Weakly ligated palladium complexes PdCl2(RCN)2 in piperidine: Versatile catalysts for Sonogashira reaction of vinyl chlorides at room temperature

Article abstract of DOI:10.1016/S0022-328X(00)00909-8

Copper iodide and weakly ligated palladium complexes PdCl₂(RCN)₂ (R = Ph, Me) catalyzed efficiently the coupling reaction of vinyl chlorides with 1-alkynes in the presence of piperidine to give the corresponding conjugated enynes in good to excellent yields. The reaction takes place rapidly and cleanly at room temperature. Application to the synthesis of terbinafine which exhibits strong antimycotic activity has been realized.

Full text of DOI:10.1016/S0022-328X(00)00909-8

Journal of Organometallic Chemistry 624 (2001) 114–123
www.elsevier.nl/locate/jorganchem
Weakly ligated palladium complexes PdCl2(RCN)2 in piperidine:
versatile catalysts for Sonogashira reaction of vinyl chlorides at
room temperature
Mouaˆd Alami *, Benoit Crousse, Fabiola Ferri
Laboratoire de Chimie The´rapeutique associe´ au CNRS (UPRES-A 8076, BIOCIS), Faculte´ de Pharmacie, rue J.B. Cle´ment 92296,
Chaˆtenay Malabry Cedex, France
Received 27 September 2000; received in revised form 15 November 2000
It is with warmest congratulations and best wishes for continued good health and happiness that this contribution is dedicated to Professor
Jean Normant on the occasion of his 65th anniversary
Abstract
Copper iodide and weakly ligated palladium complexes PdCl2(RCN)2 (R=Ph, Me) catalyzed efficiently the coupling reaction
of vinyl chlorides with 1-alkynes in the presence of piperidine to give the corresponding conjugated enynes in good to excellent
yields. The reaction takes place rapidly and cleanly at room temperature. Application to the synthesis of terbinafine which exhibits
strong antimycotic activity has been realized. © 2001 Elsevier Science B.V. All rights reserved.
Keywords: Palladium; Copper; Amino vinyl chlorides; Amino enynes; Terbinafine
1. Introduction
which are considered generally poor reactants have not
been used in such coupling. Obviously, extending the
scope of this reaction to the chloro analogues is of great
interest for synthetic laboratory, industrial chemistry and
would be a highly atom-economical approach for the
construction of conjugated enynes.
The low reactivity of vinyl chlorides is ascribed to their
much lower tendency to undergo oxidative addition to
Pd(0) in the catalytic cycle compared with vinyl iodides,
bromides or triflates [9]. In our attempts to increase the
rate of this step by varying several experimental condi-
tions, we discovered that the weakly ligated palladium
complexes PdCl2(RCN)2 (R=Ph or Me) and CuI in
piperidine catalyzed efficiently and rapidly the coupling
reaction of 1-alkynes with vinyl chlorides to give conju-
gated enynes in good to excellent yields. Herein, we wish
to detail our results previously reported [10].
The preparation of conjugated enynes [1] has been an
area of considerable activity in recent years [2] due
primarily to their use as efficient precursors of conjugated
dienes [3], as well as their occurence as natural substances
[4]. Among various approaches available for conjugated
enynes, by far the most convenient and simple method
widely used is the palladium–copper catalyzed cross
coupling reaction of terminal alkynes with vinyl halides
or triflates [5,6]. This procedure, namely Sonogashira
coupling reaction, is of great interest since the prepara-
tion of organometallic acetylide species is not required
and allows a huge range of functionalized 1-alkynes to
couple chemoselectively under very mild conditions [7].
Usually, the Sonogashira coupling reaction is effi-
ciently performed with the more reactive but expensive
vinyl iodides, bromides or triflates [7]. However, unlike
the case of 1,2-dichloro-ethylenes [7e,8], vinyl chlorides
* Corresponding author. Tel.: +33-1-46835887; fax: +33-1-
46835828.
E-mail address: mouad.alami@cep.u-psud.fr (M. Alami).
0022-328X/01/$ - see front matter © 2001 Elsevier Science B.V. All rights reserved.
PII: S0022-328X(00)00909-8

M. Alami et al. / Journal of Organometallic Chemistry 624 (2001) 114–123
115
Table 1
Cross coupling reaction of 1a with 2a: effects of palladium catalysts and amine
Entry
Amine
PdLn
Time (h)
Isolated yield of 3a (%)
1
2
3
4
5
6
7
8
BuNH2
Et2NH
Et3N
PdCl2(PPh3)2
PdCl2(PPh3)2
PdCl2(PPh3)2
PdCl2(PPh3)2
PdCl2(PPh3)2
PdCl2 + 2 PPh3
PdCl2
PdCl2 + 2 AsPh3
Pd(OAc)2 + 2 PPh3
Pd(OAc)2 + 2 AsPh3
Pd(dba)2 + 2 AsPh3
Pd(PPh3)4
PdCl2(MeCN)2
PdCl2(PhCN)2
PdCl2(PhCN)2
PdCl2(PhCN)2
PdCl2(PhCN)2
PdCl2(PhCN)2
PdCl2(PhCN)2
PdCl2(PhCN)2
PdCl2(PhCN)2
20
20
20
16
20
20
16
16
16
16
16
20
0.5
0.5
1
24
9
4
Pyrrolidine
Piperidine
Piperidine
Piperidine
Piperidine
Piperidine
Piperidine
Piperidine
Piperidine
Piperidine
Piperidine
Morpholine
Pyrrolidine
PrNH2
71
93
83
90
75
69
80
78
11
90
93
89
73
2
9
10
11
12
13
14
15
16
17
18
19
20
21
0.5
20
20
20
20
20
Et2NH
i-Pr2NH
Et3N
9
3
2
2
N-Methyl piperidine
2. Results and discussion
product. It is noteworthy that other palladium catalysts
can be used successfully (60–90% within 16–20 h,
entries 6–11).
At first, we examined the coupling reaction of 1-alky-
nes with vinyl chlorides under the standard Sonogashira
conditions [5]. Thus, reaction of vinyl chloride 1a with
1-heptyne 2a in Et2NH as solvent in the presence of
PdCl2(PPh3)2 (5%) and CuI (10%) at room temperature
for 20 h gave very low yield of enyne 3a (9%, Table 1,
entry 2) accompanied with symmetrical diyne arising
from the homocoupling of 1-heptyne. Consequently, in
order to improve this result, we decided to examine the
influence of the nature of the amine and palladium
catalysts including the effect of ligands on the course of
the reaction. The results are summarized in Table 1.
The coupling reaction of 1a with 2a was also unsuc-
cessful when using primary or tertiary amine such as
BuNH2 or Et3N (Table 1, entries 1 and 3). In contrast,
the use of cyclic secondary amine allows to improve
remarkably the yield of the cross coupling product 3a
(71–93% within 20 h, entries 4 and 5). The best result
was obtained when performing the reaction in pipe-
ridine in the presence of palladium catalysts coordi-
nated with nitrile ligands rather than triphenyl
phosphine. Under these conditions, the use of
PdCl2(PhCN)2 or PdCl2(MeCN)2 drastically accelerated
the rate of the reaction (Scheme 1), thus the coupling
reaction proceeds rapidly at room temperature within
0.5 h instead of 20 h and gave 3a in excellent yield
(90–93%, entries 13 and 14). Furthermore, the use of
nitrile rather than triphenyl phosphine as ligand in the
palladium complex simplified the purification of the
As illustrated in Table 1, the association of
PdCl2(RCN)2-cyclic secondary amine (entries 13–16)
was crucial for the success of the coupling reaction
since the use of other amines gave low yields of enyne
3a (entries 17–21).
As exemplified below the reaction is stereospecific
and proceeds with retention of the double bond geome-
try of the vinyl chloride. (Z)-1-chloro-hept-1-ene (1b)
gave (92% yield, stereoisomeric purity ]99.5%) (8Z)-
tetradec-8-en-6-yne (3b) in 100 min. The (Z)-vinyl chlo-
ride was less reactive than the corresponding (E)-isomer
(Scheme 2).
As shown in Table 2, the coupling reaction of 1a with
2a can also be performed in 90–92% yield within 5–6 h
by using 20 equivalents of piperidine in THF or NMP
as solvent. The use of other solvents gave unsatisfactory
yields of the desired enyne 3a (2–45%, Table 2).
In order to demonstrate the efficiency of this new
synthetic approach, a variety of functionalized enynes
were thus synthesized in good to excellent yields start-
ing from functionalized vinyl chlorides. As shown in
Table 3, the coupling reaction has a large scope of
application and tolerates sensitive functional groups on
either coupling partner.
An elegant illustration of the efficiency of this proce-
dure is the high yielding synthesis of terbinafine 30 a
strong antimycotic agent which is used currently for the

116
M. Alami et al. / Journal of Organometallic Chemistry 624 (2001) 114–123
Scheme 1. Reaction of 1a with 1-heptyne in piperidine in the presence of palladium catalyst (5%) and CuI (10%) at room temperature.
treatment of skin mycoses [11]. Thus, amination of
(E)-1,3-dichloropropene (28) with N-methyl-1-naphtal-
ene methanamine (27) in dry acetonitrile in the presence
of K2CO3 and a catalytic amount of KI [12] led regiose-
lectively to the (E)-vinyl chloride 29 in 81% yield
(Scheme 3). Coupling of (E)-amino vinyl chloride (29)
with tert-butyl acetylene in the presence of piperidine
and catalytic amounts of PdCl2(PhCN)2 (5%) and CuI
(10%) provided rapidly1 and stereospecifically ter-
binafine 30 in 93% isolated yield [14,15]2.
the presence of CuI and weakly ligated palladium com-
plexes to give the corresponding cross coupling prod-
ucts in high yields. The reaction is stereo- and
chemoselective since numerous functional groups are
tolerated in both coupling partners.
4. Experimental
All experiments were carried out in flame-dried glass-
ware under an inert atmosphere. All NMR spectra were
recorded on a Bruker AC 200, VM 250 or AM 400
MHz spectrometer in deuteriochloroform (CDCl3, l
(ppm), J (Hz)). Mass spectra were determined on a
Nermag R 10/10 instrument in the NH3 chemical ioni-
sation mode. IR spectra were measured on a Perkin–
As exemplified below (Scheme 4), the coupling reac-
tion from vinyl iodides, under the same conditions was
examined and afforded lower yields of coupled prod-
ucts than vinyl chlorides.
The palladium-catalyzed reaction of several metal
acetylides containing Sn, Zn, Si with vinyl iodides
[16,17] has been reported; however when heptynyl trib-
utyl stannane was treated with 1(E)-chloro-hept-1-ene
(1a) in the presence of PdCl2(PhCN)2 in DMF or
piperidine for 20 h, no reaction occured. These results
show the greater utility, both in term of efficiency and
practicability, of copper-catalyzed reactions of terminal
acetylenes over the preformed metal acetylides for the
synthesis of conjugated enynes.
Elmer
599
spectrophotometer
(neat,
cm−1).
Stereoisomeric purity of products was determined by
3. Conclusion
We have shown that vinyl chlorides readily react with
terminal alkynes, at room temperature, in piperidine in
1 The use of PdCl2(PhCN)2 as catalyst instead of PdCl2 associated
with PPh3 dramatically improved the rate of the coupling reaction
(0.5 h instead of 20 h) see Ref. [13].
Scheme 2. Reaction of 1a (E-isomer) and 1b (Z-isomer) with 1-hep-
tyne in piperidine in the presence of PdCl2(PhCN)2 (5%) and CuI
(10%) at room temperature.
2 For other syntheses of terbinafine and related compounds see
Refs. [11,15].

M. Alami et al. / Journal of Organometallic Chemistry 624 (2001) 114–123
117
Table 2
Cross coupling reaction of 1a with 2a under PdCl2(PhCN)2-catalysis: effects of solvents
a
Solvent
C6H6
21
Et2O
10
THF
92
AcOEt
24
CH3CN
45
NMP
90
DMSO
Yield of 3a (%) b
2
a 20 equivalents of piperidine were used.
b Isolated yields.
Table 3
Synthesis of functionalized enynes by coupling of vinyl chlorides with terminal alkynes

118
M. Alami et al. / Journal of Organometallic Chemistry 624 (2001) 114–123
Scheme 3.
gas chromatographic analyses performed on a model
Girdel equiped with capillary column (SGE 50 QC 2 /
BP5 0.25). Analytical TLC was performed on 0.25 mm
precoated silica gel plates (Merck). Products were
purified by distillation or by column chromatography
(silica gel 60 230–400 mesh ASTM, 0.040–0.063 mm)
purchased from E. Merck. Boiling points are uncor-
rected. PdCl2(RCN)2 (R=Ph, Me) [18], vinyl chlorides
7 [19] and 13 [20] were prepared following literature
procedure.
26.6, 30.5, 117.8, 131.7. Anal. Calc. for C6H11Cl
(118.60): C, 60.99; H, 9.39; Found: C, 61.20; H, 9.57%.
4.3. (E)-3-Chloro-prop-2-en-1-ol (5)
(E)-1,3-dichloro-prop-1-ene 28 (3.55 g, 32.2 mmol),
K2CO3 (4.66 g, 44 mmol) and 40 ml of H2O were
stirred 6 h at 100°C. The mixture was cooled and
extracted with Et2O (3×20 ml). The organic layer was
dried over MgSO4 and the solvent was removed in
vacuo. Purification by distillation afforded pure (E)-
vinylchloride 5 as a colourless oil in 69% yield (2.06 g);
b.p. 77°C (42 mmHg); IR (neat, cm−1) 3350, 3060,
4.1. (E)-1-Chloro-hept-1-ene (1a)
1
1630, 965; H-NMR (200 MHz, CDCl3): l 1.8 (s, OH),
Compound 1a was prepared following literature pro-
cedure [21]. Copper (I) chloride (11.9 g, 0.12 mol),
(1E)-1-iodo-hept-1-ene (31a) [22] (13.4 g, 0.06 mol) and
60 ml of NMP were stirred 2 h at 130°C. The mixture
was cooled, dilued with 5 N HCl and extracted with
Et2O (3×30 ml). The organic layer was dried over
MgSO4 and the solvent was removed in vacuo. Purifica-
tion by distillation afforded the vinyl chloride 1a as a
colourless oil (E stereoisomeric purity \99%) in 79%
yield (6.2 g); b.p. 140–142°C (760 mmHg); IR (neat)
4.16 (dd, J=6.0 and 1.2 Hz, 2H), 6.10 (dt, J=13.3 and
1.2 Hz, 1H), 6.27 (dt, J=13.3 and 1.2 Hz, 1H). 13C-
NMR (50 MHz, CDCl3): l 61.4, 120.5, 132.3.
4.4. (Z)-3-Chloro-prop-2-en-1-ol (6)
(Z)-1,3-dichloro-prop-1-ene (3.55 g, 32.2 mmol),
K2CO3 (4.66 g, 44 mmol) and 40 ml of H2O were
stirred 6 h at 100°C. The mixture was cooled and
extracted with Et2O (3×20 ml). The organic layer was
dried over MgSO4 and the solvent was removed in
vacuo. Purification by distillation afforded pure (Z)-
vinylchloride 6 as a colourless oil in 63% yield (1.88 g);
b.p. 74°C (40 mmHg); IR (neat, cm−1) 3350, 3060,
1630, 965; 1H-NMR (200 MHz, CDCl3): l 2.07 (s,
OH), 4.37 (dd, J=6.0 and 1.8 Hz, 2H), 6.00 (dt,
J=7.5 and 6.0 Hz, 1H), 6.14 (dt, J=7.5 and 1.8 Hz,
1H). 13C-NMR (50 MHz, CDCl3): l 58.0, 119.5, 130.7.
1
cm−1 1635; H-NMR (200 MHz, CDCl3): l 0.90 (t,
J=6.7 Hz, 3H), 1.20–1.50 (m, 6H), 2.00 (q, J=6.1 Hz,
2H), 5.90 (m, 2H). 13C-NMR (50 MHz, CDCl3): l 13.8,
22.3, 28.5, 30.8, 31.1, 116.6, 134.0. Anal. Calc. for
C7H13Cl (132.45): C, 63.42; H, 9.81; Found: C, 63.55;
H, 9.98%.
4.2. (Z)-1-Chloro-hex-1-ene (1b)
Compound 1b was prepared following literature pro-
cedure [21]. Copper (I) chloride (9.9 g, 0.10 mol),
(1Z)-1-iodo-hex-1-ene [23] (10.5 g, 0.05 mol) and 50 ml
of NMP were stirred 2 h at 130°C. The mixture was
cooled, dilued with 5 N HCl and extracted with Et2O
(3×30 ml). The organic layer was dried over MgSO4
and the solvent was removed in vacuo. Purification by
distillation afforded the vinyl chloride 1b as a colourless
oil (E stereoisomeric purity \99%) in 65% yield (3.85
g); b.p. 120–122°C (760 mmHg); IR (neat) cm−1 1630;
1H-NMR (200 MHz, CDCl3): l 0.86 (t, J=7.3 Hz,
3H), 1.20–1.40 (m, 4H), 2.15 (qd, J=7.2 and 1.5 Hz,
2H), 5.68 (q, J=7.1 Hz, 1H), 5.93 (dt, J=7.1 and 1.5
Hz, 1H). 13C-NMR (50 MHz, CDCl3): l 13.7, 22.2,
4.5. Preparation of amino 6inylchlorides: general
procedure
To a stirred solution of (E) or (Z)-1,3-dichloro-
propene or 1,2-dichloropropene (5.0 g, 45 mmol),
K2CO3 (8.3 g, 60 mmol) and KI (250 mg, 1.5 mmol) in
Scheme 4.

M. Alami et al. / Journal of Organometallic Chemistry 624 (2001) 114–123
119
acetonitrile (80 ml) were added secondary amine (30
mmol). The resulting mixture was heated to reflux.
After 6 h, the reaction was hydrolyzed with brine (20
ml) and extracted with Et2O (3×20 ml). The combined
organic layers were dried over MgSO4, and concen-
trated under vacuum. The residue was purified by silica
gel column chromatography to give pure amino
vinylchloride.
128.5, 151.7. Anal. Calc. for C13H22NO4Cl (291.78): C,
53.52; H, 7.60; Found: C, 53.21; H, 7.83%.
4.5.6. Methyl (E)-5-hydroxy-7-chloro-hept-6-enoate
(14)
To a solution of methyl (E)-7-chloro-5-oxo-hept-6-
enoate [24] (1.64 g, 8 mmol) and CeCl3; 7H2O (3.29 g,
8.8 mmol) in MeOH (20 ml) was added slowly NaBH4
(342 mg, 9.05 mmol) at room temperature (r.t.). After
complete addition, the reaction was stirred for 15 min.
and was hydrolyzed with brine (20 ml). The aqueous
layer was extracted with AcOEt (3×10 ml) and Et2O
(3×10 ml). The combined organic layers were washed
with water (15 ml), dried over MgSO4 and concentrated
under vacuum. Purification by silica gel column chro-
matography gave hydroxy vinyl chloride 14 in 91%
yield (1.5 g). IR (neat, cm−1) 3420, 1730, 1605, 1020;
1H-NMR (200 MHz, CDCl3): l 1.53 (m, 2H), 1.65 (m,
2H), 2.30 (t, 2H, J=7.2Hz), 3.60 (s, 3H), 4.08 (q,
J=7.0 Hz, 1H), 5.90 (dd, J=16.0 and 7.0 Hz, 1H),
6.15 (dd, J=16.0 and 1.5 Hz, 1H). 13C-NMR (50
MHz, CDCl3): l 174.1, 135.9, 119.7, 70.5, 51.6, 36.2,
33.6, 20.5. Anal. Calc. for C8H13O3Cl (192.64): C,
49.88; H, 6.80; Found: C, 49.98; H, 6.96%.
4.5.1. (E)-N-Benzyl-N-methyl-3-chloro-prop-2-en-
1-amine (8)
4.75 g (81%); IR (neat, cm−1) 1635, 1600, 1495,
1
1455. H-NMR (200 MHz, CDCl3): l 2.20 (s, 3H), 3.05
(d, J=6.4 Hz, 2H), 3.52 (s, 2H), 6.02 (dt, J=13.3 and
6.6 Hz, 1H), 6.15 (d, J=13.3 Hz, 1H), 7.20 (m, 5H).
13C-NMR (50 MHz, CDCl3): l 41.7, 56.8, 61.3, 120.5,
127.2, 128.3, 128.9, 130.4, 138.1. CIMS (NH3) m/e (rel.
int.) 198 (41), 196 (100), 122 (18), 120 (19), 108 (14),
106 (18). Anal. Calc. for C11H14NCl (195.69): C, 67.51;
H, 7.21; Found: C, 67.62; H, 7.30%.
4.5.2. (E)-1-(3-Chloro-prop-2-enyl)-piperidine (9)
1
4.10 g (87%); IR (neat, cm−1) 1635. H-NMR (200
MHz, CDCl3): l 1.45 (m, 2H), 1.6 (m, 4H), 2.4 (m,
4H), 2.95 (d, J=6.6 Hz, 2H), 6.01 (dt, J=14.7 and 6.6
Hz, 1H), 6.12 (d, J=14.7 Hz, 1H). 13C-NMR (50
MHz, CDCl3): l 25.9, 54.4, 55.4, 120.1, 128.8. Anal.
Calc. for C8H14NCl (159.66): C, 60.18; H, 8.84; Found:
C, 60.31; H, 8.98%.
4.6. Coupling of 6inyl chlorides with terminal alkynes:
general procedure
To a suspension of PdCl2(PhCN)2 (19 mg, 0.05
mmol), vinyl chloride (1 mmol), CuI (19 mg, 0.1 mmol)
in piperidine (3 ml) was added alkyne (2 mmol). The
reaction was stirred at r.t. and monitored by TLC
analysis until complete consumption of the vinyl chlo-
ride. After 0.5–3 h, the reaction mixture was treated
with saturated solution of NH4Cl (30 ml). The aqueous
layer was extracted with ether (3×20 ml). The com-
bined organic layers were washed successively with
aqueous HCl (0.2 M, 15 ml), NaHCO3 (10 ml) and
water (2×30 ml), dried over MgSO4 and concentrated
under vacuum. Purification by silica gel column chro-
matography afforded the corresponding pure enyne.
4.6.1. (E)-Tetradec-8-en-6-yne (3a)
4.5.3. (Z)-N-Benzyl-N-methyl-3-chloro-prop-2-en-
1-amine (10)
4.57 g (78%); IR (neat, cm−1) 1635, 1600, 1495,
1
1460. H-NMR (200 MHz, CDCl3): l 2.15 (s, 3H), 3.17
(dd, J=6.4 and 1.6 Hz, 2H), 3.44 (s, 2H), 5.86 (dt,
J=7.2 and 6.4 Hz, 1H), 6.10 (dt, J=7.2 and 1.7 Hz,
1H), 7.24 (m, 5H). 13C-NMR (50 MHz, CDCl3): l 42.2,
53.5, 61.8, 120.1, 127.1, 128.2, 129.0, 129.1, 138.6. Anal.
Calc. for C11H14NCl (195.69): C, 67.51; H, 7.21; Found:
C, 67.69; H, 7.32%.
4.5.4. 1-(2-Chloro-prop-2-enyl)-piperidine (11)
1
3.69 g (77%); IR (neat, cm−1) 1635. H-NMR (200
1
179 mg (91%); IR (neat, cm−1) 2115, 1610. H-NMR
MHz, CDCl3): l 1.31 (m, 2H), 1.51 (quint., J=5.6 Hz,
4H), 2.32 (m, 4H), 2.95 (s, 2H), 5.15 (s, 1H), 5.29 (s,
1H). 13C-NMR (50 MHz, CDCl3): l 24.3, 26.0, 54.2,
65.4, 113.7, 139.4. Anal. Calc. for C8H14NCl (159.66):
C, 60.18; H, 8.84; Found: C, 60.31; H, 9.06%.
(200 MHz, CDCl3): l 0.88 (t, J=6.9 Hz, 3H), 0.90 (t,
J=6.6 Hz, 3H), 1.20–1.60 (m, 12H), 2.08 (q, J=6.7
Hz, 2H), 2.28 (td, J=7.1 and 2.0 Hz, 2H), 5.45 (dt,
J=15.8 and 1.8 Hz, 1H), 6.06 (dt, J=15.7 and 7.2 Hz,
1H). 13C-NMR (50 MHz, CDCl3): l 13.9, 14.0, 19.3,
22.2, 22.5, 28.5, 28.6, 31.0, 31.2, 32.9, 79.1, 88.6, 109.7,
143.3. Anal. Calc. for C14H24 (192.35): C, 87.42; H,
12.58; Found: C, 87.95; H, 12.85%.
4.5.5. N,N-di-t-Butoxycarbonyl-3-chloro-prop-2-
en-1-amine (12)
7.7 g (88%); IR (neat, cm−1) 1750, 1700, 1630, 1372,
1150, 1110. 1H-NMR (200 MHz, CDCl3): l 1.45 (s,
18H), 4.12 (dd, J=6.7 and 0.9 Hz, 2H), 5.95 (dt,
J=13.3 and 6.8 Hz, 1H), 6.17 (d, J=13.3 Hz, 1H).
13C-NMR (50 MHz, CDCl3): l 27.8, 45.5, 82.4, 121.3,
4.6.2. (Z)-Tridec-5-en-7-yne (3b)
1
177 mg (91%); IR (neat, cm−1) 2120, 1600. H-NMR
(200 MHz, CDCl3): l 0.85 (2t, J=6.5 Hz, 2×3H),

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M. Alami et al. / Journal of Organometallic Chemistry 624 (2001) 114–123
1.20–1.60 (m, 10H), 2.27 (m, 4H), 5.40 (m, 1H), 5.77 (td,
J=10.6 and 7.3 Hz, 1H). 13C-NMR (50 MHz, CDCl3):
l 13.8, 13.9, 19.5, 22.2, 22.3, 28.6, 29.7, 31.0, 77.4, 94.3,
109.4, 142.4. Anal. Calc. for C13H22 (178.22): C, 87.53;
H, 12.34; Found: C, 87.62; H, 12.51%.
6.7 Hz, 3H), 1.23–1.40 (m, 6H), 2.04 (q, J=6.8 Hz, 2H),
2.48–2.60 (m, 4H), 3.68 (s, 3H), 5.40 (dt, J=15.9 and
1.7 Hz, 1H), 6.04 (dt, J=15.9 and 7.1 Hz, 1H). 13C-
NMR (50 MHz, CDCl3): l 13.9, 15.2, 22.4, 28.4, 31.2,
32.8, 33.4, 51.6, 79.8, 86.1, 109.4, 144.0, 172.3. CIMS
(NH3) m/e (rel. int.) 226 (72), 209 (100). Anal. Calc. for
C13H20O2 (208.30): C, 74.96; H, 9.68; Found: C, 75.03;
H, 9.79%.
4.6.3. (E)-1-Phenyl-non-3-en-1-yne (15a)
184 mg (93%); IR (neat, cm−1) 2190, 1590, 1485,
1440, 1300. 1H-NMR (200 MHz, CDCl3): l 0.92 (t,
J=6.8 Hz, 3H), 1.27–1.51 (m, 6H), 2.18 (qd, J=7.2
and 1.0 Hz, 2H), 5.71 (dt, J=15.8 and 1.3 Hz, 1H), 6.27
(dt, J=15.8 and 7.2 Hz, 1H), 7.27–7.46 (m, 5H).
13C-NMR (50 MHz, CDCl3): l 14.0, 22.5, 28.4, 31.3,
33.2, 88.4, 87.8, 109.5, 123.6, 127.8, 128.2, 131.4, 145.3.
CIMS (NH3) m/e (rel. int.) 216, 199, 198 (100). Anal.
Calc. for C15H18 (198.31): C, 90.85; H, 9.15; Found: C,
91.16; H, 9.42%.
4.6.8. Methyl-2-dec-2-en-4-yne (16)
1
93 mg (62%); IR (neat, cm−1) 2200, 1600. H-NMR
(200 MHz, CDCl3): l 0.85 (t, J=7.0 Hz, 3H), 1.20–1.50
(m, 6H), 1.70 (s, 3H), 1.80 (s, 3H), 2.27 (td, J=7.0 and
2.0 Hz, 2H), 5.20 (m, 1H). 13C-NMR (50 MHz, CDCl3):
l 13.9, 19.5, 20.6, 22.2, 24.4, 28.8, 31.1, 78.3, 92.0, 105.5,
146.2. Anal. Calc. for C11H18 (150.27): C, 87.93; H,
12.07; Found: C, 88.50; H, 12.42%.
4.6.9. (E)-Dec-2-en-4-yn-1-ol (17)
4.6.4. (E)-1-Trimethylsilyl-non-3-en-1-yne (15b)
134 mg (88%); IR (neat, cm−1) 3350, 2180, 1610,
1015, 950. 1H-NMR (200 MHz, CDCl3): l 0.90 (t,
J=7.0 Hz, 3H), 1.20–1.60 (m, 6H), 1.80 (s, OH), 2.30
(td, J=7.0 and 2.0 Hz, 2H), 4.40 (dd, J=5.4 and 1.7
Hz, 2H), 5.70 (dquint., J=15.9 and 2.0 Hz, 1H), 6.15
(dt, J=15.9 and 5.4 Hz, 1H). 13C-NMR (50 MHz,
CDCl3): l 13.9, 19.3, 22.1, 26.3, 31.0, 63.0, 78.3, 91.4,
111.2, 140.1. Anal. Calc. for C10H16O (152.24): C, 78.90;
H, 10.59; Found: C, 79.45; H, 10.92%.
175 mg (90%); IR (neat, cm−1) 2120, 1625, 1470, 960.
1H-NMR (200 MHz, CDCl3): l 0.16 (s, 9H), 0.86 (t,
J=6.7 Hz, 3H), 1.19–1.42 (m, 6H), 2.07 (qd, J=7.2
and 1.2 Hz, 2H), 5.47 (dt, J=15.9 and 1.5 Hz, 1H), 6.19
(dt, J=15.9 and 7.0 Hz, 1H). 13C-NMR (50 MHz,
CDCl3): l 0.03, 13.9, 22.4, 28.2, 31.2, 32.9, 92.3, 104.1,
109.5, 144.2. CIMS (NH3) m/e (rel. int.) 212 (5), 195
(60), 175 (40), 90 (100). Anal. Calc. for C12H22Si
(194.39): C, 74.14; H, 11.41; Found: C, 74.43; H, 11.65%.
4.6.10. (Z)-Dec-2-en-4-yn-1-ol (18)
4.6.5. (E)-Dec-4-en-2-yn-1-ol (15c)
129 mg (85%); IR (neat, cm−1) 3400, 2185, 1610,
1010, 950. 1H-NMR (200 MHz, CDCl3): l 0.90 (t,
J=7.0 Hz, 3H), 1.31 (m, 4H), 1.55 (m, 2H), 1.70 (s,
OH), 2.34 (td, J=7.0 and 2.1 Hz, 2H), 4.40 (d, J=6.2
Hz, 2H), 5.59 (dt, J=10.8 and 2.0 Hz, 1H), 6.01 (dt,
J=11.0 and 6.2 Hz, 1H). 13C-NMR (50 MHz, CDCl3):
l 14.8, 20.5, 23.2, 29.5, 32.0, 61.6, 77.8, 92.2, 11.3, 140.1.
Anal. Calc. for C10H16O (152.24): C, 78.90; H, 10.59;
Found: C, 79.38; H, 10.76%.
132 mg (87%); IR (neat, cm−1) 3420, 2180, 1600,
1010, 940. 1H-NMR (200 MHz, CDCl3): l 0.86 (t,
J=6.6 Hz, 3H), 1.26–1.40 (m, 6H), 1.64 (s, OH), 2.08
(q, J=6.7 Hz, 2H), 4.35 (d, J=1.8 Hz, 2H), 5.47 (dt,
J=15.9 and 1.7 Hz, 1H), 6.18 (dt, J=15.8 and 7.1 Hz,
1H). 13C-NMR (50 MHz, CDCl3): l 13.9, 22.4, 28.2,
31.1, 32.9, 51.5, 84.5, 85.5, 108.7, 145.7. CIMS (NH3)
m/e (rel. int.) 170 (72), 152 (51), 137 (100). Anal. Calc.
for C10H16O (152.24): C, 78.90; H, 10.59; Found: C,
79.12; H, 10.82%.
4.6.11. (E)-Pentadec-7-en-9-yn-6-ol (19a)
200 mg (90%); IR (neat, cm−1) 3420, 2220, 1470,
1080. 1H-NMR (200 MHz, CDCl3): l 0.85 (t, J=7.0 Hz,
3H), 0.83 (t, J=7.0 Hz, 3H), 1.10–1.55 (m, 14H and
OH), 2.25 (td, J=7.0 and 2.0 Hz, 2H), 4.06 (q, J=6.2
Hz, 1H), 5.65 (dq, J=16.0 and 2.0 Hz, 1H), 5.97 (dd,
J=16.0 and 6.5 Hz, 1H). 13C-NMR (50 MHz, CDCl3):
l 13.9, 14.0, 19.3, 22.2, 22.5, 24.9, 28.4, 31.0, 31.7, 36.9,
72.3, 78.4, 91.1, 110.4, 144.2. Anal. Calc. for C15H26O
(222.37): C, 81.02; H, 11.79; Found: C, 81.31; H, 12.02%.
4.6.6. (E)-Undec-5-en-3-yn-1-ol (15d)
146 mg (88%); IR (neat, cm−1) 3400, 2220, 1610,
1470, 1080, 960. 1H-NMR (200 MHz, CDCl3): l 0.85 (t,
J=6.6 Hz, 3H), 1.21–1.38 (m, 6H), 1.73 (s, OH), 2.06
(q, J=6.6 Hz, 2H), 2.55 (td, J=6.2 and 2.0 Hz, 2H),
3.70 (t, J=6.2 Hz, 2H), 5.42 (dt, J=15.8 and 1.8 Hz,
1H), 6.08 (dt, J=15.8 and 7.3 Hz, 1H). 13C-NMR (50
MHz, CDCl3): l 13.9, 22.4, 23.6, 28.4, 31.2, 32.9, 61.1,
81.0, 84.6, 109.3, 144.3. Anal. Calc. for C11H18O
(166.27): C, 79.46; H, 10.91; Found: C, 79.60; H, 10.98%.
4.6.12. (E)-Undec-4-en-2-yn-1,6-diol (19b)
4.6.7. Methyl (E)-dodec-6-en-4-ynoate (15e)
153 mg (84%); IR (neat, cm−1) 3400, 2260, 1470,
1180, 1030, 970. 1H-NMR (200 MHz, CDCl3): l 0.85 (t,
J=6.5 Hz, 3H), 1.10–1.55 (m, 8H and OH), 2.25 (sbr,
154 mg (74%); IR (neat, cm−1) 1740, 1600, 1440,
1
1170, 960. H-NMR (200 MHz, CDCl3): l 0.85 (t, J=

M. Alami et al. / Journal of Organometallic Chemistry 624 (2001) 114–123
121
2H), 4.10 (q, J=6.2 Hz, 1H), 4.34 (d, J=2.0 Hz, 1H),
5.70 (dq, J=16.0 and 2.0 Hz, 1H), 6.15 (dd, J=16.0
and 6.2 Hz, 1H). 13C-NMR (50 MHz, CDCl3): l 13.8,
22.3, 24.8, 31.5, 36.5, 50.6, 71.8, 83.2, 87.8, 108.9, 145.9.
Anal. Calc. for C11H18O2 (182.26): C, 72.49; H, 9.95;
Found: C, 72.75; H, 10.22%.
61.4, 80.2, 86.8, 112.8, 127.1, 128.2, 129.1, 137.9, 139.6.
CIMS (NH3) m/e (rel. int.) 230 (88), 136 (35), 122
(100), 120 (54), 108 (22), 106 (43). Anal. Calc. for
C15H19NO (229.32): C, 78.56; H, 8.35; Found: C, 78.86;
H, 8.58%.
4.6.17. (E)-1-(Piperidin-1-yl)-undec-2-en-4-yn-6-ol (21)
237 mg (95%); IR (neat, cm−1) 3400, 1625, 1600,
1165, 1015. 1H-NMR (200 MHz, CDCl3): l 0.85 (t,
J=6.8 Hz, 3H), 1.15–1.75 (m, 14H and OH), 2.35 (m,
4H), 2.95 (dd, J=6.8 and 1.3 Hz, 2H), 4.40 (td, J=6.2
and 1.3 Hz, 1H), 5.60 (dd, J=15.9 and 1.3 Hz, 1H),
6.20 (dt, J=15.9 and 6.8 Hz, 1H). 13C-NMR (50 MHz,
CDCl3): l 13.8, 22.3, 23.8, 24.8, 25.2, 31.2, 37.7, 54.1,
61.2, 61.6, 81.8, 91.1, 112.1, 140.0. Anal. Calc. for
C16H27NO (249.40): C, 77.06; H, 10.91; Found: C,
77.55; H, 11.36%.
4.6.13. (E)-N-Benzyl-N-methyl-dec-2-en-4-yn-1-amine
(20a)
220 mg (86%); IR (neat, cm−1) 2220, 1600, 1495,
1
1365, 1135, 1075, 1025. H-NMR (200 MHz, CDCl3): l
0.90 (t, J=7.2 Hz, 3H), 1.40 (m, 6H), 2.20 (s, 3H), 2.28
(dt, J=7.0 and 1.6 Hz, 2H), 3.00 (d, J=6.6 Hz, 2H),
3.50 (s, 2H), 5.64 (dt, J=15.8 and 1.6 Hz, 1H), 6.11
(dt, J=15.8 and 6.6 Hz, 1H), 7.30 (m, 5H). 13C-NMR
(50 MHz, CDCl3): l 14.0, 19.4, 22.2, 28.5, 31.1, 42.0,
59.4, 61.5, 78.6, 90.5, 113.0, 127.0, 128.1, 128.9, 138.6,
139.1. CIMS (NH3) m/e (rel. int.) 256 (69), 136 (15),
123 (13), 122 (100), 120 (31), 106 (21). Anal. Calc. for
C18H25N (255.41): C, 84.65; H, 9.87; Found: C, 84.92;
H, 10.02%.
4.6.18. (Z)-N-benzyl-N-methyl-hex-2-en-4-yn-6-
ol-1-amine (22)
138 mg (64%); IR (neat, cm−1) 3430, 1630, 1600,
1
1490, 1450, 1160 H-NMR (200 MHz, CDCl3): l 2.15
(s, 3H), 2.40 (s, OH), 3.20 (d, J=6.8 Hz, 2H), 3.50 (s,
2H), 4.32 (d, J=1.9 Hz, 2H), 5.60 (dt, J=11.1 and 1.6
Hz, 1H), 6.02 (dt, J=10.9 and 6.8 Hz, 1H), 7.23 (m,
5H). 13C-NMR (50 MHz, CDCl3): l 42.2, 51.5, 56.1,
61.7, 81.6, 93.0, 111.0, 127.0, 128.2, 129.2, 138.4, 140.7.
Anal. Calc. for C14H17NO (215.30): C, 78.10; H, 7.96;
Found: C, 78.42; H, 8.11%.
4.6.14. (E)-N-Benzyl-N-methyl-5-trimethylsilyl-
pent-2-en-4-yn-1-amine (20b)
231 mg (90%); IR (neat, cm−1) 2220, 1610, 1500,
1360, 1080. 1H-NMR (200 MHz, CDCl3): l 1.20 (s,
9H), 2.30 (s, 3H), 3.27 (dd, J=6.4 and 1.5 Hz, 2H),
3.60 (s, 2H), 5.85 (dt, J=16.0 and 1.3 Hz, 1H), 6.40
(dt, J=16.0 and 6.4 Hz, 1H), 7.40 (m, 5H). 13C-NMR
(50 MHz, CDCl3): l 42.2, 51.5, 56.1, 61.7, 81.6, 93.0,
111.0, 127.0, 128.2, 129.2, 138.4, 140.7. Anal. Calc. for
C16H23NSi (257.45): C, 74.65; H, 9.00; Found: C, 74.92;
H, 9.29%.
4.6.19. 1-(2-Methylene-non-3-ynyl)-piperidine (23a)
169 mg (77%); IR (neat, cm−1) 1630, 1605, 1450.
1H-NMR (200 MHz, CDCl3): l 0.85 (t, J=7.3 Hz,
3H), 1.40 (m, 12H), 2.26 (t, J=7.1 Hz, 2H), 2.38 (t,
J=4.8 Hz, 4H), 2.92 (t, J=1.2 Hz, 2H), 5.23 (s, 1H),
5.28 (t, J=1.2 Hz, 1H). 13C-NMR (50 MHz, CDCl3): l
14.0, 19.3, 22.2, 24.3, 26.0, 28.4, 31.0, 54.2, 64.2, 80.6,
90.4, 121.5, 128.8. Anal. Calc. for C15H25N (219.37): C,
82.13; H, 11.49; Found: C, 82.56; H, 11.92%.
4.6.15. (E)-N-Benzyl-N-methyl-hex-2-en-4-yn-6-
ol-1-amine (20c)
157 mg (73%); IR (neat, cm−1) 3400, 1630, 1600,
1
1490, 1450, 1160, 1020. H-NMR (200 MHz, CDCl3): l
2.20 (s, 3H), 3.30 (dd, J=6.6 and 1.0 Hz, 2H), 3.50 (s,
2H), 4.37 (d, J=1.8 Hz, 2H), 5.70 (dt, J=15.9 and 1.7
Hz, 1H), 6.28 (dt, J=15.9 and 6.5 Hz, 1H), 7.35 (m,
5H). 13C-NMR (50 MHz, CDCl3): l 41.5, 51.2, 58.5,
61.1, 83.2, 88.3, 113.2, 127.7, 128.5, 129.5, 136.5, 139.4.
CIMS (NH3) m/e (rel. int.) 217 (20), 216 (100), 214 (8),
198 (8), 122 (15). Anal. Calc. for C14H17NO (215.30): C,
78.10; H, 7.96; Found: C, 78.56; H, 8.28%.
4.6.20. 5-(Piperidinomethyl)-hex-5-en-3-yn-1-ol (23b)
164 mg (85%); IR (neat, cm−1) 3430, 1630, 1605,
1
1450, 1160, 1025. H-NMR (200 MHz, CDCl3): l 1.50
(m, 2H), 1.52 (m, 4H), 2.30 (m, 4H), 2.48 (t, J=5.6 Hz,
2H), 2.92 (t, J=1.1 Hz, 2H), 3.62 (t, J=5.7 Hz, 2H),
5.22 (t, J=1.6 Hz, 1H), 5.26 (s, 1H). 13C-NMR (50
MHz, CDCl3): l 23.7, 24.0, 25.3, 54.1, 60.5, 66.3, 82.6,
88.7, 121.4, 128.5. Anal. Calc. for C12H19NO (193.29):
C, 74.57; H, 9.91; Found: C, 74.92; H, 10.22%.
4.6.16. (E)-N-Benzyl-N-methyl-hept-2-en-4-yn-
7-ol-1-amine (20d)
222 mg (97%); IR (neat, cm−1) 3415, 1630, 1600,
4.6.21. 2-(Piperidinomethyl)-dec-1-en-3-yn-5-ol (23c)
1
1
1495, 1450, 1050, 965. H-NMR (200 MHz, CDCl3): l
224 mg (90%); IR (neat, cm−1) 3430, 1630. H-NMR
2.09 (s, 3H), 2.45 (dt, J=6.4 and 1.5 Hz, 2H), 2.97 (dd,
J=6.6 and 1.5 Hz, 2H), 3.41 (s, 2H), 3.60 (t, J=6.4
Hz, 2H), 5.54 (dquint, J=15.9 and 1.5 Hz, 1H), 6.05
(dt, J=15.9 and 6.6 Hz, 1H), 7.10–7.30 (m, 5H).
13C-NMR (50 MHz, CDCl3): l 23.7, 41.8, 58.9, 60.9,
(200 MHz, CDCl3): l 0.80 (t, J=7.3 Hz, 3H), 1.10–
1.70 (m, 6H), 2.23 (s, OH), 2.32 (m, 4H), 2.91 (s, 2H),
4.42 (t, J=6.4 Hz, 1H), 5.35 (s, 1H), 5.38 (s, 1H).
13C-NMR (50 MHz, CDCl3): l 13.8, 22.3, 24.0, 24.8,
25.3, 31.3, 37.35, 54.0, 61.6, 63.7, 84.0, 91.3, 123.0,

122
M. Alami et al. / Journal of Organometallic Chemistry 624 (2001) 114–123
127.7. Anal. Calc. for C16H27NO (249.40): C, 77.06; H,
10.91; Found: C, 77.88; H, 11.55%.
(dt, J=13.5 and 6.0 Hz, 1H), 6.18 (d, J=13.5 Hz, 1H),
7.60 (m, 4H), 7.82 (m, 2H), 8.32 (d, J=8.7 Hz, 1H).
13C-NMR (50 MHz, CDCl3): l 42.0, 57.2, 59.6, 120.1,
124.5, 125.1, 125.6, 125.7, 127.3, 128.0, 128.4, 130.6,
132.4, 133.6, 134.4. Anal. Calc. for C15H16NCl (245.75):
C, 73.31; H, 6.56; Found: C, 73.65; H, 6.82%.
4.6.22. (E)-N,N-di-t-Butoxycarbonyl-dec-2-en-4-yn-1-
amine (24a)
292 mg (90%); IR (neat, cm−1) 2120, 1745, 1700,
1630, 1150. 1H-NMR (200 MHz, CDCl3): l 0.90 (t,
J=7.2 Hz, 3H), 1.35 (m, 4H), 1.48 (s, 18H), 2.40 (m,
2H), 4.30 (dd, J=6.2 and 1.4 Hz, 2H), 5.60 (dt,
J=15.7 and 1.7 Hz, 1H), 5.97 (dt, J=15.7 and 6.4 Hz,
1H). 13C-NMR (50 MHz, CDCl3): l 13.8, 19.3, 22.1,
28.0, 28.3, 31.0, 47.5, 78.3, 82.4, 91.1, 112.7, 136.6,
152.0. Anal. Calc. for C20H33NO4 (351.49): C, 68.34; H,
9.46; Found: C, 68.85; H, 9.85%.
4.6.27. Terbinafine (30)
1
271 mg (93%); H-NMR (200 MHz, CDCl3): l 1.34
(s, 9H), 2.31 (s, 3H), 3.22 (dd, J=6.6 and 1.4 Hz, 2H),
3.95 (s, 2H), 5.78 (dt, J=15.8 and 1.4 Hz, 1H), 6.26
(dt, J=15.8 and 6.6 Hz, 1H), 7.55 (m, 4H), 7.90 (m,
2H), 8.36 (m, 1H). The spectral properties of ter-
binafine 30 were in good agreement with those reported
in the literature [15].
4.6.23. (E)-N,N-di-t-Butoxycarbonyl-undec-2-en-4-yn-
6-ol-1-amine (24b)
271 mg (71%); IR (neat, cm−1) 3400, 2130, 1750,
1620, 1120. 1H-NMR (200 MHz, CDCl3): l 0.90 (t,
J=7.2 Hz, 3H), 1.35 (m, 4H), 1.50 (s, 18H), 1.70 (m,
4H), 2.40 (m, 2H), 4.28 (dd, J=6.2 and 1.3 Hz, 2H),
4.55 (m, 1H), 5.70 (dt, J=15.8 and 1.6 Hz, 1H), 5.97
(dt, J=15.9 and 6.1 Hz, 1H). 13C-NMR (50 MHz,
CDCl3): l 13.7, 22.3, 24.6, 27.6, 31.1, 37.5, 47.3, 62.7,
82.5, 82.4, 90.6, 111.2, 138.5, 151.8. Anal. Calc. for
C21H35NO5 (381.52): C, 66.11; H, 9.25; Found: C,
66.21; H, 9.26%.
References
[1] (a) Review: J.F. Normant, A. Alexakis, Synthesis (1981) 841. (b)
V. Ratovelomanana, G. Linstrumelle, Tetrahedron Lett. 22
(1981) 315. (c) V. Ratovelomanana, G. Linstrumelle, Synth.
Commun 11 (1981) 917. (d) P.J. Stang, T. Kitamura, J. Am.
Chem. Soc. 109 (1987) 7561 and references therein.
[2] For more recent examples: (a) M. Alami, P. Ramiandrasoa, G.
Cahiez, Synlett (1998) 325. (b) A.L. Braga, G. Zeni, L.H. de
Andrade, C.C. Silveira, H.A. Stefani, Synthesis (1998) 39. (c) P.
Ramiandrasoa, B. Bre´hon, A. Thivet, M. Alami, G. Cahiez,
Tetrahedron Lett. 38 (1997) 2447.(d) R. Hara, Y. Liu, W.H.
Sun, T. Takahashi, Tetrahedron Lett. 38 (1997) 4103.
[3] (a) E. Negishi, G. Lew, T. Yoshida, J. Chem. Soc. Chem.
Commun. (1973) 874. (b) A. Commerc¸on, J.F. Normant, J.
Villieras, Tetrahedron 36 (1980) 1215. (c) R. Rossi, A. Carpita,
M.G. Quirici, M.L. Gaudeuzi, Tetrahedron 38 (1982) 631. (d) B.
Crousse, M. Mladenova, P. Ducept, M. Alami, G. Linstrumelle,
Tetrahedron 55 (1999) 4353 and references therein.
[4] (a) M. Gardette, A. Alexakis, J.F. Normant, J. Chem. Ecology 9
(1983) 219. (b) J.K. Stille, J.H. Simpson, J. Am. Chem. Soc. 109
(1987) 2138. (c) S.L. Schreiber, L.L. Kiessling, J. Am. Chem.
Soc. 110 (1988) 631. (d) M. Bujard, F. Ferri, M. Alami, Tetrahe-
dron Lett. 39 (1998) 4243. For Reviews see: (e) H. Lhermitte,
D.S. Grierson, Contemporary Org. Synth. 3 (1996) 41. (f) H.
Lhermitte, D.S. Grierson, Contemporary Org. Synth. 3 (1996)
93.
4.6.24. (Z)-1-Tributyltin-dec-2-en-4-yne (25)
1
264 mg (62%); IR (neat, cm−1) 2120, 1620. H-NMR
(200 MHz, CDCl3): l 0.92 (m, 18H), 1.2–1.65 (m,
18H), 2.17 (d, J=6.9 and 2.0 Hz, 2H), 2.36 (td, J=6.9
and 2.0 Hz, 2H), 5.12 (dq, J=9.5 and 2.0 Hz, 1H), 6.05
(q, J=9.5 Hz, 1H). 13C-NMR (50 MHz, CDCl3): l 9.8,
13.6, 13.9, 14.8, 19.7, 22.2, 27.3, 28.8, 29.1, 31.2, 78.2,
95.1, 102.8, 142.2. Anal. Calc. for C22H42Sn (425.27): C,
62.14; H, 9.95; Found: C, 62.68; H, 10.65%.
4.6.25. Methyl
(E)-5-Hydroxy-9-trimethylsilyl-non-6-en-8-ynoate (26)
188 mg (74%); IR (neat, cm−1) 3410, 2130, 1730,
[5] K. Sonogashira, Y. Tohda, N. Hagihara, Tetrahedron Lett.
(1975) 4467.
1
1250. H-NMR (200 MHz, CDCl3): l 0.01 (s, 9H), 1.38
[6] Recent examples of the modified Sonogashira coupling reaction:
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(q, J=7.1 Hz, 2H), 1.55 (quint., J=7.1 Hz, 2H), 2.10
(s, OH), 2.16 (t, J=7.2 Hz, 2H), 3.90 (qd, J=6.0 and
1.1 Hz, 1H), 5.55 (dd, J=16.0 and 1.4 Hz, 1H), 6.00
(dd, J=15.9 and 6.0 Hz, 1H). 13C-NMR (50 MHz,
CDCl3): l -0.5, 20.3, 33.4, 35.7, 51.3, 71.1, 94.8, 102.9,
109.6, 146.3, 173.9. CIMS (NH3) m/e (rel. int.) 237
(100). Anal. Calc. for C13H22O3Si (254.40): C, 61.38; H,
8.72; Found: C, 61.75; H, 9.03%.
4.6.26. (E)-N-Methyl N-naphtyl
methylene-3-chloro-prop-2-en-1-amine (29)
206 mg (81%); IR (neat, cm−1) 1635, 1600, 1500,
1
1460, 1365, 1135, 1025. H-NMR (200 MHz, CDCl3): l
2.25 (s, 3H), 3.12 (d, J=6.2 Hz, 2H), 3.90 (s, 2H), 6.08
.

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