Efficient synthesis of enynes by tetraphosphine-palladium-catalysed reaction of vinyl bromides with terminal alkynes

Article abstract of DOI:10.1016/j.tet.2005.09.124

Through the use of [PdCl(C₃H₅)]₂/cis,cis, cis-1,2,3,4-tetrakis(diphenylphosphinomethyl)cyclopentane as catalyst, a range of vinyl bromides undergoes Sonogashira cross-coupling reaction with a variety of alkynes, leading to

Full text of DOI:10.1016/j.tet.2005.09.124

Tetrahedron 62 (2006) 112–120
Efficient synthesis of enynes by tetraphosphine–palladium-
catalysed reaction of vinyl bromides with terminal alkynes
*
Marie Feuerstein, Ludovic Chahen, Henri Doucet and Maurice Santelli
*
` ´
Laboratoire de Synthese Organique, UMR 6180 CNRS and Universite d’Aix-Marseille III, ‘Chirotechnologies: catalyse et biocatalyse’,
´
´ ˆ
Faculte des Sciences de Saint Jerome, Avenue Escadrille Normandie-Niemen, 13397 Marseille Cedex 20, France
Received 11 July 2005; revised 28 September 2005; accepted 29 September 2005
Available online 24 October 2005
Abstract—Through the use of [PdCl(C3H5)]2/cis,cis,cis-1,2,3,4-tetrakis(diphenylphosphinomethyl)cyclopentane as catalyst, a range of
vinyl bromides undergoes Sonogashira cross-coupling reaction with a variety of alkynes, leading to the corresponding 1,3-enynes in good
yields. The reaction tolerates several alkynes such as phenylacetylene, dec-1-yne, 2-methylbut-1-en-3-yne a range of alk-1-ynols, 3,3-
diethoxyprop-1-yne and a propargyl amine. Higher reactions rates were observed in the presence of phenylacetylene, dec-1-yne, but-3-yn-1-ol,
pent-4-yn-1-ol, 3,3-diethoxyprop-1-yne or 1,1-dipropyl-2-propynylamine than with propargyl alcohol, 3-methoxy-prop-1-yne or 2-
methylbut-1-en-3-yne. This catalyst can be used at low loading even for reactions of sterically hindered vinyl bromides such as
bromotriphenylethylene or 2-bromo-3-methyl-but-2-ene.
q 2005 Elsevier Ltd. All rights reserved.
1. Introduction
catalyst in the presence of CsF at room temperature.25
Some results were reported in ionic liquids using 5%
catalyst.26 This reaction has also been performed in aqueous
media using water soluble sulfonated triphenylphosphine
ligand for the coupling of vinyl iodides.27 A few other
ligands have also been tested for this coupling. An
N-heterocyclic carbene palladium catalyst has shown
efficiency comparable to Pd(PPh3)4.28 With an imidazolium
carbene ligand good results were obtained for the coupling
of 1-bromocyclohex-1-ene using 3% of palladium cata-
lyst.29 Alami et al. obtained high yields of adducts using 5%
of PdCl2(PhCN)2 catalyst without added ligand at room
temperature for the coupling reaction between vinyl
chloride and alkynes.30 The reaction between vinyl iodides
and terminal alkynes can also be performed in aqueous
media using potassium fluoride, palladium submicron
powder, cuprous iodide and PPh3.31 Despite these recent
advances, there still remained a need for a general protocol
using low-catalyst loading for Sonogashira reactions in the
presence of vinyl halides. Moreover, the efficiency of
tetraphosphine ligands for the cross-coupling of vinyl
halides with alkynes has not been reported.
Enynes are fundamental building blocks in organic
synthesis. The palladium-catalysed so-called Sonogashira
reaction is one of the most powerful methods for the
synthesis of such compounds.1–4 Cross-coupling palladium-
catalysed reactions between aryl halides and alkynes have
been largely described.5–12 On the other hand, if the
reactions between terminal acetylene and vinyl halides
have been recognized since the mid-seventies,13–14 their
applications usually need harsh reaction conditions and high
catalyst loadings. The most widely used catalysts for this
reaction are Pd(PPh3)4 or PdCl2(PPh3)2, associated with
copper(I) iodide.15–28 But these catalysts are not very
efficient in terms of the ratio substrate/catalyst and 5–10%
catalyst had to be used.15–22 With these catalysts, several
reactions conditions have been tested in order to improve
the yields. For example, 1-trialkylsilyl-1-alkynes can be
coupled directly with vinyl triflates using 1% Pd(PPh3)4 as
catalyst in the presence of Bu4NF and AgI.23 Mori et al.
have reported the coupling of terminal alkynes with vinyl
bromides catalyzed by 1% Pd(PPh3)4 using Bu4NF as
additive.24 Polymethylhydrosiloxane in association with
PdCl2(PPh3)2 can be used to promote the reaction between
E-b-bromostyrene and 2-methyl-3-butyn-2-ol using 5%
2. Results and discussion
Keywords: Palladium; Catalysis; Sonogashira; Vinyl bromides; Alkynes.
*
In order to find stable and efficient palladium catalysts, we
have prepared the tetrapodal phosphine ligand, cis,cis,cis-
1,2,3,4-tetrakis(diphenylphosphinomethyl) cyclopentane or
Tedicyp (Fig. 1).32 We have already reported the results
Corresponding authors. Tel.: C33 4 91 28 84 16; fax: C33 4 91 98 38 65
(H.D.); tel.: C33 4 91 28 88 25 (M.S.);
e-mail addresses: henri.doucet@univ.u-3mrs.fr;
m.santelli@univ.u-3mrs.fr
0040–4020/$ - see front matter q 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2005.09.124

M. Feuerstein et al. / Tetrahedron 62 (2006) 112–120
113
First, we tried to couple phenylacetylene with a range of
vinyl bromides (Scheme 1, Table 1). As expected, the
reaction of b-bromostyrene with phenylacetylene proceeds
nicely. The reaction can be performed with as little as
0.0001% catalyst (TON: 520,000) (Table 1, entry 3). The
same reaction performed with dppe as ligand (Table 1, entry
2), led to the coupling adduct 1 in 12% yield in the presence
of 0.001% catalyst (TON: 12,000). With a mixture of Z and
E 1-bromoprop-1-ene (ratio Z/E: 45/55) a good yield was
also obtained for a ratio S/C of 10,000 (Table 1, entries 4
and 5). A selectivity of 95% in favour of E isomer was
obtained using 0.01% catalyst (Table 1, entry 5). This high
selectivity in E isomer probably comes partially from the
higher reactivity of (E)-1-bromoprop-1-ene41 and also from
partial isomerisation of (Z)-1-bromoprop-1-ene into (E)-1-
bromoprop-1-ene under basic conditions.42
Figure 1.
obtained in allylic substitution,32 in Heck reaction,33 in
Suzuki cross-coupling34 and in Sonogashira reaction35–40
using Tedicyp as ligand. For example, we obtained a
turnover number (TON) of 2,800,000 for the coupling of
3,5-bis(trifluoromethyl)bromobenzene with phenylacety-
lene.35 We have also recently reported the Sonogashira
coupling of sterically congested aryl bromides,36 of
heteroaryl halides,37 of a range of aryl chlorides with as
little as 0.01% catalyst without addition of co-catalysts,38
and also the reactivity of several alkynols39 or propargyl
amines.40 Here, we wish to report on the efficiency of
Tedicyp ligand for the reaction of vinyl bromides with
terminal alkynes such as phenylacetylene, dec-1-yne,
2-methylbut-1-en-3-yne, a range of alk-1-ynols, 3,3-
diethoxyprop-1-yne and a propargyl amine.
Then, we studied the reactivity of three a-substituted vinyl
bromides. 2-Bromoprop-1-ene, 2-bromobut-1-ene and
3-bromobut-3-en-1-ol led to the coupling 1,3-enynes 3–5
in good yields using 0.01% catalyst (Table 1, entries 6–9).
The highest TON was obtained with 2-bromobut-1-ene,
with a yield of 48% for a ratio substrate/catalyst of 50,000
(Table 1, entry 8). The synthesis of tetrasubstituted alkenes
was also possible by Sonogashira cross-coupling reactions
with this catalyst. Sterically hindered substrates bromo-
triphenylethylene or 2-bromo-3-methylbut-2-ene reacts
cleanly with phenylacetylene. For the reactions with these
substrates TONs of 3300 and 6000 were obtained,
respectively, (Table 1, entries 10–12).
For this study, based on our previous results,35–40 DMF was
chosen as the solvent and potassium carbonate as the base.
The reactions were performed at 60–100 8C under argon in
the presence of a ratio 1:2 of [Pd(C3H5)Cl]2/Tedicyp as
catalyst and 5% copper(I) iodide as co-catalyst. At higher
temperatures (120–140 8C), lower yields were obtained due
to partial polymerization of the substrates and products. The
dimerisation of the alkynes was also detected in some cases.
In order to obtain high conversions of the aryl bromides we
have used 2 equiv of alkyne for all the reactions, however,
most of the reactions should proceed with 1.2–1.5 equiv of
alkyne. Some decomposition of the products was observed
for long time reactions, so the reactions were stopped at
20 h.
Having demonstrated that a variety of vinyl bromides can be
efficiently cross-coupled with phenylacetylene, we have
investigated the scope of this reaction using dec-1-yne and
2-methylbut-1-en-3-yne (Scheme 2, Table 2), and also with
Scheme 1.
Table 1. Cross-coupling reactions of vinyl bromides with phenylacetylene (Scheme 1)
Entry
Vinyl bromide
Ratio substrate/catalyst
Temperature (8C)
Product number
Ratio Z (a)/E (b)
Yield (%)a
1
2
3
4
5
6
7
8
b-Bromostyreneb
100,000
100,000
1000,000
1000
10,000
10,000
10,000
50,000
10,000
10,000
1000
100
100
100
60
60
60
80
80
80
80
1a,b
1a,b
1a,b
2a,b
2a,b
3
4
4
5
6
10/90
10/90
10/90
05/95
05/95
—
—
—
—
—
100c
12c,d
52
b-Bromostyreneb
b-Bromostyreneb
1-Bromoprop-1-enee
1-Bromoprop-1-enee
2-Bromoprop-1-ene
2-Bromobut-1-ene
100c
85
75
100c
48
2-Bromobut-1-ene
9
3-Bromobut-3-en-1-ol
2-Bromo-3-methyl-but-2-ene
Bromotriphenylethylene
Bromotriphenylethylene
85
60
86
33c
10
11
12
100
100
7
7
—
—
10,000
a Conditions: catalyst: [ClPd(C3H5)]2/TedicypZ1:2, vinyl bromide (1 equiv), phenylacetylene (2 equiv), K2CO3 (2 equiv), CuI (0.05 equiv), DMF, 20 h,
isolated yields.
b b-Bromostyrene was a mixture of Z and E isomers, ratio Z/E: 10/90.
c GC and NMR yield.
d Reaction performed with dppe (ratio Pd/dppe: 1:2).
e 1-Bromoprop-1-ene was a mixture of Z and E isomers, ratio Z/E: 45/55.

114
M. Feuerstein et al. / Tetrahedron 62 (2006) 112–120
Scheme 2.
Table 2. Cross-coupling reactions of vinyl bromides with dec-1-yne and 2-methylbut-1-en-3-yne (Scheme 2)
Entry
Vinyl bromide
Alkyne
Ratio substrate/
catalyst
Temperature
(8C)
Product
number
Ratio Z (a)/
E (b)
Yield (%)a
1
2
3
4
5
6
7
8
b-Bromostyreneb
Bromotriphenylethylene
2-Bromobut-1-ene
2-Bromo-3-methylbut-2-ene
2-Bromo-3-methylbut-2-ene
1-Bromoprop-1-ened
1-Bromoprop-1-ened
2-Bromoprop-1-ene
2-Bromoprop-1-ene
b-Bromostyrene
Dec-1-yne
Dec-1-yne
Dec-1-yne
Dec-1-yne
Dec-1-yne
Dec-1-yne
Dec-1-yne
Dec-1-yne
10,000
100
1000
100
1000
100
1000
100
100
100
80
80
80
60
60
60
60
80
80
8a,b
9
10
11
10/90
—
—
—
—
13/87
05/95
—
—
10/90
—
90
97
99
89
11
31c
100c
65
12a,b
12a,b
13
13
14a,b
15
100c
51
9
10
11
Dec-1-yne
2-Methylbut-1-en-3-yne
2-Methylbut-1-en-3-yne
1000
100
50
59e
60e
Bromotriphenylethylene
a Conditions: catalyst: [ClPd(C3H5)]2/TedicypZ1:2, vinyl bromide (1 equiv), alkyne (2 equiv), K2CO3 (2 equiv), CuI (0.05 equiv), DMF, 20 h.
b b-Bromostyrene was a mixture of Z and E isomers, ratio Z/E: 10/90.
c GC and NMR yield.
d 1-Bromoprop-1-ene was a mixture of Z and E isomers, ratio Z/E: 45/55.
e Reaction performed in autoclave.
several functionalized alkynes: propargyl alcohol, 3-meth-
oxyprop-1-yne, but-1-yn-3-ol, but-3-yn-1-ol, pent-4-yn-1-ol,
3,3-diethoxyprop-1-yne and 1,1-dipropyl-2-propynylamine
(Scheme 2, Table 3).
(Table 3, entries 6–8). Using but-1-yn-3-ol and but-3-yn-
1-ol, the reaction with b-bromostyrene or 2-bromobut-1-
ene, gave the desired products 22–24 and 26 using 0.1–
0.01% catalyst (Table 3, entries 9–13 and 16). Slower
reactions were observed with bromotriphenylethylene,
3-bromobut-3-en-1-ol and 2-bromo-3-methyl-but-2-ene
(Table 3, entries 14, 15, 17 and 18).
2-Bromobut-1-ene, 1-bromoprop-1-ene and 2-bromoprop-
1-ene were efficiently cross-coupled with dec-1-yne using
0.1% catalyst (Table 2, entries 3, 7, 9). The best result with
dec-1-yne was obtained using b-bromostyrene (TON of
9000) (Table 2, entry 1). Sterically congested substrates,
bromotriphenylethylene (entry 2), and 2-bromo-3-methyl-
but-2-ene (Table 2, entry 4) led to the corresponding enynes
9 and 11 in good yields but 1% catalyst were used. The
reactions performed with the enyne: 2-methylbut-1-en-3-
yne were much slower. This might be due to the
coordination of the olefinic bond to palladium. With
b-bromostyrene and bromotriphenylethylene the reactions
had to be performed using 1–2% catalyst in order to obtain
satisfactory yields of adducts 14 and 15 (Table 2, entries 10
and 11).
We also performed a few reactions with pent-4-yn-1-ol
(Table 3, entries 19–26). Better yields were obtained using
the same amount of catalyst than with but-3-yn-1-ol.
b-Bromostyrene, 1-bromoprop-1-ene and 2-bromoprop-1-
ene reacts in satisfactory yields with a ratio substrate/
catalyst of 10,000 (Table 3, entries 20, 24 and 26). We had
already observed with aryl bromides a similar trend for the
reactivity of alkynols: pent-4-yn-1-ol O but-3-yn-1-ol O
propargyl alcohol.39 (E)-3-Methylpent-2-en-4-yn-1-ol
reacts cleanly with b-bromostyrene or 2-bromobut-1-ene
to give the corresponding dienyne derivatives 33 and 34
(Table 3, entries 27 and 28). The Tedicyp–palladium system
also provides an efficient catalyst for the coupling of vinyl
bromides with propiolaldehyde diethyl acetal (Table 3,
entries 29–35). With this alkyne, a very high TON of 72,000
was obtained for the coupling with b-bromostyrene. Finally,
we were pleased to observe that 1,1-dipropyl-2-propynyl-
amine with one of the less reactive vinyl bromide: 2-bromo-
3-methylbut-2-ene gave 39 with a high TON of 6300
(Table 3, entries 36–37).
Next, we studied the reactivity of functionalized alkynes
(Table 3). Several reactions were performed using a range of
alkyn-1-ol derivatives. With alkynols, relatively low TONs
were observed in comparison to those obtained with
phenylacetylene or dec-1-yne. In the presence of the most
reactive vinyl bromide: b-bromostyrene, the coupling
reaction with propargyl alcohol was successful using 0.1%
catalyst (Table 3, entry 2). With bromotriphenylethylene
1% catalyst had to be used to obtain product 17 in 74% yield
(Table 3, entry 3). A similar reactivity was obtained using
the protected propargyl alcohol: 3-methoxyprop-1-yne
In conclusion, in the presence of the Tedicyp–palladium
catalyst, Sonogashira reactions of several vinyl bromides,
including sterically demanding ones, with a wide variety of

M. Feuerstein et al. / Tetrahedron 62 (2006) 112–120
115
Table 3. Cross-coupling reactions of vinyl bromides with alkynols, 3,3-diethoxyprop-1-yne and a propargylamine (Scheme 2)
Entry
Vinyl bromide
Alkyne
Ratio substrate/
catalyst
Temperature
(8C)
Ratio Z (a)/
E (b)
Product
number
Yield
(%)a
1
2
3
4
5
6
7
8
b-Bromostyreneb
Propargyl alcohol
Propargyl alcohol
Propargyl alcohol
Propargyl alcohol
Propargyl alcohol
3-Methoxyprop-1-yne
3-Methoxyprop-1-yne
3-Methoxyprop-1-yne
But-1-yn-3-ol
But-1-yn-3-ol
But-1-yn-3-ol
But-3-yn-1-ol
But-3-yn-1-ol
But-3-yn-1-ol
But-3-yn-1-ol
But-3-yn-1-ol
But-3-yn-1-ol
But-3-yn-1-ol
Pent-4-yn-1-ol
Pent-4-yn-1-ol
Pent-4-yn-1-ol
Pent-4-yn-1-ol
Pent-4-yn-1-ol
Pent-4-yn-1-ol
Pent-4-yn-1-ol
Pent-4-yn-1-ol
(E)-3-Methylpent-2-en-4-yn-1-ol
(E)-3-Methylpent-2-en-4-yn-1-ol
3,3-Diethoxyprop-1-yne
3,3-Diethoxyprop-1-yne
3,3-Diethoxyprop-1-yne
3,3-Diethoxyprop-1-yne
3,3-Diethoxyprop-1-yne
3,3-Diethoxyprop-1-yne
3,3-Diethoxyprop-1-yne
1,1-Dipropyl-2-propynylamine
1,1-Dipropyl-2-propynylamine
100
100
100
100
80
10/90
10/90
—
—
—
10/90
10/90
—
10/90
—
—
10/90
10/90
—
—
—
—
—
10/90
10/90
—
16a,b
16a,b
17
18
19
20a,b
20a,b
21
22a,b
23
23
24a,b
24a,b
25
25
26
27
28
29a,b
29a,b
30
80
b-Bromostyreneb
1000
100
100
50
100
1000
100
1000
100
1000
1000
10,000
100
1000
1000
100
40c
74
Bromotriphenylethylene
2-Bromobut-1-ene
96
2-Bromo-3-methylbut-2-ene
b-Bromostyreneb
80
98
100
100
100
100
80
100c
75
b-Bromostyreneb
Bromotriphenylethylene
b-Bromostyreneb
2-Bromobut-1-ene
74
9
98
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
100c
56
2-Bromobut-1-ene
b-Bromostyreneb
80
100
100
100
100
80
97
b-Bromostyreneb
29c
78
Bromotriphenylethylene
Bromotriphenylethylene
2-Bromobut-1-ene
20c
83
3-Bromobut-3-en-1-ol
2-Bromo-3-methylbut-2-ene
b-Bromostyreneb
80
80
96
85
100
1000
10,000
100
1000
1000
10,000
1000
10,000
500
100
100,000
100
1000
100
100
100
100
100
60
60
60
60
100
80
100
100
100
80
80
60
60
80
95
b-Bromostyreneb
62c
98
Bromotriphenylethylene
Bromotriphenylethylene
1-Bromoprop-1-ened
1-Bromoprop-1-ened
2-Bromoprop-1-ene
2-Bromoprop-1-ene
b-Bromostyreneb
2-Bromobut-1-ene
b-Bromostyreneb
Bromotriphenylethylene
Bromotriphenylethylene
2-Bromobut-1-ene
—
30
25c
98
40/60
04/96
—
—
10/90
—
10/90
—
—
—
—
31a,b
31a,b
32
32
33a,b
34
35a,b
36
36
37
37
37c
90
28c
88
80
72
95
22c
100c
70
2-Bromobut-1-ene
1000
100
1000
1000
10,000
2-Bromoprop-1-ene
2-Bromoprop-1-ene
2-Bromo-3-methylbut-2-ene
2-Bromo-3-methylbut-2-ene
—
—
—
—
38
38
39
39
100c
68
100c
63
80
a Conditions: catalyst: [ClPd(C3H5)]2/TedicypZ1:2, vinyl bromide (1 equiv), alkyne (2 equiv), K2CO3 (2 equiv), CuI (0.05 equiv), DMF, 20 h.
b b-Bromostyrene was a mixture of Z and E isomers, ratio Z/E: 10/90.
c GC and NMR yield.
d 1-Bromoprop-1-ene was a mixture of Z and E isomers, ratio Z/E: 45/55.
terminal alkynes can be performed with as little as 0.1–
0.0001% with the most reactive vinyl bromides and several
alkynes. The highest TONs were obtained with phenyl-
acetylene, dec-1-yne, but-3-yn-1-ol, pent-4-yn-1-ol, 3,3-
diethoxyprop-1-yne or 1,1-dipropyl-2-propynylamine. The
reactions performed with propargyl alcohol, 3-methoxy-
prop-1-yne or 2-methylbut-1-en-3-yne required larger
amounts of catalyst. The most reactive vinyl bromide was
b-bromostyrene, but a-substituted vinyl bromides such as
1-bromoprop-1-ene or 2-bromobut-1-ene also gave the
coupling adducts in high TONs. Furthermore, this catalyst
can be used at low loading even for the reactions of
sterically hindered vinyl bromides such as bromotriphenyl-
ethylene or 2-bromo-3-methylbut-2-ene. We believe that
this system compares favourably with other catalysts that
have been reported for this process.
alkynes were used without purification. The reactions were
followed by GC and NMR for high boiling point substrates
1
and by GC for low boiling point substrates. H and 13C
spectrum were recorded with a Bruker 300 MHz spectro-
meter in CDCl3 solutions. GC/MS were recorded with a
Varian Saturn 2100T spectrometer. Chemical shift are
1
reported in ppm relative to CDCl3 (7.25 for H NMR and
77.0 for 13C NMR). Flash chromatographies were
performed on silica gel (230–400 mesh). GC and NMR
yields in the tables are conversions of the vinyl halides into
1
the product calculated with GC and H NMR spectrum of
the crude mixtures.
3.1. Preparation of the Pd–Tedicyp catalyst
An oven-dried 40 mL Schlenk tube equipped with a
magnetic stirring bar under argon atmosphere, was charged
with [Pd(C3H5)Cl]2 (30 mg, 81 mmol) and Tedicyp
(140 mg, 162 mmol). Ten millilitre of anhydrous DMF
were added, then the solution was stirred at room
temperature for 10 min. The appropriate catalyst concen-
tration was obtained by successive dilutions. 31P NMR
(162 MHz, CDCl3) d 25 (wZ80 Hz), 19.4 (wZ110 Hz).
3. Experimental
General remarks. All reactions were run under argon in
Schlenk tubes using vacuum lines. DMF analytical grade
was not distilled before use. Commercial potassium
carbonate (99C), CuI (98%), vinyl bromides and terminal

116
M. Feuerstein et al. / Tetrahedron 62 (2006) 112–120
3.2. General procedure
7.40 (m, 2H), 7.34–7.28 (m, 3H), 2.00 (s, 3H), 1.87 (s, 3H),
1.77 (s, 3H).
In a typical experiment, the vinyl halide (1 mmol), terminal
alkynes (2 mmol), CuI (0.05 mmol, 0.01 g) and K2CO3
(0.276 g, 2 mmol) were dissolved in DMF (3 mL) under an
argon atmosphere. The prepared Pd–Tedicyp catalyst
complex (see tables) was then transferred to the reaction
flask via cannula. The reaction mixture was stirred at the
appropriate temperature for 20 h. Then, the solution was
diluted with H2O (2 mL), and the product was extracted
three times with CH2Cl2. The combined organic layer was
dried over MgSO4 and the solvent was removed in vacuo.
The product was purified by silica gel column
chromatography.
3.2.7. 1,1,2,4-Tetraphenylbut-1-en-3-yne (7). From bromo-
triphenylethylene (0.335 g, 1 mmol) and phenylacetylene
(0.220 mL, 2 mmol), product 7 was obtained in 86%
(0.307 g) yield. H NMR (300 MHz, CDCl3) d 7.67–7.65
(m, 2H), 7.45–7.40 (m, 6H), 7.31–7.16 (m, 10H), 7.13–7.11
(m, 2H).
1
3.2.8. (Z)-1-Phenyldodec-1-en-3-yne (8a) and (E)-1-
phenyldodec-1-en-3-yne (8b). From b-bromostyrene
(0.128 mL, 1 mmol) and dec-1-yne (0.361 mL, 2 mmol),
products 8a/8b (10/90) were obtained in 90% (0.216 g)
1
yield. Compound 8a. H NMR (300 MHz, CDCl3) d 7.50–
3.2.1. (Z)-1,4-Diphenylbut-1-en-3-yne (1a) and (E)-1,4-
diphenylbut-1-en-3-yne (1b). From b-bromostyrene
(0.128 mL, 1 mmol) and phenylacetylene (0.220 mL,
2 mmol), products 1a/1b (10/90) were obtained in 52%
(0.106 g) yield. Compound 1a. 1H NMR (300 MHz, CDCl3)
d 7.47–7.43 (m, 2H), 7.35–7.32 (m, 2H), 7.28–7.20 (m, 6H),
6.62 (d, JZ12.0 Hz, 1H), 5.87 (d, JZ12.0 Hz, 1H).
Compound 1b. H NMR (300 MHz, CDCl3) d 7.47–7.43
(m, 2H), 7.35–7.32 (m, 2H), 7.28–7.20 (m, 6H), 7.03 (d, JZ
16.2 Hz, 1H), 6.36 (d, JZ16.2 Hz, 1H).
7.30 (m, 5H), 6.61 (d, JZ12.1 Hz, 1H), 5.88 (d, JZ12.1 Hz,
1H), 2.40 (t, JZ6.9 Hz, 2H), 1.64–1.55 (m, 2H), 1.46–1.32
(m, 10H), 0.90–0.87 (m, 3H). Compound 8b. 1H NMR
(300 MHz, CDCl3) d 7.50–7.30 (m, 5H), 6.90 (d, JZ
16.2 Hz, 1H), 6.18 (d, JZ16.2 Hz, 1H), 2.40 (t, JZ6.9 Hz,
2H), 1.64–1.55 (m, 2H), 1.46–1.32 (m, 10H), 0.90–0.87 (m,
3H).
1
3.2.9. 1,1,2-Triphenyldodec-1-en-3-yne (9). From bromo-
triphenylethylene (0.335 g, 1 mmol) and dec-1-yne
(0.361 mL, 2 mmol), product 9 was obtained in 97%
1
3.2.2. (Z)-1-Phenylpent-3-en-1-yne (2a) and (E)-1-
phenylpent-3-en-1-yne (2b). From 1-bromoprop-1-ene
(0.085 mL, 1 mmol) and phenylacetylene (0.220 mL,
2 mmol), products 2a/2b (05/95) were obtained in 85%
(0.121 g) yield. Compound 2a. 1H NMR (300 MHz, CDCl3)
d 7.45–7.40 (m, 2H), 7.36–7.30 (m, 3H), 6.05 (dq, JZ10.6,
6.8 Hz, 1H), 5.71 (dq, JZ10.6, 1.7 Hz, 1H), 1.98 (dd, JZ
6.8, 1.7 Hz, 3H). Compound 2b. 1H NMR (300 MHz,
CDCl3) d 7.45–7.40 (m, 2H), 7.33–7.28 (m, 3H), 6.25 (dq,
JZ15.8, 6.8 Hz, 1H), 5.71 (dq, JZ15.8, 1.7 Hz, 1H), 1.84
(dd, JZ6.8, 1.7 Hz, 3H).
(0.381 g) yield. Thick oil; H NMR (300 MHz, CDCl3) d
7.45–7.42 (m, 2H), 7.26–7.20 (m, 5H), 7.10–7.00 (m, 6H),
6.91 (m, 2H), 2.19 (t, JZ6.8 Hz, 2H), 1.38–1.19 (m, 12H),
0.87–0.83 (m, 3H); 13C NMR (75 MHz, CDCl3) d 149.0,
142.8, 141.4, 139.6, 130.6, 130.0, 128.4, 127.9, 127.8,
127.7, 127.3, 127.1, 126.8, 121.5, 91.1, 78.9, 32.5, 30.1,
29.4, 29.2, 29.2, 23.1, 18.2, 14.0; MS (70 eV); m/z (%) 392
(MC%, 100); C30H32: calcd C 91.78, H 8.22. Found C 91.89,
H 8.31.
3.2.10. 2-Ethyldodec-1-en-3-yne (10). From 2-bromobut-
1-ene (0.102 mL, 1 mmol) and dec-1-yne (0.361 mL,
2 mmol), product 10 was obtained in 99% (0.190 g) yield.
Thick oil; 1H NMR (300 MHz, CDCl3) d 5.19 (s, 1H), 5.13
(s, 1H), 2.30 (t, JZ6.8 Hz, 2H), 2.16 (q, JZ7.1 Hz, 2H),
1.55–1.50 (m, 2H), 1.42–1.39 (m, 2H), 1.30 (br s, 8H), 1.08
(t, JZ7.1 Hz, 3H), 0.88 (t, JZ6.8 Hz, 3H); 13C NMR
(75 MHz, CDCl3) d 133.8, 118.3, 90.2, 80.9, 31.8, 30.7,
29.2, 29.1, 28.8, 28.8, 22.6, 19.7, 14.1, 12.8; MS (70 eV); m/
z (%) 192 (MC%, 1), 79 (100); C14H24: calcd C 87.42, H
12.58. Found C 87.28, H 12.34.
3.2.3. 3-Methyl-1-phenylbut-3-en-1-yne (3). From 2-bro-
moprop-1-ene (0.088 mL, 1 mmol) and phenylacetylene
(0.220 mL, 2 mmol), product 3 was obtained in 75%
1
(0.107 g) yield. H NMR (300 MHz, CDCl3) d 7.48–7.46
(m, 2H), 7.33–7.28 (m, 3H), 5.43 (s, 1H), 5.33 (s, 1H), 2.02
(s, 3H).
3.2.4. 2-Ethyl-4-phenylbut-1-en-3-yne (4). From 2-bro-
mobut-1-ene (0.102 mL, 1 mmol) and phenylacetylene
(0.220 mL, 2 mmol), product 4 was obtained in 48%
1
(0.075 g) yield. H NMR (300 MHz, CDCl3) d 7.45–7.42
(m, 2H), 7.34–7.28 (m, 3H), 5.38 (s, 1H), 5.28 (s, 1H), 2.27
3.2.11. 2,3-Dimethyltridec-2-en-4-yne (11). From
2-bromo-3-methyl-but-2-ene (0.151 mL, 1 mmol) and dec-
1-yne (0.361 mL, 2 mmol), product 11 was obtained in 89%
(q, JZ7.1 Hz, 2H), 1.15 (t, JZ7.1 Hz, 3H).
1
(0.183 g) yield. Thick oil; H NMR (300 MHz, CDCl3) d
3.2.5. 3-Methylene-5-phenylpent-4-yn-1-ol (5). From
3-bromobut-3-en-1-ol (0.099 mL, 1 mmol) and phenylace-
tylene (0.220 mL, 2 mmol), product 5 was obtained in 85%
(0.146 g) yield. Thick oil; H NMR (300 MHz, CDCl3) d
7.47–7.40 (m, 2H), 7.32–7.28 (m, 3H), 5.44 (s, 1H), 5.33 (s,
2.32 (t, JZ6.8 Hz, 2H), 1.90 (s, 3H), 1.77 (s, 3H), 1.70 (s,
3H), 1.55–1.50 (m, 2H), 1.42–1.39 (m, 2H), 1.26 (br s, 8H),
0.87 (t, JZ6.4 Hz, 3H); 13C NMR (75 MHz, CDCl3) d
137.9, 111.9, 91.3, 82.3, 31.8, 29.2, 29.1, 29.1, 28.9, 23.3,
1
22.6, 19.7, 19.5, 18.9, 14.1; MS (70 eV); m/z (%) 206 (MC%
,
1H), 3.85 (t, JZ6.2 Hz, 2H), 2.44 (t, JZ6.2 Hz, 2H).
100), 107 (100); C15H26: calcd C 87.30, H 12.70. Found C
87.20, H 12.67.
3.2.6. 2,3-Dimethyl-5-phenylpent-2-en-4-yne (6). From
2-bromo-3-methylbut-2-ene (0.151 mL, 1 mmol) and phe-
nylacetylene (0.220 mL, 2 mmol), product 6 was obtained
in 60% (0.102 g) yield. 1H NMR (300 MHz, CDCl3) d 7.50–
3.2.12. (Z)-Tridecen-4-yne (12a) and (E)-tridecen-4-yne
(12b). From 1-bromoprop-1-ene (0.085 mL, 1 mmol) and
dec-1-yne (0.361 mL, 2 mmol), products 12a/12b (05/95)

M. Feuerstein et al. / Tetrahedron 62 (2006) 112–120
117
1
were obtained in 65% (0.116 g) yield. Compound 12a. H
121.5, 91.1, 84.7, 51.0; MS (70 eV); m/z (%) 310 (MC%
,
NMR (300 MHz, CDCl3) d 5.86 (dq, JZ10.4, 6.6 Hz, 1H),
5.35 (dq, JZ10.4, 1.7 Hz, 1H), 2.25 (t, JZ6.7 Hz, 2H), 1.87
(dd, JZ6.6, 1.7 Hz, 3H), 1.55–1.50 (m, 2H), 1.42–1.39 (m,
2H), 1.30 (br s, 8H), 0.88 (t, JZ6.8 Hz, 3H). Compound
12b. 1H NMR (300 MHz, CDCl3) d 6.02 (dq, JZ15.7,
6.8 Hz, 1H), 5.45 (dq, JZ15.7, 1.7 Hz, 1H), 2.25 (t, JZ
6.7 Hz, 2H), 1.73 (dd, JZ6.8, 1.7 Hz, 3H), 1.55–1.50 (m,
2H), 1.42–1.39 (m, 2H), 1.30 (br s, 8H), 0.88 (t, JZ6.8 Hz,
3H).
100); C23H18O: calcd C 89.00, H 5.85. Found C 88.90, H
5.62.
3.2.18. 4-Ethylpent-4-en-2-yn-1-ol (18). From 2-bromo-
but-1-ene (0.102 mL, 1 mmol) and propargyl alcohol
(0.116 mL, 2 mmol), product 18 was obtained in 96%
(0.106 g) yield. 1H NMR (300 MHz, CDCl3) d 5.28 (s, 1H),
5.21 (s, 1H), 4.36 (s, 2H), 2.14 (q, JZ7.5 Hz, 2H), 1.06 (t,
JZ7.5 Hz, 3H); 13C NMR (75 MHz, CDCl3) d 132.6, 120.3,
87.0, 85.6, 51.3, 30.1, 12.7; C7H10O: calcd C 76.33, H 9.15.
Found C 76.52, H 9.27.
3.2.13. 2-Methyldodec-1-en-3-yne (13). From 2-bromo-
prop-1-ene (0.088 mL, 1 mmol) and dec-1-yne (0.361 mL,
2 mmol), product 13 was obtained in 51% (0.091 g) yield.
1H NMR (300 MHz, CDCl3) d 5.18 (s, 1H), 5.11 (s, 1H),
2.28 (t, JZ6.8 Hz, 2H), 1.86 (s, 3H), 1.54–1.47 (m, 2H),
1.40–1.27 (m, 10H), 0.88 (t, JZ6.6 Hz, 3H).
3.2.19. 4,5-Dimethylhex-4-en-2-yn-1-ol (19). From
2-bromo-3-methylbut-2-ene (0.151 mL, 1 mmol) and pro-
pargyl alcohol (0.116 mL, 2 mmol), product 19 was
obtained in 98% (0.122 g) yield. Thick oil; 1H NMR
(300 MHz, CDCl3) 4.42 (s, 2H), 1.92 (s, 3H), 1.79 (s, 3H),
1.74 (s, 3H); 13C NMR (75 MHz, CDCl3) d 140.8, 111.0,
88.3, 87.6, 51.8, 23.5, 19.9, 18.5.
3.2.14. (Z)-5-Methyl-1-phenyl-1,5-hexadien-3-yne (14a)
and (E)-5-methyl-1-phenyl-1,5-hexadien-3-yne (14b).
From b-bromostyrene (0.128 mL, 1 mmol) and
2-methylbut-1-en-3-yne (0.190 mL, 2 mmol), products
14a/14b (10/90) were obtained in 59% (0.099 g) yield.
3.2.20. (Z)-1-Methoxy-5-phenylpent-4-en-2-yne (20a)
and (E)-1-methoxy-5-phenylpent-4-en-2-yne (20b).
From b-bromostyrene (0.128 mL, 1 mmol) and 3-methoxy-
prop-1-yne (0.169 mL, 2 mmol), products 20a/20b (10/90)
1
Compound 14a. H NMR (300 MHz, CDCl3) d 7.43–7.28
(m, 5H), 6.68 (d, JZ12.1 Hz, 1H), 5.86 (d, JZ12.1 Hz,
1H), 5.40 (s, 1H), 5.34 (s, 1H), 2.03 (s, 3H). 14b. 1H NMR
(300 MHz, CDCl3) d 7.43–7.28 (m, 5H), 6.99 (d, JZ
16.2 Hz, 1H), 6.33 (d, JZ16.2 Hz, 1H), 5.40 (s, 1H), 5.31 (s,
1H), 2.00 (s, 3H); 13C NMR (75 MHz, CDCl3) d 141.1,
136.3, 128.7, 128.5, 128.1, 126.2, 121.8, 108.1, 92.9, 87.9,
23.4; C13H12: calcd C 92.81, H 7.19. Found C 92.68, H 7.30.
1
were obtained in 75% (0.129 g) yield. Compound 20a. H
NMR (300 MHz, CDCl3) d 7.37–7.26 (m, 5H), 6.60 (d, JZ
12.1 Hz, 1H), 5.86 (d, JZ12.1 Hz, 1H), 4.00 (s, 2H), 3.10 (s,
3H). Compound 20b. H NMR (300 MHz, CDCl3) d 7.37–
1
7.26 (m, 5H), 6.96 (d, JZ16.5 Hz, 1H), 6.17 (d, JZ16.5 Hz,
1H), 4.00 (s, 2H), 3.10 (s, 3H); 13C NMR (75 MHz, CDCl3)
d 141.1, 136.1, 128.8, 128.3, 126.2, 111.3, 91.1, 84.7, 61.0,
52.8; MS (70 eV); m/z (%): 172 (MC%, 65), 128 (100);
C12H12O: calcd C 83.69, H 7.02. Found C 83.91, H 7.14.
3.2.15. 5-Methyl-1,1,2-triphenylhexa-1,5-dien-3-yne
(15). From bromotriphenylethylene (0.335 g, 1 mmol) and
2-methylbut-1-en-3-yne (0.190 mL, 2 mmol), product 15
1
was obtained in 60% (0.192 g) yield. Thick oil; H NMR
(300 MHz, CDCl3) d 7.45–7.42 (m, 2H), 7.26–7.20 (m, 5H),
7.10–7.00 (m, 6H), 6.91 (m, 2H), 5.19 (s, 1H), 5.17 (s, 1H),
1.83 (s, 3H); 13C NMR (75 MHz, CDCl3) d 149.0, 142.8,
141.4, 139.6, 130.6, 131.7, 130.0, 128.4, 128.0, 127.8,
127.7, 127.3, 127.1, 126.8, 121.8, 121.5, 91.2, 90.9, 22.1;
MS (70 eV); m/z (%): 320 (MC%, 100); C25H20: calcd C
93.71, H 6.29. Found C 93.54, H 6.38.
3.2.21. 5-Methoxy-1,1,2-triphenylpent-1-en-3-yne (21).
From bromotriphenylethylene (0.335 g, 1 mmol) and
3-methoxyprop-1-yne (0.169 mL, 2 mmol), product 21
1
was obtained in 74% (0.240 g) yield. Thick oil; H NMR
(300 MHz, CDCl3) d 7.53–7.50 (m, 2H), 7.34–7.30 (m, 5H),
7.16–7.10 (m, 6H), 7.01–6.99 (m, 2H), 4.15 (s, 2H), 3.19 (s,
3H); 13C NMR (75 MHz, CDCl3) d 149.0, 142.8, 141.4,
139.6, 130.6, 130.0, 128.4, 128.0, 127.8, 127.7, 127.3,
127.1, 126.8, 121.5, 91.1, 85.6, 60.3, 52.8; MS (70 eV); m/z
(%): 324 (MC%, 100); C24H20O: calcd C 88.85, H 6.21.
Found C 88.72, H 6.10.
3.2.16. (Z)-5-Phenylpent-4-en-2-yn-1-ol (16a) and (E)-5-
phenylpent-4-en-2-yn-1-ol (16b). From b-bromostyrene
(0.128 mL, 1 mmol) and propargyl alcohol (0.116 mL,
2 mmol), products 16a/16b (10/90) were obtained in 80%
(0.126 g) yield. Compound 16a. 1H NMR (300 MHz,
CDCl3) d 7.37–7.26 (m, 5H), 6.60 (d, JZ12.1 Hz, 1H),
5.86 (d, JZ12.1 Hz, 1H), 4.44 (s, 2H), 2.25 (s, 1H).
3.2.22. (Z)-1-Phenylhex-1-en-3-yn-5-ol (22a) and (E)-1-
phenylhex-1-en-3-yn-5-ol (22b). From b-bromostyrene
(0.128 mL, 1 mmol) and but-1-yn-3-ol (0.157 mL,
2 mmol), products 22a/22b (10/90) were obtained in 98%
(0.168 g) yield. Compound 22a. 1H NMR (300 MHz,
CDCl3) d 7.38–7.29 (m, 5H), 6.69 (d, JZ12.1 Hz, 1H),
5.72 (d, JZ12.1 Hz, 1H), 4.70 (q, JZ6.4 Hz, 1H), 2.06 (s,
1
Compound 16b. H NMR (300 MHz, CDCl3) d 7.37–7.26
(m, 5H), 6.96 (d, JZ16.5 Hz, 1H), 6.17 (d, JZ16.5 Hz,
1H), 4.44 (s, 2H), 2.25 (s, 1H).
3.2.17. 1,1,2-Triphenylpent-1-en-3-yn-5-ol (17). From
bromotriphenylethylene (0.335 g, 1 mmol) and propargyl
alcohol (0.116 mL, 2 mmol), product 17 was obtained in
74% (0.230 g) yield. Thick oil; 1H NMR (300 MHz, CDCl3)
d 7.53–7.50 (m, 2H), 7.34–7.30 (m, 5H), 7.16–7.10 (m, 6H),
7.01–6.99 (m, 2H), 4.45 (s, 2H), 2.24 (s, 1H); 13C NMR
(75 MHz, CDCl3) d 148.6, 142.9, 141.3, 139.6, 130.5,
130.1, 128.4, 128.0, 127.8, 127.7, 127.3, 127.1, 126.8,
1
1H), 1.50 (d, JZ6.4 Hz, 3H). Compound 22b. H NMR
(300 MHz, CDCl3) d 7.38–7.29 (m, 5H), 6.94 (d, JZ
16.1 Hz, 1H), 6.15 (d, JZ16.1 Hz, 1H), 4.70 (q, JZ6.4 Hz,
1H), 2.06 (s, 1H), 1.50 (d, JZ6.4 Hz, 3H); 13C NMR
(75 MHz, CDCl3) d 141.7, 136.1, 128.7, 128.6, 126.2,
107.4, 93.1, 83.2, 58.9, 24.3; C12H12O: calcd C 83.69, H
7.02. Found C 83.87, H 7.18.

118
M. Feuerstein et al. / Tetrahedron 62 (2006) 112–120
3.2.23. 2-Ethylhex-1-en-3-yn-5-ol (23). From 2-bromobut-
1-ene (0.102 mL, 1 mmol) and but-1-yn-3-ol (0.157 mL,
2 mmol), product 23 was obtained in 56% (0.069 g) yield.
1H NMR (300 MHz, CDCl3) d 5.28 (s, 1H), 5.22 (s, 1H),
4.65 (q, JZ6.4 Hz, 1H), 2.14 (q, JZ7.5 Hz, 2H), 1.88 (s,
1H), 1.47 (d, JZ6.4 Hz, 3H), 1.07 (t, JZ7.5 Hz, 3H); 13C
NMR (75 MHz, CDCl3) d 132.6, 120.2, 90.7, 84.4, 58.8,
30.2, 24.4, 12.7; C8H12O: calcd C 77.38, H 9.74. Found C
77.54, H 9.57.
(70 eV); m/z (%): 138 (MC%, 100); C9H14O: calcd C 78.21,
H 10.21. Found C 78.04, H 10.34.
3.2.29. (Z)-1-Phenylhept-1-en-3-yn-7-ol (29a) and (E)-1-
phenylhept-1-en-3-yn-7-ol (29b). From b-bromostyrene
(0.128 mL, 1 mmol) and pent-4-yn-1-ol (1.86 mL, 20 mmol),
products 29a/29b (10/90) were obtained in 95% (0.177 g)
yield. Compound 29a. 1H NMR (300 MHz, CDCl3) d 7.36–
7.27 (m, 5H), 6.65 (d, JZ11.9 Hz, 1H), 5.87 (d, JZ11.9 Hz,
1H), 3.76 (t, JZ6.4 Hz, 2H), 2.26 (t, JZ6.3 Hz, 2H), 1.86
(tt, JZ6.4, 6.3 Hz, 2H). Compound 29b. 1H NMR
(300 MHz, CDCl3) d 7.36–7.27 (m, 5H), 6.90 (d, JZ
16.2 Hz, 1H), 6.14 (d, JZ16.2 Hz, 1H), 3.76 (t, JZ6.4 Hz,
2H), 2.26 (t, JZ6.3 Hz, 2H), 1.86 (tt, JZ6.4, 6.3 Hz, 2H).
3.2.24. (Z)-1-Phenylhex-1-en-3-yn-5-ol (24a) and (E)-1-
phenylhex-1-en-3-yn-5-ol (24b). From b-bromostyrene
(0.128 mL, 1 mmol) and but-3-yn-1-ol (0.151 mL,
2 mmol), products 24a/24b (10/90) were obtained in 97%
(0.167 g) yield. Compound 24a. 1H NMR (300 MHz,
CDCl3) d 7.40–7.24 (m, 5H), 6.62 (d, JZ12.0 Hz, 1H),
5.87 (d, JZ12.0 Hz, 1H), 3.76 (t, JZ6.3 Hz, 2H), 2.64 (t,
3.2.30. 1,1,2-Triphenylhept-1-en-3-yn-7-ol (30). From
bromotriphenylethylene (0.335 g, 1 mmol) and pent-4-yn-
1-ol (1.86 mL, 20 mmol), product 30 was obtained in 98%
1
JZ6.3 Hz, 2H), 2.44 (s, 1H). 24b. H NMR (300 MHz,
CDCl3) d 7.40–7.24 (m, 5H), 6.90 (d, JZ16.4 Hz, 1H), 6.14
(d, JZ16.4 Hz, 1H), 3.76 (t, JZ6.3 Hz, 2H), 2.64 (t, JZ
6.3 Hz, 2H), 2.44 (s, 1H).
1
(0.331 g) yield. Thick oil; H NMR (300 MHz, CDCl3) d
7.50–7.47 (m, 2H), 7.34–7.26 (m, 5H), 7.13–7.09 (m, 6H),
6.98 (m, 2H), 3.75 (t, JZ6.4 Hz, 2H), 2.26 (t, JZ6.3 Hz,
2H), 1.86 (tt, JZ6.4, 6.3 Hz, 2H); 13C NMR (75 MHz,
CDCl3) d 147.7, 143.0, 141.4, 139.7, 130.9, 130.2, 129.8,
127.8, 127.7, 127.6, 127.4, 127.0, 126.8, 121.8, 93.3, 83.5,
61.4, 30.8, 16.1; MS (70 eV); m/z (%): 338 (MC%, 100);
C25H22O: calcd C 88.72, H 6.55. Found C 88.87, H 6.41.
3.2.25. 1,1,2-Triphenylhex-1-en-3-yn-5-ol (25). From
bromotriphenylethylene (0.335 g, 1 mmol) and but-3-yn-1-
ol (0.151 mL, 2 mmol), product 25 was obtained in 78%
1
(0.253 g) yield. Thick oil; H NMR (300 MHz, CDCl3) d
7.50–7.37 (m, 2H), 7.35–7.28 (m, 5H), 7.17–7.10 (m, 6H),
6.98 (m, 2H), 3.55 (t, JZ5.8 Hz, 2H), 2.50 (t, JZ5.8 Hz,
2H), 1.50 (s, 1H); 13C NMR (75 MHz, CDCl3) d 149.0,
142.8, 141.4, 139.6, 130.6, 130.0, 129.4, 128.0, 127.8,
127.7, 127.3, 127.1, 126.8, 121.5, 93.5, 83.4, 61.8, 21.2; MS
(70 eV); m/z (%): 324 (MC%, 100), 293 (10), 215 (14);
C24H20O: calcd C 88.85, H 6.21. Found C 88.74, H 6.35.
3.2.31. (Z)-Oct-6-en-4-yn-1-ol (31a) and (E)-oct-6-en-4-
yn-1-ol (31b). From 1-bromoprop-1-ene (0.085 mL,
1 mmol) and pent-4-yn-1-ol (1.86 mL, 20 mmol), products
31a/31b (40/60) were obtained in 98% (0.122 g) yield.
1
Compound 31a. H NMR (300 MHz, CDCl3) d 5.88 (dq,
JZ10.8, 6.8 Hz, 1H), 5.42 (dtq, JZ10.8, 1.9, 1.7 Hz, 1H),
3.75 (t, JZ6.2 Hz, 2H), 2.46 (td, JZ6.9, 1.9 Hz, 2H), 1.75
(m, 5H). Compound 31b. H NMR (300 MHz, CDCl3) d
3.2.26. 2-Ethylhex-1-en-3-yn-5-ol (26). From 2-bromobut-
1-ene (0.102 mL, 1 mmol) and but-3-yn-1-ol (0.151 mL,
2 mmol), product 26 was obtained in 83% (0.103 g) yield.
Thick oil; 1H NMR (300 MHz, CDCl3) d 5.22 (s, 1H), 5.16
(s, 1H), 3.71 (t, JZ6.2 Hz, 2H), 2.58 (t, JZ6.2 Hz, 2H),
2.12 (q, JZ7.1 Hz, 2H), 1.06 (t, JZ7.1 Hz, 3H); 13C NMR
(75 MHz, CDCl3) d 133.1, 119.4, 85.9, 82.9, 61.1, 30.5,
23.7, 12.8; MS (70 eV); m/z (%): 124 (MC%, 69), 79 (100);
C8H12O: calcd C 77.38, H 9.74. Found C 77.50, H 9.70.
1
6.05 (dq, JZ15.9, 6.8 Hz, 1H), 5.44 (dtq, JZ15.9, 2.1,
1.7 Hz, 1H), 3.75 (t, JZ6.2 Hz, 2H), 2.46 (td, JZ6.8,
2.1 Hz, 2H), 1.82 (m, 5H).
3.2.32. 2-Methylhept-1-en-3-yn-7-ol (32). From 2-bromo-
prop-1-ene (0.088 mL, 1 mmol) and pent-4-yn-1-ol
(1.86 mL, 20 mmol), product 32 was obtained in 90%
(0.112 g) yield. 1H NMR (300 MHz, CDCl3) d 5.20 (s, 1H),
5.14 (s, 1H), 3.76 (t, JZ6.3 Hz, 2H), 2.43 (t, JZ7.0 Hz,
2H), 1.86 (s, 3H), 1.76 (tt, JZ7.0, 6.3 Hz, 2H).
3.2.27. 5-Methylenhept-3-yn-1,7-diol (27). From 3-bromo-
but-3-en-1-ol (0.099 mL, 1 mmol) and but-3-yn-1-ol
(0.151 mL, 2 mmol), product 27 was obtained in 96%
1
(0.134 g) yield. Thick oil; H NMR (300 MHz, CDCl3) d
3.2.33. (E,Z)-3-Methyl-7-phenylhepta-2,6-dien-4-yn-1-ol
(33a) and (E,E)-3-methyl-7-phenylhepta-2,6-dien-4-yn-
1-ol (33b). From b-bromostyrene (0.128 mL, 1 mmol) and
(E)-3-methylpent-2-en-4-yn-1-ol (0.192 g, 2 mmol),
product 33a/33b (10/90) were obtained in 88% (0.175 g)
yield. Compound 33a. 1H NMR (300 MHz, CDCl3) d 7.38–
7.24 (m, 5H), 6.63 (d, JZ11.8 Hz, 1H), 6.04 (tq, JZ6.8,
1.3 Hz, 1H), 5.80 (d, JZ11.8 Hz, 1H), 4.24 (d, JZ6.8 Hz,
5.33 (s, 1H), 5.23 (s, 1H), 3.75 (t, JZ6.3 Hz, 2H), 3.70 (t,
JZ6.2 Hz, 2H), 2.53 (t, JZ6.3 Hz, 2H), 2.35 (t, JZ6.2 Hz,
2H); 13C NMR (75 MHz, CDCl3) d 128.6, 123.4, 87.7, 82.5,
61.4, 61.4, 40.9, 24.0; MS (70 eV); m/z (%): 140 (MC%, 3),
91 (100); C8H12O2: calcd C 68.54, H 8.63. Found C 68.61,
H 8.80.
1
3.2.28. 2,3-Dimethylhept-2-en-4-yn-7-ol (28). From
2-bromo-3-methylbut-2-ene (0.151 mL, 1 mmol) and but-
3-yn-1-ol (0.151 mL, 2 mmol), product 28 was obtained in
85% (0.117 g) yield. Thick oil; 1H NMR (300 MHz, CDCl3)
d 3.75 (t, JZ6.2 Hz, 2H), 2.69 (t, JZ6.2 Hz, 2H), 1.89 (s,
3H), 1.76 (s, 3H), 1.70 (s, 3H); 13C NMR (75 MHz, CDCl3)
d 139.2, 111.4, 86.9, 84.4, 61.4, 23.9, 23.4, 19.7, 18.8; MS
2H), 1.88 (d, JZ1.3 Hz, 3H). Compound 33b. H NMR
(300 MHz, CDCl3) d 7.38–7.24 (m, 5H), 6.93 (d, JZ
16.0 Hz, 1H), 6.27 (d, JZ16.0 Hz, 1H), 6.04 (tq, JZ6.8,
1.3 Hz, 1H), 4.24 (d, JZ6.8 Hz, 2H), 1.88 (s, 3H); 13C NMR
(75 MHz, CDCl3) d 141.0, 136.2, 135.5, 128.7, 128.5,
126.2, 120.8, 108.0, 93.9, 87.2, 59.0, 17.5; C14H14O: calcd
C 84.81, H 7.12. Found C 84.70, H 7.07.

M. Feuerstein et al. / Tetrahedron 62 (2006) 112–120
119
3.2.34. (E)-6-Ethyl-3-methylhepta-2,6-dien-4-yn-1-ol
(34). From 2-bromobut-1-ene (0.102 mL, 1 mmol) and
(E)-3-methylpent-2-en-4-yn-1-ol (0.192 g, 2 mmol),
Thick oil; 1H NMR (300 MHz, CDCl3) d 3.55 (s, 2H), 2.43
(t, JZ7.6 Hz, 4H), 1.92 (s, 3H), 1.79 (s, 3H), 1.72 (s, 3H),
1.48 (tq, JZ7.6, 7.3 Hz, 4H), 0.89 (t, JZ7.3 Hz, 6H); 13C
NMR (75 MHz, CDCl3) d 138.9, 111.6, 86.7, 85.4, 55.8,
42.6, 23.5, 20.7, 19.7, 18.9, 11.9; MS (70 eV); m/z (%): 208
(MC%, 18), 178 (100); C14H25N: calcd C 81.09, H 12.15.
Found C 80.90, H 12.28.
1
product 34 was obtained in 80% (0.120 g) yield. H NMR
(300 MHz, CDCl3) d 5.97 (tq, JZ6.8, 1.3 Hz, 1H), 5.26 (s,
1H), 5.20 (s, 1H), 4.20 (d, JZ6.8 Hz, 2H), 2.18 (q, JZ
7.6 Hz, 2H), 1.84 (d, JZ1.3 Hz, 3H), 1.08 (t, JZ7.6 Hz,
3H); 13C NMR (75 MHz, CDCl3) d 135.2, 133.1, 120.8,
119.8, 91.3, 88.1, 59.1, 30.3, 17.5, 12.8; C10H14O: calcd C
79.96, H 9.39. Found C 79.87, H 9.50.
Registry No.: 1a, 13343-78-7; 1b, 13343-79-8; 2, 21979-82-
8; 3, 10469-89-3; 4, 732284-08-1; 5, 124475-73-6; 6a,
31552-04-2; 6b, 31552-03-1; 7, 1463-04-3; 8a, 845749-45-
3; 8b, 220185-68-2; 12a, 171781-58-1; 12b, 243870-53-3;
13, 71313-54-7; 16a, 374897-65-1; 16b, 103606-73-1; 19,
6822-09-9; 20a, 845749-46-4; 22a, 180787-32-0; 24,
53081-56-4; 29a, 114092-63-6; 29b, 114092-61-4; 31,
258819-00-0; 32, 69719-47-7; 38, 32365-41-6.
3.2.35. (Z)-5,5-Diethoxy-1-phenylpent-1-en-3-yne (35a)
and (E)-5,5-diethoxy-1-phenylpent-1-en-3-yne (35b).
From b-bromostyrene (0.128 mL, 1 mmol) and 3,3-diethoxy-
prop-1-yne (0.287 mL, 2 mmol), products 35a/35b (10/90)
1
were obtained in 72% (0.166 g) yield. Compound 35a. H
NMR (300 MHz, CDCl3) d 7.40–7.24 (m, 5H), 6.69 (d, JZ
12.1 Hz, 1H), 5.80 (d, JZ12.1 Hz, 1H), 5.29 (s, 1H), 3.80
(m, 2H), 3.65 (m, 2H), 1.25 (dd, JZ7.2, 7.0 Hz, 6H).
Acknowledgements
1
Compound 35b. H NMR (300 MHz, CDCl3) d 7.39–7.29
(m, 5H), 7.01 (d, JZ16.2 Hz, 1H), 6.17 (d, JZ16.2 Hz,
1H), 5.48 (s, 1H), 3.76 (dq, JZ9.5, 7.0 Hz, 2H), 3.61 (dq,
JZ9.5, 7.2 Hz, 2H), 1.25 (dd, JZ7.2, 7.0 Hz, 6H); 13C
NMR (75 MHz, CDCl3) d 142.7, 135.8, 128.8, 128.6, 126.3,
106.7, 91.7, 86.3, 84.4, 60.8, 15.0; C15H18O2: calcd C 78.23,
H 7.88. Found C 78.46, H 7.91.
´ ´
We thank the CNRS and the ‘Conseil General des Bouches-
ˆ
du-Rhone, Fr’ for financial support and M. F. is grateful to
the Ministere de la Recherche et de la Technologie for a
`
grant.
3.2.36. 5,5-Diethoxy-1,1,2-triphenylpent-1-en-3-yne (36).
From bromotriphenylethylene (0.335 g, 1 mmol) and 3,3-
diethoxyprop-1-yne (0.287 mL, 2 mmol), product 36 was
obtained in 95% (0.363 g) yield. Thick oil; 1H NMR
(300 MHz, CDCl3) d 7.46–7.44 (m, 2H), 7.33–7.30 (m, 2H),
7.29–7.26 (m, 3H), 7.16–7.08 (m, 6H), 7.03–6.99 (m, 2H),
5.30 (s, 1H), 3.48 (m, 4H), 1.15 (dd, JZ7.2, 7.0 Hz, 6H);
13C NMR (75 MHz, CDCl3) d 150.8, 143.0, 141.5, 139.5,
131.3, 130.6, 130.4, 128.3, 128.2, 128.2, 128.1, 127.8,
127.5, 120.9, 92.2, 88.3, 87.7, 61.1, 15.5; C27H26O2: calcd C
84.78, H 6.85. Found C 84.61, H 7.01.
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