm) 7.41±7.24 (m, 5H); 6.42 (d, Jˆ11.5 Hz,
1H); 5.50 (dd, Jˆ11.4, 10.5 Hz, 1H); 5.37±5.27 (m, 1H);
4.15±4.10 (m, 4H); 3.49±3.44 (m, 1H); 2.27±2.22 (m, 2H);
1.82±1.32 (m, 4H); 1.37 (t, Jˆ7.1 Hz, 6H). 13C NMR
(75 MHz, CDCl3) d (ppm) 148.6, 137.3, 135.6, 128.7,
128.6, 128.3, 126.8, 113.6, 64.2, 64.1, 33.5, 28.8, 27.6,
21.0, 16.2, 16.1. IR (cm21) (neat) 2985, 2936, 1677, 1446,
1368, 1273, 1141, 1098, 1029, 920, 702. LRMS m/z (rel.
int.) 336 (26) (M1), 307 (14), 279 (3), 251 (2), 199 (8), 182
(10), 167 (100), 154 (44), 91 (49), 81.(36), 77 (21), 65 (11).
Anal. calcd for C18H25PO4: C, 64.27, H, 7.44. Found: C,
63.95, H, 7.56.
Trimethyl({3-[(1Z,3E)-5-(tetrahydro-2H-pyran-2-yloxy)-
1,3-pentadienyl]-1-cyclohexen-1-yl}oxy)silane
(17d).
1
Yield: 0.43 g (65%), H NMR (200 MHz, CDCl3) d (ppm)
6.57 (dd, Jˆ11.2, 15.0 Hz, 1H); 5.93 (dd, Jˆ10.8, 11.0 Hz,
1H); 5.77 (dt, Jˆ6.4, 15.0 Hz, 1H); 5.28 (t, Jˆ10.2 Hz, 1H);
4.66±4.64 (m, 2H); 4.28 (dd, Jˆ6.4, 12.7 Hz, 1H); 4.02 (dd,
Jˆ6.4, 12.8 Hz, 1H); 3.88±3.83 (m, 1H); 3.54±3.48 (m,
1H); 3.30±3.20 (m, 1H); 1.99±1.52 (m, 12H); 0.18 (s,
9H). 13C NMR (50 MHz, CDCl3) d (ppm) 151.0, 137.2,
129.3, 127.9, 126.3, 107.2, 97.7, 67.4, 62.0, 33.5, 30.5,
29.5, 29.2, 25.4, 21.4, 19.4, 0.2. IR (cm21) (neat) 2932,
2861, 1716, 1661, 1450, 1368, 1252, 1189, 1117, 986,
952, 906, 847. LRMS m/z (rel. int.) 336 (25) (M1), 281
(7), 263 (4), 251 (31), 234 (7), 208 (52), 131 (6), 93 (21),
4,4-Dimethyl-3-[(Z)-2-phenylethenyl]-1-cyclohexen-1-yl
diethyl phosphate (18b). Yield: 0.65 g (90%), H NMR
1
(200 MHz, CDCl3) d (ppm) 7.35±7.20 (m, 5H); 6.50 (d,
Jˆ11.6 Hz, 1H); 5.49 (dd, Jˆ11.4, 11.3 Hz, 1H); 5.31±
5.31 (m, 1H); 4.15±4.10 (m, 4H); 3.20±3.15 (m, 1H);
2.25±2.10 (m, 2H); 1.67±1.46 (m, 2H); 1.34 (t, Jˆ7.1 Hz,

3334
D. N. Moraes et al. / Tetrahedron 56 (2000) 3327±3337
6H); 0.88 (s, 3H); 0.85 (s, 3H). 13C NMR (50 MHz, CDCl3)
d (ppm) 147.3, 137.3, 132.3, 129.8, 128.5, 128.1, 126.5,
112.7, 64.1, 63.9, 42.8, 34.1, 31.7, 27.6, 25.4, 23.5, 16.1,
15.9. IR (cm21) (neat) 3449, 3056, 2983, 2937, 2911, 1737,
1656, 1446, 1343, 1277, 1219, 1167, 1034, 968, 701. LRMS
m/z (rel. int.) 364 (13) (M1), 308 (38), 251 (9), 231 (36), 175
(12), 154 (100), 128 (7), 91 (43), 81 (26). Anal. calcd for
C20H29PO4: C, 65.93, H 7.96. Found: C, 65.92, H, 7.75.
(s, 3H); 2.50±2.46 (m, 2H); 2.04±1.60 (m, 4H); 1.38±1.32
(m, 6H). 13C NMR (125 MHz, CDCl3) d (ppm) 166.8,
151.7, 137.4, 133.6, 130.6, 130.2, 128.7, 128.4, 127.0,
119.5, 64.7, 51.5, 34.5, 28.8, 28.6, 19.9, 16.3. IR (cm21
)
(neat) 3055, 2986, 2946, 1726, 1670, 1276, 1032. LRMS
m/z (rel. int.) 362 (100), 334 (14), 288 (7), 226 (92), 179
(38), 141 (21), 91 (27). Anal. calcd for C20H27PO6: C, 60.91,
H, 6.90. Found: C, 60.81, H, 7.13.
Diethyl 3-[(Z)-2-phenylethenyl]-1-cyclopenten-1-yl phos-
phate (18c). Yield: 0.51 g (80%), 1H NMR (200 MHz,
CDCl3) d (ppm) 7.41±7.24 (m, 5H); 6.44 (d, Jˆ11.5 Hz,
1H); 5.61 (t, Jˆ10.8 Hz, 1H), 5.22±5.20 (m, 1H); 4.15±4.10
(m, 4H); 3.90±3.84 (m, 1H); 2.61±2.56 (m, 2H); 2.37±2.22
(m, 1H); 1.80±1.73 (m, 1H), 1.25 (t, Jˆ7.1 Hz, 6H). 13C
NMR (50 MHz, CDCl3) d (ppm) 150.8, 137.1, 128.6, 128.3,
128.2, 128.1, 126.6, 112.3, 64.4, 64.3, 40.1, 34.8, 31.3, 29.3,
26.9, 16.1, 15.9. IR (cm21) (neat) 2984, 2935, 2911, 1701,
1656, 1275, 1218, 1167, 1034, 968, 700. LRMS m/z (rel.
int.) 322 (41) (M1), 293 (8), 265 (4), 231 (4), 190 (8), 167
(100), 153 (42), 91 (41), 81 (39). Anal. calcd for C17H23PO4:
C, 63.35, H, 7.33. Found: C, 63.35, H, 7.14.
General procedure for the 1,4 addition of higher order
mixed cyanocuprates 6 to enones followed by
O-functionalization by N-phenyltri¯uoromethane-
sulfonamide (16)
Methyl lithium (4.0 mmol, 1.0 M in THF/Cumene, 4.0 mL)
was added to a suspension of CuCN (2.0 mmol, 0.18 g) in
THF (10 mL) at 2758C. The reaction mixture was then
stirred until a clear solution was obtained and allowed to
warm to room temperature. The appropriate Z-vinyl butyl
telluride 4 (2.0 mmol) was added and stirred for 45 min. The
solution was cooled back to 2758C and the corresponding
enone 7 (1.1 mmol) was added. After 20 min, HMPA
(6.0 mmol, 0.6 mL) and N-phenyltri¯uoromethanesulfona-
mide (16) (2.6 mmol, 0.6 g) in THF (5 mL) were added and
the solution was allowed to warm to room temperature. The
reaction mixture was stirred for 4 h and then treated with 1:1
solution of saturated aqueous NH4Cl/NH4OH (20 mL),
extracted with ethyl acetate (3£20 mL), dried, evaporated
and the residue was puri®ed by ¯ash silica gel chroma-
tography using hexane as eluent affording the vinyl tri¯ates
19.
3-((1Z,3E)-5-{[tert-Butyl(dimethyl)silyl]oxy}-1,3-penta-
dienyl)-1-cyclohexen-1-yl diethyl phosphate (18d). Yield:
0.57 g (67%), H NMR (500 MHz, CDCl3) d (ppm) 6.51
1
(dd, Jˆ11.2, 15.1 Hz, 1H); 5.97 (dd, Jˆ10.9, 11.0 Hz, 1H);
5.76 (dt, Jˆ5.1, 15.1 Hz, 1H); 5.30±5.29 (m, 1H); 5.25 (dd,
Jˆ10.1, 10.3 Hz, 1H); 4.24 (d, Jˆ5.1 Hz, 2H); 4.19±4.12
(m, 4H); 3.36±3.35 (m, 1H); 2.24±2.21 (m, 2H); 1.86±1.82
(m, 1H); 1.78±1.72 (m, 2H); 1.69±1.65 (m, 1H); 1.34 (t,
Jˆ7.1 Hz, 6H); 0.92 (s, 9H); 0.08 (s, 6H). 13C NMR
(125 MHz, CDCl3) d (ppm) 148.4, 134.4, 133.4, 127.6,
124.8, 113.8, 64.1, 63.6, 33.4, 28.8, 27.6, 27.5, 28.9, 25.2,
21.1, 18.4, 16.2, 16.1, 0.5, 0.2. IR (cm21) (neat) 3467, 2933,
2857, 1678, 1652, 1446, 1436, 1369, 1273, 1143, 1102,
1037, 968, 837, 778. LRMS m/z (rel. int.) 430 (8) (M1),
373 (26), 285 (100), 257 (10), 197 (6), 155 (28), 73 (32).
Anal. calcd for C21H39PO5Si: C, 58.58, H, 9.13. Found: C,
58.24, H, 9.01.
3-[(Z)-2-Phenylethenyl]-1-cyclohexen-1-yl tri¯uoromethane-
1
sulfonate (19a). Yield: 0.39 g (60%), H NMR (300 MHz,
CDCl3) d (ppm) 7.36±7.19 (m, 5H); 6.49 (d, Jˆ11.4 Hz,
1H); 5.64±5.63 (m, 1H); 5.46 (dd, Jˆ11.4, 10.5 Hz, 1H);
3.46±3.60 (m, 1H); 2.33±2.31 (m, 2H); 1.98±1.63 (m, 3H);
1.48±1.35 (m, 1H). 13C NMR (75 MHz, CDCl3) d (ppm)
149.9, 136.8, 133.3, 129.9, 128.5, 128.4, 127.1, 121.2, 118.4
(quart., JC±Fˆ318 Hz), 33.9, 28.2, 27.4, 21.0. IR (cm21
)
(neat) 3014, 2945, 1684, 1418, 1212, 1143, 900, 701.
LRMS m/z (rel. int.) 332 (20) (M1), 199 (26), 181 (71),
141 (79), 128 (68), 115 (50), 91 (100), 55 (64). Anal.
calcd for C15H15O3SF3: C, 54.21, H, 4.55. Found: C,
54.11, H, 4.73.
Diethyl 3-[(Z)-1-octen-3-ynyl]-1-cyclohexen-1-yl phos-
phate (18e). Yield: 0.44 g (65%), 1H NMR (500 MHz,
CDCl3) d (ppm) 5.65 (dd, Jˆ10.1, 10.0 Hz, 1H); 5.44 (dt,
Jˆ10.5, 1.9 Hz, 1H); 5.37±5.34 (m, 1H); 4.18±4.12 (m,
4H); 3.55±3.40 (m, 1H); 2.32 (td, Jˆ6.9, 1.9 Hz, 2H);
2.22±2.12 (m, 2H); 1.84±1.79 (m, 2H); 1.67±1.81 (m,
2H); 1.52 (quint., Jˆ7.0 Hz, 2H); 1.43 (sext., Jˆ7.3 Hz,
2H); 1.35 (t, Jˆ7.1 Hz, 6H); 0.92 (t, Jˆ7.2 Hz, 3H). 13C
NMR (125 MHz, CDCl3) d (ppm) 148.3, 144.5, 113.0,
109.2, 95.1, 76.8, 64.1, 64.0, 35.5, 30.8, 27.7, 27.4, 21.8,
20.9, 19.1, 16.0, 15.9, 13.4. IR (cm21) (neat) 2982, 2957,
2933, 2865, 1678, 1368, 1273, 1147, 1030, 972, 932, 918.
LRMS m/z (rel. int.) 340 (2) (M1), 283 (24), 255 (8), 227
(13), 186 (40), 144 (73), 129 (100), 99 (43), 79 (12). HRMS
exact mass calcd for C18H29PO4: 340.18035. Found:
340.18066.
3-[(Z)-2-Phenylethenyl]-1-cyclopenten-1-yl tri¯uorometh-
anesulfonate (19b). Yield: 0.31 g (50%), 1H NMR
(500 MHz, CDCl3) d (ppm) 7.35±7.20 (m, 5H); 6.46 (d,
Jˆ11.4 Hz, 1H); 5.55 (d, Jˆ1.9 Hz, 1H); 5.52 (dd,
Jˆ10.5, 11.4 Hz, 1H); 3.91±3.90 (m, 1H); 2.69±2.59 (m,
2H); 2.34±2.29 (m, 1H); 1.86±1.79 (m, 1H). 13C NMR
(125 MHz, CDCl3) d (ppm) 150.1, 136.8, 132.8, 129.6,
128.6, 128.3, 127.0, 122.3, 118.6 (quart., JC±Fˆ318 Hz),
40.2, 31.1, 29.7. IR (cm21) (neat) 3024, 2958, 2937, 1684,
1419, 1208, 1144, 900. LRMS m/z (rel. int.): 318 (19) (M1),
185 (35), 141 (100), 128 (79), 91 (41), 69 (25). Anal. calcd
for C14H13O3SF3: C, 52.83, H, 4.09. Found: C, 52.86, H,
4.20.
Methyl
ethenyl]-1-cyclohexene-1-carboxylate
2-[(diethoxyphosphoryl)oxy]-6-[(Z)-2-phenyl-
(18f). Yield:
1
0.55 g (70%), H NMR (500 MHz, CDCl3) d (ppm) 7.36±
7.24 (m, 5H); 6.44 (d, Jˆ11.5 Hz, 1H); 5.52 (dd, Jˆ10.7,
11.4 Hz, 1H); 4.24±4.02 (m, 4H); 3.97±3.90 (m, 1H); 3.55
3-((1Z,3E)-5-{[tert-Butyl(dimethyl)silyl]oxy}-1,3-penta-
dienyl)-1-cyclohexen-1-yl tri¯uoromethanesulfonate (19c).
1
Yield: 0.55 g (65%), H NMR (300 MHz, CDCl3) d (ppm)

D. N. Moraes et al. / Tetrahedron 56 (2000) 3327±3337
3335
6.54±6.45 (m, 1H); 6.03 (dd, Jˆ11.0, 10.8 Hz, 1H); 5.80
(dt, Jˆ15.1, 5.1 Hz, 1H); 5.58±5.57 (m, 1H); 5.22 (dd,
Jˆ17.0, 10.0 Hz, 1H); 4.25 (d, Jˆ5.1 Hz, 2H); 3.47±3.42
(m, 1H); 2.34±2.32 (m, 2H); 1.96±1.70 (m, 4H); 0.92 (s,
9H); 0.08 (s, 6H). 13C NMR (75 MHz, CDCl3) d (ppm)
196.7, 149.7, 134.4, 131.9, 128.7, 124.0, 121.4, 118.4
(quart., JC±Fˆ318 Hz), 63.4, 33.7, 28.2, 27.4, 25.9, 21.1,
18.4. IR (cm21) (neat) 2952, 2934, 2858, 1684, 1418,
1248, 1212, 1143, 837, 778, 610. LRMS m/z (rel. int.):
369 (4), 313 (4), 145 (100), 117 (70), 91 (68). Anal. calcd
for C18H29O4SiSF3: C, 50.68, H, 6.85. Found: C, 50.79, H,
6.57.
(rel. int.) 157 (12), 129 (83), 115 (38), 91 (100), 77 (30), 69
(52). Anal. calcd for C13H13O3SF3: C, 50.68, H, 6.87. Found:
C, 50.79, H, 6.57.
General procedure for the preparation of vinylic
telluride 28 from enolphosphate 18f
To a suspension of tellurium powder (200 mesh, 0.254 g,
2.0 mmol) in THF (2 mL) at room temperature was added
n-BuLi (1.4 M in hexanes, 0.7 mL, 2.0 mmol). The dark
mixture turned a pale yellow clear solution, which was
cooled to 08C. The enolphosphate 18f (0.54 g, 1.5 mmol)
was then added dropwise. After 30 min, ethyl acetate
(20 mL) was added and the organic layer was washed
with brine (3£10 mL), dried with magnesium sulphate and
the solvent was evaporated. The residue was puri®ed by
silica gel column chromatography eluting with a mixture
of hexane/ethyl acetate (9:1). Compound 28 was isolated
as yellow oil.
3-[(Z)-1-Octen-3-ynyl]-1-cyclohexen-1-yl tri¯uorometh-
anesulfonate (19d). Yield: 0.37 g (55%), 1H NMR
(500 MHz, CDCl3) d (ppm) 5.64 (d, Jˆ2.2 Hz, 1H); 5.61
(t, Jˆ10.6 Hz, 1H); 5.50 (d, Jˆ10.6 Hz, 1H); 3.59±3.56 (m,
1H); 2.38±2.29 (m, 4H); 1.91±1.77 (m, 3H); 1.50 (quint.,
Jˆ7.1 Hz, 2H); 1.45±1.35 (m, 3H); 0.93 (t, Jˆ7.3 Hz, 3H).
13C NMR (125 MHz, CDCl3) d (ppm) 149.8, 142.2, 120.7,
118.0 (quart., JC±Fˆ318 Hz), 110.7, 96.3, 77.2, 35.9, 30.7,
27.4, 27.2, 21.9, 21.0, 19.2, 13,5. IR (cm21) (neat) 2906,
2869, 1659, 1424, 1213, 1142, 917, 700. LRMS m/z (rel.
int.) 336 (3) (M1), 203 (18), 147 (20), 105 (59), 91 (78), 55
(100). Anal. calcd for C15H19O3SF3: C, 53.56, H, 5.69.
Found: C, 53.46, H, 5.76.
Methyl 6-[(Z)-2-phenylethenyl]-2-(butyl telluro)-1-cyclo-
hexene-1-carboxylate (28). Yield: 0.68 g (80%), H NMR
1
(300 MHz, CDCl3) d (ppm) 7.35±7.23 (m, 5H); 6.37 (d,
Jˆ11.4 Hz, 1H); 5.57 (dd, Jˆ11.4, 10.8 Hz, 1H); 3.98 (m,
1H); 3.47 (s, 3H); 2.78±2.71 (m, 1H); 2.58±2.50 (m, 3H),
1.86±1.84 (m, 3H); 1.72±1.63 (m, 3H); 1.41 (sext.,
Jˆ7.2 Hz, 2H); 0.95 (t, Jˆ7.2 Hz, 3H). 13C NMR
(75 MHz, CDCl3) d (ppm) 169.5, 141.9, 138.1, 135.4,
128.7, 128.5, 128.3, 126.7, 51.7, 35.8, 33.4, 29.2, 25.6,
20.9, 13.7, 6.7. IR n (cm21) (neat) 3007, 2953, 2930,
2870, 1715, 1678, 1435, 1273, 1255, 702. LRMS m/z (rel.
int.) 426 (16), 371 (91), 181 (88), 91 (100), 57 (55). Anal.
calcd for C20H26O2Te: C, 56.39, H, 6.15. Found: C, 56.74,
H, 6.50.
3-[(Z)-4-(Trimethylsilyl)-1-buten-3-ynyl]-1-cyclohexen-
1-yl tri¯uoromethanesulfonate (19e). Yield: 0.45 g (65%),
1H NMR (500 MHz, CDCl3) d (ppm) 5.70 (dd, Jˆ10.7,
9.8 Hz, 1H); 5.63±5.61 (m, 1H); 5.50 (d, Jˆ10.7 Hz, 1H);
3.58±3.50 (m, 1H); 2.40±2.30 (m, 2H); 1.80±1.70 (m, 3H);
1.39±1.36 (m, 1H); 0.16 (s, 9H). 13C NMR (125 MHz,
CDCl3) d (ppm) 149.9, 149.0, 120.3, 118.4 (quart., JC±F
ˆ
318 Hz), 110.3, 100.8, 100.5, 41.4, 27.2, 27.0, 20.9. IR
(cm21) (neat) 2958, 2152, 1686, 1418, 1250, 1212, 1143,
900, 844, 632. LRMS m/z (rel. int.): 352 (3) (M1), 337 (5),
219 (35), 187 (12), 145 (29), 75 (56), 69 (100). Anal. calcd
for C14H19O3SiSF3: C, 47.73, H, 5.39. Found: C, 47.42, H,
5.41.
Transformation of the enolphosphate 18a into vinyl
iodides 27a and 27b
To a mixture of the vinyl phosphate 18a (3.30 g,
10.0 mmol), sodium iodide (4.50 g, 30.0 mmol) and aceto-
nitrile (20 mL) under nitrogen and magnetic stirring, at
room temperature, was added chlorotrimethylsilane
(3.24 g, 30.0 mmol). After 15 min at room temperature the
reaction was ®ltered, the solvent was evaporated and the
residue was dissolved in CH2Cl2, washed with saturated
aqueous solution of sodium bicarbonate and aqueous
sodium thiosulfate. The aqueous phase was extracted
twice with CH2Cl2. The organic extracts were dried with
magnesium sulfate and evaporated. The residue was chro-
matographed on silica gel eluting with hexane. The product
was isolated as a 1:1 mixture of 27a and b.
Methyl 6-[(Z)-2-phenylethenyl]-2-{[(tri¯uoromethyl)sul-
fonyl]oxy}-1-cyclohexene-1-carboxylate (19f). Yield:
1
0.46 g (60%), H NMR (500 MHz, CDCl3) d (ppm) 7.35±
7.24 (m, 5H); 6.52 (d, Jˆ10.0 Hz, 1H); 5.51 (t, Jˆ10.0 Hz,
1H); 4.05±4.03 (m, 1H); 3.65 (s, 3H); 2.46±2.41 (m, 2H);
1.90±1.62 (m, 4H). 13C NMR (125 MHz, CDCl3) d (ppm)
164.8, 150.6, 136.7, 131.5, 131.2, 128.4, 128.3, 127.1,
126.5, 119.6, 118.3 (quart., JC±Fˆ318 Hz), 51.9, 35.0,
28.2, 28.1, 19.7. IR (cm21) (neat) 3022, 2952, 1733, 1679,
1423, 1249, 1211, 1140, 1056, 911, 701, 618. LRMS m/z
(rel. int.): 225 (100), 183 (3), 141 (17), 69 (15). Anal. calcd
for C17H17O5SF3: C, 51.31, H, 4.39. Found: C, 51.44, H,
4.38.
1-Iodo-3-[(Z)-2-phenylethenyl]-1-cyclohexene (27a) and
1-iodo-5-[(Z)-2-phenylethenyl]-1-cyclohexene (27b). Yield:
1.92 g (60 %), 1H NMR (200 MHz, CDCl3) d (ppm) 7.37±
7.20 (m, 5 H); 6.45 (d, Jˆ11.5 Hz, 1 H); 6.41 (d, Jˆ11.5 Hz,
1H); 6.35±6.34 (m, 1H); 6.27±6.24 (m, 1H); 5.55±5.43 (m,
1H); 3.45±3.41 (m, 1H); 2.67±2.46 (m, 2H); 2.16±2.10 (m,
1H); 1.87±1.40 (m, 3H). 13C NMR (50 MHz, CDCl3) d
(ppm) 139.4, 137.2, 136.9, 136.9, 135.5, 134.4, 128.9,
128.6, 128.5, 128.2, 126.8, 126.7, 98.2, 94.9, 45.2, 39.1,
38.5, 35.4, 27.9, 27.3, 23.6. LRMS m/z (rel. int.) 320 (62)
(M1), 219 (1), 183 (61), 155 (12), 141 (100), 91 (59), 77
(4Z)-1-Methyl-5-phenyl-1,4-pentadienyl tri¯uoromethane-
1
sulfonate (19g). Yield: 0.30 g (50%), H NMR (500 MHz,
CDCl3) d (ppm) 7.36±7.23 (m, 5H); 6.52 (d, Jˆ11.5 Hz,
1H); 5.61±5.55 (m, 1H); 5.27 (t, Jˆ7.2 Hz, 1H); 3.17 (t,
Jˆ7.2 Hz, 2H); 2.07 (s, 3H). 13C NMR (125 MHz, CDCl3) d
(ppm) 145.4, 136.6, 130.9, 128.6, 128.3, 128.3, 127.5,
127.0, 118.6 (quart., JC±Fˆ318 Hz), 25.3, 19.7. IR (cm21
)
(neat) 3020, 2955, 2930, 1680, 1420, 1245, 900. LRMS m/z

3336
D. N. Moraes et al. / Tetrahedron 56 (2000) 3327±3337
(25), 65 (10), 51 (12). IR (cm21) (®lm) 3024, 3005, 2930,
2854, 1638, 1493, 1446, 1430, 794, 768, 736, 699. Anal.
calcd for C14H15I: C, 54.21, H, 4.84. Found: C, 54.02, H,
4.82.
(125 MHz, CDCl3) d (ppm) 143.2, 137.6, 137.5, 135.7,
134.9, 128.7, 128.6, 128.2, 126.7, 104.8, 104.5, 100.4,
35.4, 29.1, 27.0, 21.1, 0.2. LRMS m/z (rel. int.): 306 (2)
(M1), 263 (1), 233 (29), 191 (11), 128 (9), 91 (14), 73
(100). IR (cm21) (®lm) 3009, 2957, 2932, 2138, 2097,
1946, 1613, 1493, 1447, 1406, 1250, 1000, 845, 761, 700,
635. Anal. calcd for C21H26Si: C, 82.29, H, 8.55. Found: C,
82.38, H, 8.27.
General procedure for the cross-coupling reaction
between enol tri¯ate 19a and Z-vinylic zinc chloride 30,
catalyzed by Pd[P(Ph)3]4
n-Butyl lithium (1.2 mmol, 2.5 M in hexane, 0.40 mL) was
added to a solution of the appropriate Z-vinyl butyl telluride
4 (1.2 mmol) in THF (5.0 mL) at 2758C and stirred for
45 min. After this time, ZnCl2 (1.2 mmol, 1.0 M in THF,
1.20 mL) was added and the mixture was warmed up to
room temperature. This solution was transferred via cannula
General procedure for the coupling reaction between
enol tri¯ate 19a and terminal alkynes 21, catalyzed by
Pd[P(Ph)3]4
Enol tri¯ate 19a, (1.0 mmol, 0.33 g) was added to a stirred
suspension containing a mixture of Pd[P(Ph)3]4 (10.0
mmol%, 0.1 mmol, 0.11 g) and pyrrolidine (2.0 mL). The
mixture was stirred for 15 min and the appropriate terminal
alkyne 21 (1.2 mmol) was then added, dropwise, at room
temperature. The reaction was monitored by TLC until all
the starting material was consumed. The reaction times are
described below. After this, CH2Cl2 (30.0 mL) was added
and the organic phase was washed with brine (3£20.0 mL),
dried, evaporated and the residue was puri®ed by ¯ash silica
gel chromatography using hexane as eluent.
to
a
previously prepared mixture of Pd[P(Ph)3]4
(10.0 mmol%, 0.1 mmol, 0.11 g) and the enol tri¯ate 19a
(1.0 mmol, 0.33 g) in THF (5.0 mL). The reaction was
monitored by TLC until all the starting material was
consumed. The reaction times are described below. After
this, CH2Cl2 (30.0 mL) was added and the organic phase
was washed with brine (3£20.0 mL), dried, evaporated
and the residue was puri®ed by ¯ash silica gel chroma-
tography using hexane as eluent.
1,3-bis[(Z)-2-Phenylethenyl]-1-cyclohexene (25a). Yield:
0.21 g (75%). Reaction time: 10 h, H NMR (500 MHz,
3-[(Z)-2-Phenylethenyl]-1-(2-phenylethynyl)-1-cyclohex-
ene (26a). Yield: 0.21 g (75%). Reaction time: 30 min, H
1
1
CDCl3) d (ppm) 7.31±7.19 (m, 10H); 6.39 (d, Jˆ11.5 Hz,
1H); 6.35 (d, Jˆ12.2 Hz, 1H); 6.09 (d, Jˆ12.2 Hz, 1H);
5.64±5.60 (m, 1H); 5.49±5.45 (dd, Jˆ10.5, 11.5 Hz, 1H);
3.40±3.38 (m, 1H); 1.95±1.91 (m, 2H); 1.79±1.69 (m, 2H);
1.39±1.35 (m, 2H). 13C NMR (125 MHz, CDCl3) d (ppm)
136.1, 133.3, 130.1, 129.0, 128.8, 128.3, 128.2, 128.1,
127.8, 126.5, 35.1, 29.2, 27.9, 21.3. LRMS m/z (rel. int.):
286 (100) (M1), 195 (45), 167 (75), 128 (32), 91 (70). IR
(cm21) (®lm) 3055, 2954, 2930, 2861, 1601, 1448, 1430,
1303, 853, 766, 699. Anal. calcd for C22H22: C, 92.26, H,
7.98. Found: C, 92.59, H, 8.03.
NMR (500 MHz, CDCl3) d (ppm) 7.43±7.23 (m, 10H); 6.45
(d, Jˆ11.4 Hz, 1H); 6.10±6.09 (m, 1H); 5.50 (t, Jˆ11.4 Hz,
1H); 3.48±3.46 (m, 1H); 2.25±2.24 (m, 2H); 1.84±1.81 (m,
2H); 1.61±1.41 (m, 2H). 13C NMR (125 MHz, CDCl3) d
(ppm) 137.2, 136.9, 135.0, 131.4, 128.9, 128.4, 128.3,
128.2, 126.8, 123.5, 121.6, 90.8, 87.6, 34.1, 29.2, 28.6,
21.2. LRMS m/z (rel. int.): 284 (72) (M1), 241 (51), 178
(100), 165 (94), 128 (51), 115 (86), 91 (69), 77 (44). IR
(cm21) (®lm) 3009, 2930, 2216, 1601, 1449, 770, 700.
Anal. calcd for C22H20: C, 92.96, H, 7.04. Found: C,
92.44, H, 7.28.
(Z)-1-{3-[(Z)-2-Phenylethenyl]-1-cyclohexen-1-yl}-1-octen-
3-yne (25b). Yield: 0.22 g (75%). Reaction time: 24 h, H
3-{3-[(Z)-2-Phenylethenyl]-1-cyclohexen-1-yl}-2-propyn-
1-ol (26b). Yield: 0.19 g (80%). Reaction time: 20 min, 1H
NMR (500 MHz, CDCl3) d (ppm) 7.36±7.20 (m, 5H); 6.43
(d, Jˆ11.4 Hz, 1H); 6.01±5.95 (m, 1H); 5.45 (t, Jˆ11.4 Hz,
1H); 4.36 (s, 2H); 3.40±3.39 (m, 1H); 2.13±2.11 (m, 2H);
1.80±1.76 (m, 3H); 1.57±1.37 (m, 2H). 13C NMR
(125 MHz, CDCl3) d (ppm) 137.2, 137.1, 134.8, 128.9,
128.5, 128.4, 126.7, 120.9, 86.9, 85.4, 51.3, 34.9, 28.8,
28.5, 21.0. LRMS m/z (rel. int.) 238 (40) (M1), 205 (27),
154 (50), 128 (50), 115 (55), 91 (100). IR (cm21) (®lm)
3309, 3053, 3007, 2933, 2218, 1600, 1446, 1213, 1015,
701. Anal. calcd for C17H18O: C, 85.71, H, 7.56. Found:
C, 85.11, H, 7.71.
1
NMR (500 MHz, CDCl3) d (ppm) 7.34±7.22 (m, 5H); 6.43
(d, Jˆ11.5 Hz, 1H); 6.05 (d, Jˆ11.9 Hz, 1H); 5.84±5.82
(m, 1H); 5.50 (t, Jˆ10.8 Hz, 1H); 5.35 (dt, Jˆ2.2,
11.5 Hz, 1H); 3.51±3.45 (m, 1H); 2.66±2.63 (m, 1H);
2.35±2.31 (m, 2H); 1.84±1.82 (m, 2H); 1.55±1.51 (m,
4H); 1.44±1.39 (m, 3H); 0.90 (t, Jˆ7.4 Hz, 3H). 13C
NMR (125 MHz, CDCl3) d (ppm) 141.1, 137.9, 136.6,
133.8, 129.2, 129.1, 128.8, 127.2, 126.3, 105.9, 96.7, 80.1,
35.8, 31.3, 29.5, 27.5, 22.5, 21.6, 19.9, 13.9. LRMS m/z (rel.
int.): 233 (100), 205 (62), 141 (28), 129 (42), 91 (43). IR
(cm21) (®lm) 3055, 3297, 3445, 1948, 1753, 1629, 1574,
1262, 862, 767. Anal. calcd for C22H26: C, 90.22, H, 9.77.
Found: C, 90.34, H, 9.13.
1-(1-Hexynyl)-3-[(Z)-2-phenylethenyl]-1-cyclohexene (26c).
Yield: 0.19 g (75%). Reaction time: 45 min, 1H NMR
(300 MHz, CDCl3) d (ppm) 7.34±7.19 (m, 5H); 6.42 (d,
Jˆ11.4 Hz, 1H); 5.90±5.82 (m, 1H); 5.47 (dd, Jˆ10.5,
11.4 Hz, 1H); 3.32±3.47 (m, 1H); 2.32±2.27 (m, 2H);
2.13±2.11 (m, 2H); 1.81±1.73 (m, 2H); 1.60±1.31 (m,
6H); 0.93±0.88 (m, 3H). 13C NMR (75 MHz, CDCl3) d
(ppm) 138.4, 135.5, 135.1, 128.6, 128.2, 126.7, 122.1,
88.4, 81.9, 34.9, 31.0, 29.5, 28.8, 21.9, 20.9, 19.0, 13.7.
LRMS m/z (rel. int.): 264 (100) (M1), 207 (41), 179 (61),
Trimethyl((Z)-4-{3-[(Z)-2-phenylethenyl]-1-cyclohexen-
1-yl}-3-buten-1-ynyl)silane (25c). Yield: 0.24 g (80%).
Reaction time: 12 h, H NMR (500 MHz, CDCl3) d (ppm)
1
7.34±7.21 (m, 5H); 6.44 (d, Jˆ11.4 Hz, 1H); 6.14 (d,
Jˆ12.1 Hz, 1H); 5.87 (m, 1H); 5.50 (dd, Jˆ10.5, 11.3 Hz,
1H); 5.36 (d, Jˆ12.1 Hz, 1H); 3.52±3.47 (m, 1H); 2.55±
2.50 (m, 1H); 1.86±1.79 (m, 2H); 1.59±1.55 (m, 1H); 1.43±
1.39 (m, 1H); 1.26±1.23 (m, 1H); 0.18 (s, 9H). 13C NMR

D. N. Moraes et al. / Tetrahedron 56 (2000) 3327±3337
3337
173 (10), 115 (37), 91 (93), 77 (16). IR (cm21) (®lm) 3025,
2957, 2931, 2860, 2837, 1449, 700. Anal. calcd for C20H24:
C, 90.90, H, 9.09. Found: C, 90.87, H, 9.25.
V. B. Organometallics 1989, 8, 1661. (b) Dabdoub, M. J.;
Dabdoub, V. B.; Comasseto, J. V. Tetrahedron Lett. 1992, 33,
2261. (c) Dabdoub, M. J.; Dabdoub, V. B. Tetrahedron 1995, 51,
9839.
Trimethyl(2-{3-[(Z)-2-phenylethenyl]-1-cyclohexen-1-yl}-
ethynyl)silane (26d). Yield: 0.22 g (78%). Reaction time:
30 min, 1H NMR (500 MHz, CDCl3) d (ppm) 7.33±7.20 (m,
5H); 6.43 (d, Jˆ11.5 Hz, 1H); 6.07±6.05 (m, 1H); 5.45 (dd,
Jˆ10.4, 11.5 Hz, 1H); 3.42±3.39 (m, 1H); 2.15±2.13 (m,
2H); 1.79±1.75 (m, 2H); 1.55±1.51 (m, 1H); 1.40±1.36 (m,
1H); 0.18 (s, 9H). 13C NMR (125 MHz, CDCl3) d (ppm)
137.9, 137.2, 134.9, 128.9, 128.6, 128.2, 126.7, 121.6,
106.7, 91.8, 35.0, 28.8, 28.5, 20.7, 0.1. LRMS m/z (rel.
int.) 280 (27) (M1), 265 (17), 207 (18), 154 (28), 91 (21),
73 (100). IR (cm21) (®lm) 3444, 2958, 2930, 2141, 1445,
1250, 1168, 873, 846, 763, 702, 660, 531. Anal. calcd for
C19H24Si: C, 81.36, H, 8.62. Found: C, 80.76, H, 8.78.
3. Kauffmann, T. Angew. Chem., Int. Ed. Engl. 1982, 94, 401.
4. Barros, S. M.; Comasseto, J. V.; Berriel, J. N. Tetrahedron Lett.
1989, 30, 7353.
5. (a) Hiiro, T.; Kambe, N.; Ogawa, A.; Miyoshi, N.; Murai, S.;
Sonoda, N. Angew. Chem., Int. Ed. Engl. 1987, 26, 1187. (b)
Kanda, T.; Sugino, T.; Kambe, N.; Sonoda, N. Phosphorus Sulfur
Silicon Relat. Elem. 1992, 67, 103.
6. Tucci, F.; Chief®, A.; Comasseto, J. V.; Marino, J. P. J. Org.
Chem. 1996, 61, 4975.
7. Wipf, P. Synthesis 1993, 537.
8. Casson, S.; Kocienski, P. In Organometallic Reagents in
Organic Synthesis, Batesson, J. H., Mitchell, M. B., Eds.;
Academic Press: London, 1994; Vol. 7, pp 129±159 (Chapter 7).
9. (a) Comasseto, J. V.; Berriel, J. Synth. Commun. 1990, 20, 1681.
(b) Tucci, F. C.; Chief®. A.; Comasseto. J. V. Tetrahedron Lett.
1992, 33, 5721. (c) Marino, J. P.; Tucci, F. C.; Comasseto, J. V.
Â
Synlett 1993, 1145. (d) Araujo, M. A.; Barrientos-Astigarraga,
R. E.; Ellensohn, R. M.; Comasseto, J. V. Tetrahedron Lett.
1999, 40, 5115.
tert-Butyl(dimethyl)[((E)-5-{3-[(Z)-2-phenylethenyl]-1-
cyclopenten-1-yl}-2-penten-4-ynyl)oxy] (26e). Yield:
0.29 g (80%). Reaction time: 40 min, H NMR (500 MHz,
1
CDCl3) d (ppm) 7.34±7.22 (m, 5H); 6.41 (d, Jˆ11.4 Hz,
1H); 6.19 (dt, Jˆ15.7, 4.3 Hz, 1H); 5.91±5.90 (m, 2H); 5.50
(dd, Jˆ11.4, 10.0 Hz, 1H); 3.95±4.02 (m, 1H); 2.56±2.44
(m, 2H); 2.24±2.20 (m, 1H); 1.73±1.66 (m, 1H); 0.91 (s,
9H); 0.06 (s, 6H). 13C NMR (125 MHz, CDCl3) d (ppm)
142.2, 139.8, 137.3, 134.9, 128.7, 128.6, 128.2, 126.8,
125.7, 108.8, 89.7, 86.6, 62.9, 44.9, 36.1, 31.8, 25.9, 18.3,
25.3. LRMS m/z (rel. int.) 364 (16) (M1); 307 (38); 233
(38); 141 (100); 91 (19); 75 (59). IR (cm21) (®lm) 3007,
2953, 2931, 2857, 2186, 1600, 1466, 1377, 1255, 1129, 953,
838, 778. Anal. calcd for C24H32OSi: C, 79.16, H, 8.85.
Found C, 79.59, H, 8.93.
Â
10. Araujo, M. A.; Comasseto, J. V. Synlett 1995, 1145.
11. Marino, J. P.; Simonelli, F.; Stengel, P. J.; Ferreira, J. T. B.
J. Braz. Chem. Soc. 1998, 9, 345 (and references cited therein).
12. (a) Ireland, R. E.; P®ster, G. Tetrahedron 1969, 2145. (b)
Muchmore, D. C. Org. Synth. 1972, 52, 109. (c) Heathcock,
C. H.; Delmar, E. G.; Graham, S. L. J. Am. Chem. Soc. 1982,
104, 1907.
13. Moorhoff, C. M.; Schneider, D. F. Tetrahedron 1998, 54, 3279
(and references cited therein).
14. For a review see: Ritter, K. Synthesis 1993, 8, 735.
15. Taylor, R. J. K. Synthesis 1985, 364.
Acknowledgements
16. Lee, K.; Wiemer, D. F. Tetrahedron Lett. 1993, 34, 2433.
17. Barrientos-Astigarraga, R. E.; Castelani, P.; Sumida, C. Y.;
Comasseto, J. V. Tetrahedron Lett. 1999, 40, 7717.
18. Barrientos-Astigarraga, R. E.; Moraes, D. N.; Comasseto, J. V.
Tetrahedron Lett. 1999, 40, 265.
The authors acknowledge CNPq and FAPESP for ®nancial
support.
19. Knochel, P. Synlett 1995, 393.
20. Perrin, D. D.; Amarego, W. L. F. Puri®cation of Laboratory
Chemicals, 2nd ed.; Pergamon: London, 1980.
References
1. For reviews see: (a) Comasseto, J. V. Rev. Hetereoatom. Chem.
1993, 9, 61. (b) Comasseto, J. V.; Ling, L. W.; Petragnani. N.;
Stefani, H. A. Synthesis 1997, 373.
21. (a) Hendrickson, J. B.; Bergeron, R. Tetrahedron Lett. 1973,
39, 3839. (b) Hendrickson, J. B.; Bergeron, R. Tetrahedron Lett.
1973, 46, 4607.
2. (a) Barros, S. M.; Comasseto, J. V.; Dabdoub, M. J.; Dabdoub,