Stereoselective syntheses of (E)- and (Z)-1-arylalk-3-en-1-ynes and (E,E)-, (Z,E)-, (E,Z)-, and (Z,Z)-alka-1,5-dien-3-ynes via a one-pot multicomponent coupling reaction

Article abstract of DOI:10.1055/s-2005-869955

Both 1-arylalk-3-en-1-ynes and alka-1,5-dien-3-ynes have been synthesized under extremely mild reaction conditions in good to high yields via a sequential Suzuki-type and Sonogashira reaction in a one-pot manner. Thus, the protocol involves Cu-mediated cross-coupling reaction of (E)- or (Z)- alkenyldisiamylborane with (trimethylsilyl)ethynyl bromide in the presence of 1M NaOMe and Pd/Cu-catalyzed cross-coupling reaction with aryl or alkenyl iodide in the presence of aqueous n-Bu₄NOH. The reaction with aryl iodide is tolerant of a wide variety of functional groups on the aromatic ring and leads to the stereoselective formation of (E)- and (Z)-1-arylalk-3-en-1-ynes. In addition, the reactions with (E)- and (Z)-1-iodoalk-1-enes have accomplished the construction of all possible combinations of geometrical isomers, (E,E)-, (Z,E)-, (E,Z)-, and (Z,Z)-alka-1,5-dien-3-ynes. Georg Thieme Verlag Stuttgart.

Full text of DOI:10.1055/s-2005-869955

PAPER
1991
Stereoselective Syntheses of (E)- and (Z)-1-Arylalk-3-en-1-ynes and (E,E)-,
(Z,E)-, (E,Z)-, and (Z,Z)-Alka-1,5-dien-3-ynes via a One-Pot Multicomponent
Coupling Reaction
Stereoselective
Synthe
a
sis of 1-Ary
s
lalk-3-en-
a
1-yne and
y
A
lka-1,5-die
u
n-3-yne ki Hoshi,* Hidenori Nakayabu, Kazuya Shirakawa
Department of Applied and Environmental Chemistry, Kitami Institute of Technology, 165 Koen-cho, Kitami, Hokkaido 090-8507, Japan
Fax +81(157)247719; E-mail: hoshi-m@chem.kitami-it.ac.jp
Received 13 January 2005; revised 25 February 2005
step.8 Suzuki–Miyaura reaction9 and Sonogashira–Hagi-
Abstract: Both 1-arylalk-3-en-1-ynes and alka-1,5-dien-3-ynes
hara reaction10 are used complementarily in such con-
have been synthesized under extremely mild reaction conditions in
struction. Thus, the former can perform the desired
coupling upon reaction of alkenyl- or arylborane with alk-
good to high yields via a sequential Suzuki-type and Sonogashira
reaction in a one-pot manner. Thus, the protocol involves Cu-medi-
ated cross-coupling reaction of (E)- or (Z)-alkenyldisiamylborane 1-ynyl halide, and the latter can perform the same one
with (trimethylsilyl)ethynyl bromide in the presence of 1 M NaOMe
upon reaction of alk-1-yne with alkenyl or aryl halide. In
and Pd/Cu-catalyzed cross-coupling reaction with aryl or alkenyl
the former alkenyl group functions as nucleophile, while
iodide in the presence of aqueous n-Bu4NOH. The reaction with
in the latter alkenyl and aryl groups function as electro-
aryl iodide is tolerant of a wide variety of functional groups on the
philes. If sp2 carbon atom is introduced into each end of
ethynyl unit in a different manner with each other, the pro-
tocol will provide an intriguing access to conjugated
dienyne and arylenyne.
aromatic ring and leads to the stereoselective formation of (E)- and
(Z)-1-arylalk-3-en-1-ynes. In addition, the reactions with (E)- and
(Z)-1-iodoalk-1-enes have accomplished the construction of all pos-
sible combinations of geometrical isomers, (E,E)-, (Z,E)-, (E,Z)-,
and (Z,Z)- alka-1,5-dien-3-ynes.
We have recently reported the stereoselective synthesis of
(E)- and (Z)-alk-3-en-1-ynes 1 and 2 from (E)- and (Z)-
alk-1-enyldisiamylboranes and (trimethylsilyl)ethynyl
bromide through a Suzuki-type reaction (Scheme 1).11
Thus, the cross-coupling reaction proceeds in the presence
of a catalytic amount of Cu(acac)2 and an excess amount
of 1 M NaOMe at –15 °C to room temperature to afford
products 1 and 2, desilylated during the reaction, respec-
tively. The terminal conjugated enyne, where an alkenyl
group has already been introduced into one end of ethynyl
unit, has the feasibility of assembling p-extended conju-
gation taking advantage of Sonogashira reaction. We now
report the stereoselective synthesis of conjugated enynes
tethering aryl or alkenyl substituent to the alkynyl carbon,
in which a sequential three-component cross-coupling re-
action of (trimethylsilyl)ethynyl bromide as an ethynyl
unit can be achieved under extremely mild conditions.12
Key words: alkenylborane, (trimethylsilyl)ethynyl bromide, cross-
coupling, 1-arylalk-3-en-1-yne, alka-1,5-dien-3-yne
Construction of conjugated compounds bearing alkynyl
moieties is of great significance due to the fact that they
are found in diverse fields ranging from natural products1
and pharmaceuticals2 to functional materials.3 Among the
conjugated systems, the system having sp2 carbon atoms
at both ends of ethynyl unit, unexpectedly, is found in bio-
active natural products including phytotoxin4 and mitotic
inhibitor.5 Furthermore, the conjugated dienyne system is
employed for forming soluble polymers by anionic
polymerization6 and chrysene derivatives by tandem cy-
clizations.7 For the formation of sp–sp2 carbon bond, tran-
sition metal-catalyzed cross-coupling reaction is the key
H
B
H
C
CH
2
C
R1
C
C
C
R1
C
C
R2
R2
Me3SiC CBr
Cu(acac)2/1 M NaOMe
1
2
R
2 = H, R1
–15 °C to r.t., overnight
H
B
I
H
H
B
H
H
C
2
LiBEt3H
C
C
C
R1
C
R1
R1
CH
2
Scheme 1
SYNTHESIS 2005, No. 12, pp 1991–2007
x
x.
x
x
.
2
0
0
5
Advanced online publication: 20.06.2005
DOI: 10.1055/s-2005-869955; Art ID: F00705SS
© Georg Thieme Verlag Stuttgart · New York

1992
M. Hoshi et al.
PAPER
On the basis of our synthetic route to (E)- and (Z)-alk-3- Table 1 Effect of Base for Cross-Coupling Reaction of 1aa with 3ab
en-1-ynes 1 and 2, we investigated the one-pot synthesis
Entry
Base
Yield of 4aa (%)c
of 1-arylalk-3-en-1-yne by means of Sonogashira cou-
pling with aryl halides. (E)-Dec-3-en-1-yne (1a) and iodo-
benzene (3a) were chosen as model substrates for the
coupling. The choice of iodide was to make the room
temperature cross-coupling reaction feasible. Thus, the
reaction of (E)-oct-1-enyldisiamylborane with (trimethyl-
silyl)ethynyl bromide was conducted in the same manner
as previously reported,11 except for the amount of 1 M
NaOMe13 to generate 1a, which was subjected to the reac-
tion with 3a (1 equiv) under PdCl2(PPh3)2/CuI catalyst
conditions, a typical combination of catalysts for the So-
nogashira reaction (Scheme 2). We initially examined the
effect of base, one of important experimental variables.
The cross-coupling reaction was carried out in the pres-
ence of PdCl2(PPh3)2 (0.02 equiv), CuI (0.04 equiv) and
base (2 equiv) at room temperature for one hour under ar-
gon to afford the corresponding conjugated arylenyne,
(E)-1-phenyldec-3-en-1-yne (4aa), with retention of con-
figuration at the double bond (Scheme 2). Some bases
were employed, and the results are shown in Table 1. Use
of Et3N, an amine base for the Sonogashira reaction, gave
a 54% yield of 4aa along with a significant amount of un-
reacted 3a (entry 1). By using pyrrolidine instead of Et3N,
the yield of 4aa was increased to 86%; however, unde-
fined by-products were observed in the reaction mixture
(entry 2). Mori and co-workers reported that quaternary
ammonium compounds such as n-Bu4NF, n-Bu4NOH and
NH4OH promoted the Sonogashira reaction in the absence
of amine base.14 Although the reactions using n-Bu4NF
and NH4OH led to the formation of 4aa, whose yields
were far inferior to those of amine bases under the stated
conditions (entries 3 and 4). When n-Bu4NOH was used,
the reaction was completed within one hour to afford 4aa
in 90% yield with good purity compared with pyrrolidine
(entry 5). It is noteworthy that the synthesis of 4aa was
achieved in high yield without isolation of 1a. The re-
duced amount of either n-Bu4NOH or PdCl2(PPh3)2/CuI
catalyst retarded the reaction (entries 6 and 7).
1
2
3
4
5
6
7
Et3N
54
86
43
32
90
68d
60e
Pyrrolidine
n-Bu4NF (1 M solution in THF)
NH4OH (1 M solution in H2O)
n-Bu4NOH (40 wt% in H2O)
n-Bu4NOH (40 wt% in H2O)
n-Bu4NOH (40 wt% in H2O)
a Compound 1a was prepared by the reaction of (E)-oct-1-enyldi-
siamylborane (1 mmol) with (trimethylsilyl)ethynyl bromide (0.67
mmol) in the presence of Cu(acac)2 (0.05 mmol) and 1 M NaOMe
(0.75 mmol) at –15 °C to r.t. for overnight.
b Unless otherwise stated, the reaction with 3a (0.5 mmol) was carried
out using PdCl2(PPh3)2 (0.01 mmol), CuI (0.02 mmol) and base (1.0
mmol) at r.t. for 1 h.
c The yields were estimated by GC and based on 3a.
d n-Bu4NOH (0.5 mmol) was used.
e PdCl2(PPh3)2 (0.005 mmol) and CuI (0.01 mmol) were used.
veloped for preparing conjugated enynes, the transition
metal-catalyzed dimerization of terminal alkynes is a
practical and straightforward method for the synthesis of
them. There are many reports on the preparation of conju-
gated enynes with the same two aryl groups15 or a phenyl
group16 using the dimerization reaction. It should be noted
that the present reaction regio- and stereoselectively fur-
nishes products 4aa, 4ba and 4da (entries 1, 2, and 4) as
if a stereospecific head-to-head cross-dimerization were
realized. The other methods, including cross-coupling re-
action, were also reported for the synthesis of conjugated
enynes with phenyl group(s).17 We continued to examine
the cross-coupling reaction of (E)-oct-3-en-1-yne (1f),
bearing an alkyl substituent, with a range of aryl iodides
at room temperature. The reactions with electron-donat-
ing aryl iodides proceeded without any trouble in good
yields (entries 6 and 7). Electron-deficient aryl iodides
also coupled with 1f in good to high yields (entries 8–11).
A free aniline, a ketone, and a nitro group all proved to be
compatible with our reaction conditions. It is well-known
that the relative reactivity of aryl halide is ArI >> ArBr >
ArCl. Indeed, the reactions with 1-bromo-4-iodobenzene
(3g) and 1-chloro-4-iodobenzene (3h) afforded (E)-1-(4-
bromophenyl)oct-3-en-1-yne (4fg) and (E)-1-(4-chlo-
rophenyl)oct-3-en-1-yne (4fh), respectively, suitable for
With our optimized reaction conditions in hand (Table 1,
entry 5), we then carried out the coupling reaction of dif-
ferent types of 1 with a wide range of 3. Table 2 shows
that this method is applicable to a diversity of substrates
and compatible with a variety of functional groups. This
coupling reaction was successfully applied to 1 bearing
alkyl substituent(s) as well as unsaturated one, affording
the corresponding phenylated enynes 4ba–ea in good to
excellent yields with high stereoselectivity (≥ 99%) (en-
tries 2–5). Although a plethora of methods have been de-
I
3a
Me3SiC CBr
Cu(acac)2/1 M NaOMe
H
B
H
H
C
H
CH
H
C
H
C
2
PdCl2(PPh3)2/CuI/Base
r.t., 1 h
C
C
C
C
C C
n-C6H13
n-C6H13
n-C6H13
4aa
1a
Scheme 2
Synthesis 2005, No. 12, 1991–2007 © Thieme Stuttgart · New York

PAPER
Stereoselective Synthesis of 1-Arylalk-3-en-1-ynes and Alka-1,5-dien-3-ynes
1993
further functionalization (entries 10 and 11). Heteroaro- from PdCl2(PPh3)2 to PdCl2(dppf)·CH2Cl2 improved the
matic compounds such as 2-iodothiophene (3i) and 3-io- yield of product 4fk significantly. Moreover, addition of
dopyridine (3j) reacted with 1f as well to give the AsPh3 (0.02 equiv) was found to make the reaction clean18
corresponding products 4fi and 4fj in good yields, respec- while giving the same yield (entry 15) as the reaction in
tively (entries 12 and 13). In contrast, sterically demand- the absence of AsPh3. The use of PdCl2(dppf)·CH2Cl2 to-
ing 2-iodotoluene (3k) and 1-iodonaphthalene (3l) gether with AsPh3 improved the yield of product 4fl like-
coupled with 1f in rather moderate yields (entries 14 and wise (entry 17) and resulted in a dramatic increase of the
16), and more sterically hindered 2-iodocumene (3m) yield of product 4fm (entry 19). The effectiveness of
gave only 7% yield of product 4fm under the same reac- PdCl2(dppf)·CH2Cl2 as superior to that of PdCl2(PPh3)2
tion conditions (entry 18). It is interesting to note that the could be attributable to its structure.19
ligand on palladium center played a crucial role in the
present reaction. Thus, changing the palladium catalyst
Table 2 Cross-Coupling Reaction of (E)-Alk-3-en-1-yne with Aryl Iodidea
Y
I
3
Y
H
B
H
C
C
H
C
CH Pd(II)/CuI/n-Bu4NOH
r.t.
R2
2
C
C
C
C
C
C
R1
R1
R1
R2
R2
1
4
Entry
1
R1
R2
H
Aryl Iodide (R3)
Product
Yield (%)b
83
n-C6H13
t-C4H9
4aa
I
2
3
H
H
H
4ba
4ca
95
82
I
I
I
4
5
6
4da
4ea
4fc
75
77
80
n-C3H7
n-C4H9
n-C3H7
H
CH3O
NH2
I
7
8
n-C4H9
n-C4H9
H
H
4fd
4fe
67
72
I
I
O
CH3C
I
9
10
11
12
13
n-C4H9
n-C4H9
n-C4H9
n-C4H9
n-C4H9
H
H
H
H
H
4ff
4fg
4fh
4fi
77
85
82
75
82
NO2
Br
I
Cl
I
I
S
N
4fj
I
Synthesis 2005, No. 12, 1991–2007 © Thieme Stuttgart · New York

1994
M. Hoshi et al.
PAPER
Table 2 Cross-Coupling Reaction of (E)-Alk-3-en-1-yne with Aryl Iodidea (continued)
Y
I
3
Y
H
B
H
C
C
H
C
CH Pd(II)/CuI/n-Bu4NOH
r.t.
R2
2
C
C
C
C
C
C
R1
R1
R1
R2
R2
1
4
Entry
14
R1
R2
H
Aryl Iodide (R3)
Product
Yield (%)b
60
CH3
n-C4H9
n-C4H9
n-C4H9
4fk
15
16
H
H
80c
52
I
4fl
I
17
n-C4H9
H
78c
18
19
n-C4H9
n-C4H9
H
H
4fm
7
i-C3H7
I
70c
a The reaction was carried out using PdCl2(PPh3)2 (0.04 mmol), CuI (0.08 mmol), 3 (2.0 mmol), and n-Bu4NOH (4.0 mmol) at r.t. for 1 h to
4 h, unless otherwise noted.
b Isolated yields based on 3.
c PdCl2(dppf)·CH2Cl2 (0.04 mmol) and AsPh3 (0.08 mmol) were used instead of PdCl2(PPh3)2.
Next we examined the cross-coupling reaction of (Z)-alk- 12–14). Therefore, the present reaction provides not only
3-en-1-ynes 2, which were generated by treatment of (Z)- (E)- but also (Z)-1-arylalk-3-en-1-yne that is the same
1-iodoalk-1-enyldisiamylboranes with LiBEt3H,20 fol- product as if a stereoselective head-to-head cross-dimer-
lowed by cross-coupling reaction with (trimethylsi- ization of terminal alkynes were realized.
lyl)ethynyl bromide as illustrated in Scheme 1, with aryl
Our attention was then turned to the cross-coupling reac-
iodide (3), and the results are summarized in Table 3. The
tion of (E)- and (Z)-alk-3-en-1-ynes 1 and 2 with alkenyl
reaction of (Z)-dec-3-en-1-yne (2a) with iodobenzene
iodide for the stereoselective synthesis of alka-1,5-dien-3-
ynes. We applied the optimized conditions for the synthe-
sis of 1-arylalk-3-en-1-ynes to the cross-coupling reac-
tions with (E)- and (Z)-1-iodoalk-1-enes 6 and 7. It was
found that most of the reactions proceeded smoothly to
furnish the desired cross-coupling products (Scheme 3).
(3a) was carried out under the same conditions as de-
scribed for the reaction of (E)-dec-3-en-1-yne (1a). It was
found that the cross-coupling reaction proceeded to com-
pletion in one hour and afforded the desired product, (Z)-
1-phenyldec-3-en-1-yne (5aa), in 85% yield with high
stereoselectivity (≥ 98%) (entry 1). The identical condi-
The reaction between (E)-oct-3-en-1-yne (1f), generated
tions were applied to the reaction of (Z)-1-phenylbut-1-
by the reaction of (E)-hex-1-enyldisiamylborane with (tri-
en-3-yne (2c) with 3a, giving a moderate yield of product
methylsilyl)ethynyl bromide, and (E)-1-iodohex-1-ene
5ca (entry 2); however, switching the palladium catalyst
(6a) (1 equiv) was carried out in the presence of
PdCl2(PPh3)2 (0.02 equiv), CuI (0.04 equiv) and n-
Bu4NOH (2 equiv) at room temperature under argon.
from PdCl2(PPh3)2 to PdCl2(dppf)·CH2Cl2 and adding
AsPh3 resulted in a significant increase of the yield (entry
3). In this case, why the reaction using PdCl2(dppf)·CH2Cl2
Thus the reaction was completed within 1 h to afford the
together with AsPh3 gave a better yield than PdCl2(PPh3)2
corresponding conjugated dienyne, (5E,9E)-tetradeca-
remains unclear at present. We also explored the n-
5,9-dien-7-yne (8fa), in 80% yield with retention of con-
Bu4NOH-promoted reaction of a variety of functionalized
figuration at both double bonds (Scheme 4) (Table 4, en-
aryl iodides 3. Electron-donating, electron-deficient, and
try 1). Reducing the catalyst loading showed retardation
heteroaromatic aryl iodides could undergo the cross-cou-
of the reaction, analogous to the aforementioned reaction
pling reaction with (Z)-oct-3-en-1-yne (2f) under
of (E)-dec-3-en-1-yne (1a) with iodobenzene (3a). Differ-
ent types of 1 could couple with 6a to give the correspond-
ing conjugated E,E-dienynes in good yields (Scheme 4)
PdCl2(PPh3)2/CuI catalyst conditions, leading to the for-
mation of (Z)-1-aryloct-3-en-1-ynes, 5fb–fj, in good to
high yields (entries 4–11). On the other hand, the cross-
(Table 4, entries 2–4 and 15). The above conditions could
coupling reaction of sterically demanding aryl iodides
be also applied to the cross-coupling reaction of (Z)-oct-
3-en-1-yne (2f), affording the desired product, (5Z,9E)-
tetradeca-5,9-dien-7-yne (9fa), in 78% yield with high
stereoselectivity (≥ 98%) (Scheme 4) (Table 4, entry 5).
with 2f could be performed under PdCl2(dppf)·CH2Cl2/
AsPh3/CuI catalyst conditions, affording the correspond-
ing products 5fk–fm in moderate to high yields (entries
Synthesis 2005, No. 12, 1991–2007 © Thieme Stuttgart · New York

PAPER
Stereoselective Synthesis of 1-Arylalk-3-en-1-ynes and Alka-1,5-dien-3-ynes
1995
Table 3 Cross-Coupling Reaction of (Z)-Alk-3-en-1-yne with Aryl Iodidea
Y
I
3
H
H
H
H
B
H
C
Pd(II)/CuI/n-Bu4NOH
r.t.
H
C
C
C
C
C
C
Y
R1
R1
R1
CH
C
C
2
2
5
Entry
1
R1
Aryl Iodide (R3)
Product
5aa
Yield (%)b
85
n-C6H13
I
2
3
5ca
52
I
72c
4
5
6
n-C4H9
n-C4H9
n-C4H9
5fb
5fc
5fd
85
82
91
CH3
I
CH3O
NH2
I
I
O
7
8
n-C4H9
n-C4H9
n-C4H9
n-C4H9
n-C4H9
5fe
5ff
5fg
5fi
5fj
80
82
86
75
84
CH3C
I
NO2
Br
I
9
I
10
11
I
S
N
I
I
CH3
12
13
14
n-C4H9
n-C4H9
n-C4H9
5fk
5fl
86c
I
89c
i-C3H7
I
5fm
58c,d
a The reaction was carried out using PdCl2(PPh3)2 (0.04 mmol), CuI (0.08 mmol), 3 (2.0 mmol), and n-Bu4NOH (4.0 mmol) at r.t. for 1–4 h,
unless otherwise noted.
b Isolated yields based on 3.
c PdCl2(dppf)·CH2Cl2 (0.04 mmol) and AsPh3 (0.08 mmol) were used instead of PdCl2(PPh3)2.
d The reaction time was prolonged to 8 h.
Having achieved the one-pot synthesis of 9fa as well as (7a) produced high yields of (5E,9Z)-tetradeca-5,9-dien-
8fa, we made an effort to construct all possible combina- 7-yne (10fa) and (5Z,9Z)-tetradeca-5,9-dien-7-yne (11fa)
tions of geometrical isomers of alka-1,5-dien-3-ynes 8, 9, in the reactions with 1f and 2f (entries 6 and 7), except that
10, 11 using representative substrates (Scheme 3), and the 10fa is the same product as 9fa. On the other hand, use of
results are summarized in Table 4. (Z)-1-Iodohex-1-ene (Z)-1-bromohex-1-ene instead of 7a yielded no product
Synthesis 2005, No. 12, 1991–2007 © Thieme Stuttgart · New York

1996
M. Hoshi et al.
PAPER
R4
R4
R1
R1
R1
(E,E)-8
(Z,E)-9
1 or 2
R4
R4
R4
I
6 or 7
R1
R1
(Z,Z)-11
(E,Z)-10
Scheme 3
H
B
2
C
R1
C
C
R2
R1
C4H9-n
8fa: R1 = n-C4H9, R2 = H
8ba: R1 = t-C4H9, R2 = H
H
C
CH
C
H
I
C4H9-n
R1
R2
R2
6a
C
C
1
8ca: R1
8da: R1
=
, R2 = H
, R2 = H
H
PdCl2(PPh3)2/CuI/n-Bu4NOH
r.t.
=
8ea: R1 = n-C3H7, R2 = n-C3H7
H
H
C
C4H9-n
9fa: R1 = n-C4H9
C
C
C
R1
CH
R1
2
H
H
B
H
B
I
2
C
C C
R1
R1
2
Scheme 4
and resulted in the recovery of the bromide under the same This prompted us to carry out the coupling of 1f with 7b
reaction conditions. The reactions of (E)-1-iodo-2-phe- in the presence of LiI (2 equiv) otherwise under the same
nylethene (6b) also proceeded with high yields and stereo- conditions, thereby leading to a marked increase in the
selectivity (entries 8 and 9), while the reaction of (Z)-1- yield of 10fb (from 5 to 64%) (entry 11). Moreover, using
iodo-2-phenylethene (7b) gave only 5% yield of product PdCl2(dppf)·CH2Cl2 together with AsPh3 in place of
10fb (entry 10). In contrast, the cross-coupling of 2f with PdCl2(PPh3)2, combined with LiI, led to 72% yield (entry
7b gave a higher yield (45%) of product 11fb under the 12). When the cross-coupling of 2f with 7b was carried
identical conditions (entry 13). We were aware that the out under PdCl2(dppf)·CH2Cl2/AsPh3/CuI catalyst condi-
difference between the two reactions was the presence or tions, the yield of 11fb increased to 77% in a similar man-
absence of LiI, which was formed in the step of the gener- ner as described above (entry 14). Amatore and Jutand
ation of 2f as shown in Scheme 5.
have reported that the oxidative addition to Pd(0) is faster
in the presence of a lithium cation due to the generation of
H
B
I
H
H
B
2
LiBEt3H
C
C
C
C
+ Et3B + LiI
n-C4H9
n-C4H9
2
2f
Scheme 5
Synthesis 2005, No. 12, 1991–2007 © Thieme Stuttgart · New York

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Stereoselective Synthesis of 1-Arylalk-3-en-1-ynes and Alka-1,5-dien-3-ynes
1997
a more active Pd(0) complex.21 Although we have no clear sults to those described above. Consequently, LiI as well
evidence for the remarkable effect on LiI in the present re- as PdCl2(dppf)·CH2Cl2 is necessary to accomplish the
action, the in situ generation of such a reactive Pd cross-coupling reaction with 7b in good yields. The catal-
catalyst22 possibly plays a critical role in the reaction ysis of PdCl2(dppf)·CH2Cl2 superior to that of
mechanism. It is interesting to note that addition of LiCl PdCl2(PPh3)2 would be attributable to its structure.19 The
instead of LiI led to the same result. The reactions of (E)- present protocol allowed us to synthesize all the four geo-
and (Z)-4-phenylbut-3-en-1-ynes (1c and 2c) with 1-io- metrical isomers of conjugated alka-1,5-dien-3-ynes in
doalk-1-ene, except for 7b, under PdCl2(PPh3)2/CuI cata- good to high yields with high stereoselectivity.
lyst conditions afforded the corresponding conjugated
dienynes in good to high yields (entries 15–20). In the re-
actions with 7b (entries 21–25), we observed similar re-
Table 4 Cross-Coupling Reaction of (E)- and (Z)-Alk-3-en-1-ynes 1 and 2 with (E)- and (Z)-1-Iodoalk-1-enes 6 and 7a
Entry
1
Alk-3-en-1-yne
1-Iodoalk-1-ene (R4)
Product
Yield (%)b
80
n-C4H9
n-C4H9
n-C4H9
n-C4H9
I
n-C4H9
n-C4H9
1f
6a
6a
8fa
2
3
4
79
66
65
t-C4H9
t-C4H9
1b
8ba
6a
6a
1d
8da
8ea
n-C3H7
n-C3H7
n-C4H9
n-C3H7
n-C3H7
1e
n-C4H9
5
6
6a
78
77
n-C4H9
n-C4H9
2f
9fa
n-C4H9
n-C4H9
1f
2f
1f
I
n-C4H9
7a
10fa
n-C4H9
7
8
7a
85
80
n-C4H9
11fa
8fb
I
n-C4H9
6b
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1998
M. Hoshi et al.
PAPER
Table 4 Cross-Coupling Reaction of (E)- and (Z)-Alk-3-en-1-ynes 1 and 2 with (E)- and (Z)-1-Iodoalk-1-enes 6 and 7a (continued)
Entry
9
Alk-3-en-1-yne
1-Iodoalk-1-ene (R4)
Product
Yield (%)b
76
2f
1f
6b
n-C4H9
9fb
10
5
I
n-C4H9
11
12
64c
72d
7b
10fb
13
2f
7b
45
n-C4H9
14
15
11fb
77e
78
n-C4H9
6a
6a
1c
8ca
n-C4H9
16
17
63
69
2c
1c
9ca
n-C4H9
7a
7a
6b
10ca
n-C4H9
18
19
2c
1c
57
53
11ca
8cb
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Stereoselective Synthesis of 1-Arylalk-3-en-1-ynes and Alka-1,5-dien-3-ynes
1999
Table 4 Cross-Coupling Reaction of (E)- and (Z)-Alk-3-en-1-ynes 1 and 2 with (E)- and (Z)-1-Iodoalk-1-enes 6 and 7a (continued)
Entry
20
Alk-3-en-1-yne
1-Iodoalk-1-ene (R4)
Product
Yield (%)b
2c
6b
57
9cb
21
22
23
1c
7b
4
21c
59d
10cb
24
2c
7b
24
25
11cb
60e
a The reaction was carried out using PdCl2(PPh3)2 (0.04 mmol), CuI (0.08 mmol), 6 or 7 (2.0 mmol), and n-Bu4NOH (4.0 mmol) at r.t. for 1 to
4 h, unless otherwise noted.
b Isolated yields based on 6 or 7.
c Before the reaction with 7b, LiI (4 mmol) was added to the reaction mixture containing (E)-alk-3-en-1-yne, and the mixture was stirred for
0.5 h at r.t.
d In the presence of LiI (4 mmol), PdCl2(dppf)·CH2Cl2 (0.04 mmol) and AsPh3 (0.08 mmol) were used instead of PdCl2(PPh3)2.
e PdCl2(dppf)·CH2Cl2 (0.04 mmol) and AsPh3 (0.08 mmol) were used instead of PdCl2(PPh3)2.
To the best of our knowledge, there have been a few re- en-1-yne and alka-1,5-dien-3-yne via a three-component
ports on the synthesis of conjugated alka-1,5-dien-3-ynes. coupling in which (trimethylsilyl)ethynyl bromide reacts
Hiyama and co-workers reported that trimethylsilyl(tri- with alkenyldisiamylborane and aryl or alkenyl iodide in
methylstannyl)ethyne could couple sequentially with two turn. The first cross-coupling forms (E)- and (Z)-alk-3-en-
different alkenyl iodides in the presence of the same pal- 1-ynes whose alkenyl group is introduced as nucleophile
ladium catalyst, where the reaction required a wide tem- into the sp carbon atom attached to bromine atom. In the
perature (from –78 to 50 °C) and a large excess amount of second cross-coupling, aryl or alkenyl group is introduced
expensive tris(dimethylamino)sulfur (trimethylsilyl)di- as electrophile into the other sp carbon atom. Thus, (tri-
fluoride.23 Rossi and co-workers converted trimethylsilyl- methylsilyl)ethynyl bromide is used as an ethynyl unit,
ethynylzinc chloride into alka-1,5-dien-3-yne upon the and sp2 carbon atom can be introduced into each end of the
stepwise procedure, coupling with alkenyl halide, desilyl- ethynyl unit by employing a Suzuki-type reaction and the
ation, and coupling with another alkenyl halide.24 Tellier Sonogashira reaction. The second cross-coupling with
and co-workers also reported that butenynylzinc bromide aryl iodide is tolerant of a wide variety of functional
derived from 1,1-difluoroethene was coupled with alkenyl groups on the aromatic ring under the present conditions
iodide to give terminal 1,5-dien-3-yne, where the reaction and leads to the stereoselective and efficient formation of
required a very low temperature (–100 °C).25 The present (E)- and (Z)-1-arylalk-3-en-1-ynes. Moreover, the reac-
protocol has some advantageous properties over other tions with (E)- and (Z)-1-iodoalk-1-enes effect the assem-
methods: low toxicity, inexpensive reagents, operational bly of (E,E)-, (Z,E)-, (E,Z)-, and (Z,Z)- alka-1,5-dien-3-
simplicity, and easy operating conditions (from –15 °C to ynes, in good yields with high stereoselectivity. Synthetic
room temperature).
application of this protocol is currently under investiga-
tion.
In summary, we have successfully developed a one-pot
method for the stereoselective syntheses of 1-arylalk-3-
Synthesis 2005, No. 12, 1991–2007 © Thieme Stuttgart · New York

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M. Hoshi et al.
PAPER
NMR spectra were recorded on a JEOL JNM-A-500 spectrometer
with TMS as internal standard. IR spectra were recorded on a Shi-
madzu FT-IR 8300 spectrometer, and only the strongest/structurally
most important absorption peaks are listed. Mass spectra determina-
tions were performed on a JEOL JMS-SX102A spectrometer (EI,
70 eV). GC analyses were performed with a Shimadzu GC-14B gas
chromatograph equipped with a glass column (5% FFAP on Uniport
B, 1 m or 5% Silicone SE-30 on Uniport B, 1 m), a flame ionization
detector, and a Shimadzu C-R8A digital integrator-recorder. TLC
analyses were carried out using aluminum sheets pre-coated with
silica gel 60 F254 purchased from Merck. Purification of product was
performed by flash chromatography using Merck silica gel (Silica
gel 60, 40–63 mm) or column chromatography using Merck alumi-
num oxide (aluminum oxide 60 active basic, 70–230 mm). All reac-
tions were carried out under an argon atmosphere. Unless otherwise
noted, commercially available materials were used without any pu-
rification. Alkyne and 2-methylbut-2-ene were used after distilla-
tion over CaH2 under argon. THF was distilled from sodium
benzophenone ketyl under argon before use. (Trimethylsilyl)ethy-
nyl bromide,26 1-iodoalk-1-yne,27 (E)-1-iodoalk-1-ene,28 (Z)-1-io-
doalk-1-ene,29 and a solution of BH3 in THF30 were prepared
according to the literature procedures.
(Z)-alk-1-enyldisiamylborane was treated as described above for
the General Procedure for 4, 8 and 10. In the cases of synthesis of
5ca, 5fk, 5fl, 5fm, 11fb, and 11cb, PdCl2(dppf)·CH2Cl2 and AsPh3
instead of PdCl2(PPh3)2 were employed. Work-up procedure was
the same as described above, except for extracting with Et2O for 5fe
and 5ff and purifying by column chromatography on aluminum ox-
ide (basic) for 5fd, 5fm, 9cb,31 and 11cb.31
(E)-1-Phenyldec-3-en-1-yne (4aa)
Eluent: pentane.
IR (neat): 3020, 2954, 2927, 2854, 1596, 1488, 952, 754, 690 cm–1.
1H NMR (500 MHz, CDCl3): d = 0.89 (t, J = 7.0 Hz, 3 H), 1.25–
1.45 m, 8 H), 2.1–2.2 (m, 2 H), 5.70 (dt, J = 16.0, 1.5 Hz, 1 H), 6.22
(dt, J = 16.0, 7.0 Hz, 1 H), 7.25–7.3 (m, 3 H), 7.4–7.45 (m, 2 H).
13C NMR (125 MHz, CDCl3): d = 14.0 (CH3), 22.6 (CH2), 28.7 (2
CH2), 31.6 (CH2), 33.2 (CH2), 87.9 (≡C), 88.4 (≡C), 109.5 (=CH),
123.7 (=C), 127.8 (=CH), 128.2 (2 =CH), 131.4 (2 =CH), 145.1
(=CH).
EI-MS: m/z (%) = 212 (50, [M+]), 155 (23), 142 (17), 141 (78), 129
(16), 128 (100), 115 (40), 91 (12).
HRMS (EI): m/z calcd for C16H20 [M+]: 212.1565; found: 212.1541.
(E)-1-Aryl-3-alken-1-ynes 4, (E,E)-Alka-1,5-dien-3-ynes 8 and
(E,Z)-Alka-1,5-dien-3-ynes 10; General Procedure
(E)-5,5-Dimethyl-1-phenylhex-3-en-1-yne (4ba)
Eluent: pentane.
To a solution of BH3 (4 mmol) in THF (0.33 M solution) was added
2-methylbut-2-ene (0.56 g, 8 mmol) dropwise at – 15 °C under ar-
gon, and the reaction mixture was stirred for 2 h at 0 °C to form a
solution of disiamylborane in THF. To this was added alkyne (4
mmol) dropwise at – 15 °C and the mixture was stirred for 2 h at 0
°C. To the solution of alkenyldisiamylborane in THF thus prepared,
was added Cu(acac)2 (0.052 g, 0.2 mmol) under an argon flow, fol-
lowed by dropwise addition of (trimethylsilyl)ethynyl bromide
(0.474 g, 2.68 mmol) and 1 M NaOMe (3 mL, 3 mmol), and the re-
sulting mixture was allowed to warm gradually to r.t. and stirred
overnight. After the mixture was cooled to 0 °C, PdCl2(PPh3)2
(0.028 g, 0.04 mmol) and CuI (0.015 g, 0.08 mmol) were added to
the cooled mixture under an argon flow followed by dropwise addi-
tion of n-Bu4NOH (40 wt% solution in H2O) (2.66 mL, 4 mmol) and
aryl or alkenyl iodide (2 mmol). [For the preparation of 4fk, 4fl, and
4fm, PdCl2(dppf)·CH2Cl2 (0.033 g, 0.04 mmol) and AsPh3 (0.027 g,
0.08 mmol) were employed instead of PdCl2(PPh3)2. For the prepa-
ration of 10fb and 10cb, the following procedure was used. After
the reaction mixture was cooled to 0 °C, LiI (0.535 g, 4 mmol) was
added under an argon flow, and then the mixture was stirred for 0.5
h at r.t. Except for the use of PdCl2(dppf)·CH2Cl2 and AsPh3 in place
of PdCl2(PPh3)2, subsequent operations were the same as described
above]. After stirring for 1 to 4 h at r.t., the mixture was treated with
aq 3 M NaOH (4 mL) and H2O2 (30 wt% solution in H2O) (2 mL)
at 0 °C and stirred for 1 h at the same temperature to decompose the
residual organoboron compound. The resultant mixture was extract-
ed with pentane or Et2O (for 4fe and 4ff), washed with brine, dried
(Na2SO4), and concentrated under vacuo. Purification by flash chro-
matography on silica gel or column chromatography on aluminum
oxide (basic) (for 4fd, 8cb, and 10cb31) provided product 4, 8, or 10.
IR (neat): 3020, 2960, 2902, 2866, 1595, 1490, 1363, 1255, 960,
754, 690 cm–1.
1H NMR (500 MHz, CDCl3): d = 1.06 (s, 9 H), 5.63 (d, J = 16.1 Hz,
1 H), 6.29 (d, J = 16.1 Hz, 1 H), 7.27–7.32 (m, 3 H), 7.4–7.44 (m, 2
H).
13C NMR (125 MHz, CDCl3): d = 29.0 (3 CH3), 34.1 (C), 88.2 (≡C),
88.4 (≡C), 105.0 (=CH), 123.6 (=C), 127.8 (=CH), 128.2 (2 =CH),
131.3 (2 =CH), 155.3 (=CH).
EI-MS: m/z (%) = 184 (87, [M+]), 170 (14), 169 (100), 167 (12),
155 (13), 154 (63), 153 (32), 152 (25), 141 (25), 129 (12), 128 (17),
115 (22), 91 (34).
HRMS (EI): m/z calcd for C14H16 [M+]: 184.1252; found: 184.1277.
(E)-1,4-Diphenylbut-1-en-3-yne (4ca)
Eluent: pentane–CH2Cl2 (9:1).
IR (neat): 3053, 3031, 1487, 1446, 1070, 950, 750, 688 cm–1.
1H NMR (500 MHz, CDCl3): d = 6.39 (d, J = 16.1 Hz, 1 H), 7.04 (d,
J = 16.1 Hz, 1 H), 7.27–7.37 (m, 6 H), 7.42–7.5 (m, 4 H).
13C NMR (125 MHz, CDCl3): d = 88.8 (≡C), 91.7 (≡C), 108.1
(=CH), 123.4 (=C), 126.3 (2 =CH), 128.1 (=CH), 128.3 (2 =CH),
128.6 (=CH), 128.7 (2 =CH), 131.5 (2 =CH), 136.3 (=C), 141.2
(=CH).
EI-MS: m/z (%) = 204 (100, [M+]), 203 (79), 202 (77), 201 (10),
101 (14).
HRMS (EI): m/z calcd for C16H12 [M+]: 204.0939; found: 204.0868.
(E)-1-(Cyclohex-1-enyl)-4-phenylbut-1-en-3-yne (4da)
Eluent: pentane.
(Z)-1-Arylalk-3-en-1-ynes 5, (Z,E)-Alka-1,5-dien-3-ynes 9 and
(Z,Z)-Alka-1,5-dien-3-ynes 11; General Procedure
To a solution of disiamylborane (4 mmol) in THF (12 mL) was add-
ed 1-iodoalk-1-yne (4 mmol) dropwise at – 15 °C under argon, and
the reaction mixture was stirred for 2 h at 0 °C to form a solution of
(Z)-1-iodoalk-1-enyldisiamylborane in THF. The mixture was
cooled to –25 °C, and 1 M LiBEt3H (4 mL, 4 mmol) in THF was
added dropwise, and the mixture was allowed to warm gradually to
r.t. over 1 h. Triethylborane, liberated from LiBEt3H, was removed
under reduced pressure, accompanied by the solvent. After addition
of THF (12 mL) to the residue under argon, the resulting solution of
IR (neat): 3020, 2929, 2858, 1624, 1587, 1488, 1440, 950, 754, 690
cm–1.
1H NMR (500 MHz, CDCl3): d = 1.57–1.72 (m, 4 H), 2.12–2.2 (m,
2 H), 5.69 (d, J = 16.1 Hz, 1 H), 5.87–5.9 (m, 1 H), 6.68 (d, J = 16.1
Hz, 1 H), 7.27–7.32 (m, 3 H), 7.4–7.44 (m, 2 H).
13C NMR (125 MHz, CDCl3): d = 22.2 (2 CH2), 23.8 (CH2), 26.1
(CH2), 89.6 (≡C), 90.4 (≡C), 103.9 (=CH), 123.7 (=C), 127.7
Synthesis 2005, No. 12, 1991–2007 © Thieme Stuttgart · New York

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Stereoselective Synthesis of 1-Arylalk-3-en-1-ynes and Alka-1,5-dien-3-ynes
2001
(=CH), 128.2 (2 =CH), 131.3 (2 =CH), 132.8 (=CH), 135.6 (=C),
145.0 (=CH).
(E)-1-(4-Acetoxyphenyl)oct-3-en-1-yne (4fe)
Eluent: CH2Cl2.
EI-MS: m/z (%) = 208 (100, [M+]), 207 (17), 193 (12), 181 (14),
180 (90), 179 (64), 178 (60), 167 (65), 166 (21), 165 (80), 153 (13),
152 (32), 151 (10), 139 (11), 131 (11), 128 (16), 126 (10), 117 (23),
115 (36), 91 (28), 89 (13), 77 (15).
IR (neat): 2956, 2927, 2871, 2858, 2198, 1685, 1598, 1402, 1357,
1263, 1178, 956, 839 cm–1.
1H NMR (500 MHz, CDCl3): d = 0.91 (t, J = 7.3 Hz, 3 H), 1.31–
1.47 (m 4 H), 2.16–2.22 (m, 2 H), 2.58 (s, 3 H), 5.71 (dt, J = 15.8,
1.5 Hz, 1 H), 6.30 (dt, J = 15.8, 7.3 Hz, 1 H), 7.46–7.5 (m, 2 H),
7.86–7.9 (m, 2 H).
HRMS (EI): m/z calcd for C16H16 [M+]: 208.1252; found: 208.1267.
(E)-1-Phenyl-3-propylhept-3-en-1-yne (4ea)
Eluent: pentane.
13C NMR (125 MHz, CDCl3): d = 13.8 (CH3), 22.1 (CH2), 26.5
(CH3CO), 30.7 (CH2), 33.0 (CH2), 87.1 (≡C), 91.9 (≡C), 109.1
(=CH), 128.2 (2 =CH), 128.6 (=C), 131.4 (2 =CH), 135.8 (=C),
146.6 (=CH), 197.3 (=C).
IR (neat): 3018, 2958, 2929, 2869, 1595, 1488, 1458, 1442, 754,
690 cm–1.
1H NMR (500 MHz, CDCl3): d = 0.94 (t, J = 7.3 Hz, 3 H), 0.95 (t,
J = 7.3 Hz, 3 H), 1.43 (sext J = 7.3 Hz, 2 H), 1.61 (sext, J = 7.3 Hz,
2 H), 2.12 (q J = 7.3 Hz, 2 H), 2.20 (t, J = 7.3 Hz, 2 H), 5.98 (t,
J = 7.3 Hz, 1 H), 7.23–7.32 (m, 3 H), 7.4–7.44 (m, 2 H).
13C NMR (125 MHz, CDCl3): d = 13.7 (CH3), 13.9 (CH3), 21.7
(CH2), 22.5 (CH2), 30.4 (CH2), 32.6 (CH2), 86.5 (≡C), 91.8 (≡C),
123.0 (=C), 123.9 (=C), 127.6 (=CH), 128.2 (2 =CH), 131.4
(2 =CH), 138.5 (=CH).
EI-MS: m/z (%) = 226 (100, [M+]), 211 (33), 184 (10), 183 (64),
170 (38), 156 (10), 155 (82), 152 (10), 141 (13), 140 (24), 139 (32),
127 (11).
HRMS (EI): m/z calcd for C16H18O [M+]: 226.1358; found:
226.1372.
(E)-1-(4-Nitrophenyl)oct-3-en-1-yne (4ff)
Eluent: pentane–CH2Cl2 (8:2).
EI-MS: m/z (%) = 212 (100, [M+]), 184 (14), 183 (77), 170 (10),
169 (28), 168 (11), 167 (14), 165 (18), 156 (10), 155 (46), 154 (25),
153 (30), 152 (31), 143 (10), 142 (55), 141 (79), 139 (18), 129 (21),
128 (29), 127 (17), 126 (11), 115 (66), 91 (38), 77 (18).
IR (neat): 2958, 2929, 2871, 2858, 2200, 1591, 1517, 1490, 1342,
1107, 956, 854, 750, 688 cm–1.
1H NMR (500 MHz, CDCl3): d = 0.92 (t, J = 7.3 Hz, 3 H), 1.32–
1.44 (m, 4 H), 2.17–2.23 (m, 2 H), 5.72 (dt, J = 16.1, 1.5 Hz, 1 H),
6.35 (dt, J = 16.1, 7.3 Hz, 1 H), 7.52–7.56 (m, 2 H), 8.14–8.19 (m,
2 H).
HRMS (EI): m/z calcd for C16H20 [M+]: 212.1565; found: 212.1550.
(E)-1-(4-Methoxyphenyl)oct-3-en-1-yne (4fc)
Eluent: pentane–CH2Cl2 (8:2).
13C NMR (125 MHz, CDCl3): d = 13.8 (CH3), 22.1 (CH2), 30.7
(CH2), 33.0 (CH2), 86.2 (≡C), 94.0 (≡C), 108.8 (=CH), 123.5
(2 =CH), 130.7 (=C), 132.0 (2 =CH), 146.6 (=C), 147.8 (=CH).
EI-MS: m/z (%) = 229 (52, [M+]), 186 (26), 174 (11), 173 (100),
154 (10), 143 (10), 140 (20), 139 (33), 127 (10), 115 (10).
HRMS (EI): m/z calcd for C14H15NO2 [M+]: 229.1103; found:
229.1096.
IR (neat): 3001, 2956, 2927, 2869, 2856, 2837, 1604, 1508, 1463,
1440, 1288, 1247, 1172, 1105, 1035, 954, 831 cm–1.
1H NMR (500 MHz, CDCl3): d = 0.90 (t, J = 7.3 Hz, 3 H), 1.3–1.44
(m, 4 H), 2.12–2.18 (m, 2 H), 3.78 (s, 3 H), 5.67 (dt, J = 15.8, 1.5
Hz, 1 H), 6.19 (dt, J = 15.8, 7.3 Hz, 1 H), 6.8–6.85 (m, 2 H), 7.33–
7.38 (m, 2 H).
13C NMR (125 MHz, CDCl3): d = 13.8 (CH3), 22.1 (CH2), 30.9
(CH2), 32.8 (CH2), 55.2 (OCH3), 86.9 (≡C), 87.7 (≡C), 109.6
(=CH), 113.9 (2 =CH), 115.7 (=C), 132.8 (2 =CH), 144.4 (=CH),
159.3 (=C).
EI-MS: m/z (%) = 214 (73, [M+]), 185 (43), 172 (16), 171 (100),
158 (24), 141 (11), 128 (38), 121 (12), 115 (17).
(E)-1-(4-Bromophenyl)oct-3-en-1-yne (4fg)
Eluent: pentane.
IR (neat): 2956, 2927, 2869, 2860, 1485, 1465, 1070, 1010, 956,
823 cm–1.
1H NMR (500 MHz, CDCl3): d = 0.92 (t, J = 7.0 Hz, 3 H), 1.3–1.45
(m, 4 H), 2.15–2.21 (m, 2 H), 5.66 (d, J = 15.8 Hz, 1 H), 6.25 (dt,
J = 15.8, 7.0 Hz, 1 H), 7.25–7.3 (m, 2 H), 7.4–7.45 (m, 2 H).
HRMS (EI): m/z calcd for C15H18O [M+]: 214.1358; found:
214.1357.
13C NMR (125 MHz, CDCl3): d = 13.8 (CH3), 22.1 (CH2), 30.8
(CH2), 32.9 (CH2), 86.7 (≡C), 89.5 (≡C), 109.2 (=CH), 121.9 (=C),
122.6 (=C), 131.5 (2 =CH), 132.8 (2 = CH), 145.8 (=CH).
EI-MS: m/z (%) = 264 (72, [M+]), 262 (75, [M+]), 222 (10), 221
(64), 220 (11), 219 (67), 208 (85), 207 (10), 206 (85), 195 (14), 193
(14), 168 (15), 155 (22), 154 (86), 153 (34), 152 (28), 141 (35), 140
(100), 139 (94), 128 (11), 127 (38), 126 (15), 115 (16), 114 (27),
113 (23), 87 (12), 75 (14), 63 (18).
HRMS (EI): m/z calcd for C14H1581Br [M+]: 264.0338; found:
264.0368.
HRMS (EI): m/z calcd for C14H1579Br [M+]: 262.0357; found:
262.0394.
(E)-1-(4-Aminophenyl)oct-3-en-1-yne (4fd)
Eluent: pentane–Et2O (7:3).
IR (neat): 3471, 3381, 3030, 2956, 2925, 2869, 2856, 2192, 1618,
1604, 1512, 1290, 1176, 954, 827 cm–1.
1H NMR (500 MHz, CDCl3): d = 0.90 (t, J = 7.1 Hz, 3 H), 1.3–1.42
(m, 4 H), 2.1–2.18 (m, 2 H), 3.75 (br s, 2 H), 5.67 (dt, J = 15.8, 1.5
Hz, 1 H), 6.15 (dt, J = 15.8, 7.1 Hz, 1 H), 6.61–6.65 (m, 2 H), 7.2–
7.24 (m, 2 H).
13C NMR (125 MHz, CDCl3): d = 13.8 (CH3), 22.1 (CH2), 30.9
(CH2), 32.8 (CH2), 86.2 (≡C), 88.4 (≡C), 109.7 (=CH), 113.0 (=C),
114.7 (2 =CH), 132.7 (2 =CH), 143.7 (=CH), 146.3 (=C).
EI-MS: m/z (%) = 199 (92, [M+]), 170 (58), 157 (17), 156 (100),
154 (16), 143 (14), 142 (10), 141 (14), 130 (22), 128 (18), 117 (12),
106 (12).
(E)-1-(4-Chlorophenyl)oct-3-en-1-yne (4fh)
Eluent: pentane.
IR (neat): 2956, 2927, 2871, 2860, 1488, 1465, 1091, 1014, 956,
827 cm–1.
HRMS (EI): m/z calcd for C14H17N [M+]: 199.1361; found:
199.1376.
Synthesis 2005, No. 12, 1991–2007 © Thieme Stuttgart · New York

2002
M. Hoshi et al.
PAPER
1H NMR (500 MHz, CDCl3): d = 0.90 (t, J = 7.0 Hz, 3 H), 1.3–1.5
(m, 4 H), 2.1–2.2 (m, 2 H), 5.67 (d, J = 15.8 Hz, 1 H), 6.24 (dt,
J = 15.8, 7.0 Hz, 1 H), 7.24–7.28 (m, 2 H), 7.31–7.35 (m, 2 H).
EI-MS: m/z (%) = 198 (100, [M+]), 169 (37), 156 (12), 155 (86),
154 (41), 153 (50), 152 (30), 143 (12), 142 (77), 141 (66), 139 (12),
129 (38), 128 (55), 127 (30), 116 (13), 115 (57), 91 (10), 77 (18).
13C NMR (125 MHz, CDCl3): d = 13.8 (CH3), 22.1 (CH2), 30.8
(CH2), 32.9 (CH2), 86.7 (≡C), 89.3 (≡C), 109.2 (=CH), 122.1 (=C),
128.5 (2 =CH), 132.5 (2 =CH), 133.7 (=C), 145.7 (=CH).
HRMS (EI): m/z calcd for C15H18 [M+]: 198.1409; found: 198.1364.
(E)-1-(1-Naphthyl)oct-3-en-1-yne (4fl)
Eluent: pentane–CH2Cl2 (9:1).
IR (neat): 3057, 2956, 2927, 2869, 2856, 1396, 954, 798, 773 cm–1.
EI-MS: m/z (%) = 220 (22, [M+]), 218 (69, [M+]), 189 (18), 177
(29), 176 (13), 175 (86), 164 (33), 163 (12), 162 (100), 154 (22),
153 (27), 152 (19), 151 (16), 149 (37), 141 (18), 140 (29), 139 (48),
127 (19), 125 (15), 114 (10), 113 (13), 63 (10).
HRMS (EI): m/z calcd for C14H1537Cl [M+]: 220.0836; found:
220.0808.
1H NMR (500 MHz, CDCl3): d = 0.93 (t, J = 7.0 Hz, 3 H), 1.35–
1.49 (m, 4 H), 2.18–2.23 (m, 2 H), 5.84 (dt, J = 15.8, 1.5 Hz, 1 H),
6.36 (dt, J = 15.8, 7.0 Hz, 1 H), 7.38–7.42 (m, 1 H), 7.48–7.57 (m,
2 H), 7.63–7.65 (m, 1 H), 7.76–7.79 (m, 1 H), 7.81–7.84 (m, 1 H),
8.32–8.35 (m, 1 H).
13C NMR (125 MHz, CDCl3): d = 13.9 (CH3), 22.2 (CH2), 30.9
(CH2), 32.9 (CH2), 85.9 (≡C), 93.3 (≡C), 109.6 (=CH), 121.3
(=CH), 125.2 (=C), 126.2 (=CH), 126.3 (=C), 126.5 (=CH), 128.2
(=CH), 128.3 (=CH), 130.0 (=CH), 133.1 (=CH), 133.2 (=C), 145.4
(=CH).
HRMS (EI): m/z calcd for C14H1535Cl [M+]: 218.0862; found:
218.0893.
(E)-1-(2-Thienyl)oct-3-en-1-yne (4fi)
Eluent: pentane.
IR (neat): 3018, 2956, 2927, 2869, 2858, 1197, 954, 848, 827, 698
cm–1.
1H NMR (500 MHz, CDCl3): d = 0.90 (t, J = 7.3 Hz, 3 H), 1.3–1.44
(m, 4 H), 2.13–2.19 (m, 2 H), 5.68 (dt, J = 15.8, 1.5 Hz, 1 H), 6.23
(dt, J = 15.8, 7.3 Hz, 1 H), 6.95 (dd, J = 5.1, 3.6 Hz, 1 H), 7.15 (dd,
J = 3.6, 1.2 Hz, 1 H), 7.21 (dd, J = 5.1, 1.2 Hz, 1 H).
EI-MS: m/z (%) = 234 (100, [M+]), 205 (42), 203 (18), 202 (17),
192 (16), 191 (84), 190 (64), 189 (79), 179 (13), 178 (54), 176 (14),
165 (28), 164 (11), 163 (17), 152 (24).
HRMS (EI): m/z calcd for C18H18 [M+]: 234.1409; found: 234.1410.
(E)-1-(2-Isopropylphenyl)oct-3-en-1-yne (4fm)
Eluent: pentane.
IR (neat): 3022, 2958, 2927, 2869, 1483, 1463, 1444, 954, 756 cm–1.
13C NMR (125 MHz, CDCl3): d = 13.8 (CH3), 22.1 (CH2), 30.8
(CH2), 32.9 (CH2), 80.9 (≡C), 92.1 (≡C), 109.2 (=CH), 123.7 (=C),
126.7 (=CH), 126.9 (=CH), 131.3 (=CH), 145.4 (=CH).
EI-MS: m/z (%) = 190 (69, [M+]), 161 (37), 148 (13), 147 (100),
134 (51), 128 (13), 121 (19), 115 (13), 103 (12), 77 (10).
HRMS (EI): m/z calcd for C12H14S [M+]: 190.0816; found:
190.0818.
1H NMR (500 MHz, CDCl3): d = 0.92 (t, J = 7.3 Hz, 3 H), 1.25 (d,
J = 6.8 Hz, 6 H), 1.32–1.46 (m, 4 H), 2.14–2.2 (m, 2 H), 3.44 (hept,
J = 6.8 Hz, 1 H), 5.73 (dt, J = 15.6, 1.4 Hz, 1 H), 6.22 (dt, J = 15.6,
7.3 Hz, 1 H), 7.09–7.13 (m, 1 H), 7.24–7.26 (m, 2 H), 7.38–7.41 (m,
1 H).
(E)-1-(3-Pyridyl)oct-3-en-1-yne (4fj)
Eluent: pentane–Et2O (7:3).
13C NMR (125 MHz, CDCl3): d = 13.9 (CH3), 22.2 (CH2), 23.1
[CH(CH3)2], 30.9 (CH2), 31.5 (CH2), 32.9 [CH(CH3)2], 86.5 (≡C),
91.9 (≡C), 109.7 (=CH), 122.3 (=C), 124.8 (=CH), 125.4 (=CH),
128.2 (=CH), 132.1 (=CH), 144.6 (=CH), 150.2 (=C).
EI-MS: m/z (%) = 226 (100, [M+]), 184 (13), 183 (82), 170 (10),
169 (27), 168 (30), 167 (24), 166 (10), 165 (25), 156 (22), 155 (80),
154 (14), 153 (34), 152 (25), 144 (12), 143 (48), 142 (24), 141 (58),
129 (39), 128 (30), 127 (10), 115 (28), 91 (11), 55 (17), 42 (14).
IR (neat): 3026, 2956, 2927, 2871, 2858, 1475, 1406, 956, 804, 704
cm–1.
1H NMR (500 MHz, CDCl3): d = 0.91 (t, J = 7.3 Hz, 3 H), 1.32–
1.46 (m, 4 H), 2.16–2.21 (m, 2 H), 5.69 (dt, J = 15.8, 1.5 Hz, 1 H),
6.30 (dt, J = 15.8, 7.3 Hz, 1 H), 7.23 (ddd, J = 7.9, 4.9, 0.9 Hz, 1 H),
7.69 (dt, J = 7.9, 1.8 Hz, 1 H), 8.49 (dd, J = 4.9, 1.5 Hz, 1 H), 8.65
(d, J = 1.5 Hz, 1 H).
HRMS (EI): m/z calcd for C17H22 [M+]: 226.1722; found: 226.1699.
13C NMR (125 MHz, CDCl3): d = 13.8 (CH3), 22.1 (CH2), 30.7
(CH2), 32.9 (CH2), 84.3 (≡C), 91.7 (≡C), 108.9 (=CH), 120.9 (=C),
123.0 (=CH), 138.2 (=CH), 146.5 (=CH), 148.0 (=CH), 151.9
(=CH).
(Z)-1-Phenyldec-3-en-1-yne (5aa)
Eluent: pentane.
IR (neat): 3020, 2956, 2927, 2856, 1488, 754, 690 cm–1.
EI-MS: m/z (%) = 185 (74, [M+]), 156 (25), 143 (13), 142 (64), 141
(22), 130 (14), 129 (100), 128 (12), 116 (15), 115 (18).
HRMS (EI): m/z calcd for C13H15N [M+]: 185.1204; found:
185.1190.
1H NMR (500 MHz, CDCl3): d = 0.88 (t, J = 7.0 Hz, 3 H), 1.25–
1.45 (m, 8 H), 2.35–2.45 (m, 2 H), 5.68 (dt, J = 10.7, 1.5 Hz, 1 H),
5.96 (dt, J = 10.7, 7.0 Hz, 1 H), 7.25–7.3 (m, 3 H), 7.4–7.45 (m, 2
H).
13C NMR (125 MHz, CDCl3): d = 14.0 (CH3), 22.6 (CH2), 28.8 (2
CH2), 30.4 (CH2), 31.7 (CH2), 86.5 (≡C), 93.4 (≡C), 109.0 (=CH),
123.8 (=C), 127.9 (=CH), 128.2 (2 =CH), 131.4 (2 =CH), 144.3
(=CH).
EI-MS: m/z (%) = 212 (48, [M+]), 155 (32), 142 (15), 141 (59), 129
(16), 128 (100), 115 (40), 91 (13).
HRMS (EI): m/z calcd for C16H20 [M+]: 212.1565; found: 212.1559.
(E)-1-(2-Methylphenyl)oct-3-en-1-yne (4fk)
Eluent: pentane.
IR (neat): 3020, 2956, 2927, 2871, 2858, 1483, 1456, 954, 756 cm–1.
1H NMR (500 MHz, CDCl3): d = 0.91 (t, J = 7.0 Hz, 3 H), 1.32–
1.45 (m, 4 H), 2.15–2.2 (m, 2 H), 2.42 (s, 3 H), 5.73 (dt, J = 15.8,
1.5 Hz, 1 H), 6.23 (dt, J = 15.8, 7.0 Hz, 1 H), 7.08–7.13 (m, 1 H),
7.15–7.18 (m, 2 H), 7.37–7.39 (m, 1 H).
(Z)-1,4-Diphenylbut-1-en-3-yne (5ca)
Eluent: pentane–CH2Cl2 (9:1).
IR (neat): 3060, 3020, 1488, 1446, 783, 754, 688 cm–1.
13C NMR (125 MHz, CDCl3): d = 13.9 (CH3), 20.6 (ArCH3), 22.2
(CH2), 30.9 (CH2), 32.9 (CH2), 86.7 (≡C), 92.2 (≡C), 109.6 (=CH),
123.4 (=C), 125.4 (=CH), 127.8 (=CH), 129.3 (=CH), 131.7 (=CH),
139.9 (=C), 144.8 (=CH).
Synthesis 2005, No. 12, 1991–2007 © Thieme Stuttgart · New York

PAPER
Stereoselective Synthesis of 1-Arylalk-3-en-1-ynes and Alka-1,5-dien-3-ynes
2003
1H NMR (500 MHz, CDCl3): d = 5.91 (d, J = 11.9 Hz, 1 H), 6.69 (d,
J = 11.9 Hz, 1 H), 7.27–7.4 (m, 8 H), 7.47–7.52 (m, 1 H), 7.9–7.95
(m, 1 H).
HRMS (EI): m/z calcd for C14H17N [M+]: 199.1361; found:
199.1389.
(Z)-1-(4-Acetoxyphenyl)oct-3-en-1-yne (5fe)
Eluent: CH2Cl2.
13C NMR (125 MHz, CDCl3): d = 88.2 (≡C), 95.8 (≡C), 107.3
(=CH), 123.4 (=C), 128.2 (2 =CH), 128.3 (=CH), 128.4 (2 =CH),
128.5 (=CH), 128.7 (2 =CH), 131.4 (2 =CH), 136.5 (=C), 138.6
(=CH).
IR (neat): 3020, 2958, 2929, 2871, 2858, 2194, 1685, 1596, 1404,
1357, 1263, 839 cm–1.
EI-MS: m/z (%) = 204 (100, [M+]), 203 (84), 202 (79), 201 (11),
200 (10), 101 (16).
HRMS (EI): m/z calcd for C16H12 [M+]: 204.0939; found: 204.0941.
1H NMR (500 MHz, CDCl3): d = 0.94 (t, J = 7.3 Hz, 3 H), 1.36–
1.49 (m, 4 H), 2.38–2.43 (m, 2 H), 5.69 (dt, J = 10.6, 1.5 Hz, 1 H),
6.04 (dt, J = 10.6, 7.3 Hz, 1 H), 7.48–7.51 (m, 2 H), 7.88–7.91 (m,
2 H).
(Z)-1-(2-Methylphenyl)oct-3-en-1-yne (5fb)
Eluent: pentane.
13C NMR (125 MHz, CDCl3): d = 13.9 (CH3), 22.2 (CH2), 26.6
(CH3CO), 30.2 (CH2), 30.9 (CH2), 89.9 (≡C), 92.6 (≡C), 108.6
(=CH), 128.2 (2 =CH), 128.6 (=C), 131.4 (2 =CH), 135.9 (=C),
145.7 (=CH), 197.2 (=C).
EI-MS: m/z (%) = 226 (100, [M+]), 211 (31), 183 (49), 170 (44),
169 (11), 156 (11), 155 (91), 153 (13), 152 (13), 141 (16), 140 (24),
139 (35), 127 (11), 115 (12).
IR (neat): 3026, 2956, 2927, 2869, 2860, 2187, 1508, 1465, 1458,
815 cm–1.
1H NMR (500 MHz, CDCl3): d = 0.92 (t, J = 7.3 Hz, 3 H), 1.34–1.5
(m, 4 H), 2.33 (s, 3 H), 2.37–2.42 (m, 2 H), 5.66 (d, J = 10.6 Hz, 1
H), 5.94 (dt, J = 10.6, 7.3 Hz, 1 H), 7.11 (d, J = 8.2 Hz, 2 H), 7.32
(d, J = 8.2 Hz, 2 H).
HRMS (EI): m/z calcd for C16H18O [M+]: 226.1358; found:
226.1386.
13C NMR (125 MHz, CDCl3): d = 13.9 (CH3), 21.4 (ArCH3), 22.2
(CH2), 30.0 (CH2), 31.0 (CH2), 85.8 (≡C), 93.5 (≡C), 109.0 (=CH),
120.6 (=C), 129.0 (=CH), 131.2 (=CH), 138.0 (=C), 143.9 (=CH).
EI-MS: m/z (%) = 198 (79, [M+]), 170 (11), 169 (55), 156 (19), 155
(100), 154 (33), 153 (31), 152 (23), 143 (11), 142 (67), 141 (35),
139 (18), 129 (28), 128 (33), 127 (19), 116 (10), 115 (32), 105 (14),
91 (10), 77 (12).
(Z)-1-(4-Nitrophenyl)oct-3-en-1-yne (5ff)
Eluent: pentane–CH2Cl2 (8:2).
IR (neat): 2958, 2929, 2869, 2858, 2194, 1589, 1517, 1340, 1107,
852, 748 cm–1.
1H NMR (500 MHz, CDCl3): d = 0.94 (t, J = 7.3 Hz, 3 H), 1.35–1.5
(m, 4 H), 2.39–2.44 (m, 2 H), 5.70 (dt, J = 10.7, 1.5 Hz, 1 H), 6.10
(dt, J = 10.7, 7.3 Hz, 1 H), 7.53–7.57 (m, 2 H), 8.16–8.20 (m, 2 H).
HRMS (EI): m/z calcd for C15H18 [M+]: 198.1409; found: 198.1452.
(Z)-1-(4-Methoxyphenyl)oct-3-en-1-yne (5fc)
Eluent: pentane–CH2Cl2 (8:2).
13C NMR (125 MHz, CDCl3): d = 13.9 (CH3), 22.2 (CH2), 30.3
(CH2), 30.8 (CH2), 91.6 (≡C), 91.9 (≡C), 108.3 (=CH), 123.6
(2 =CH), 130.7 (=C), 132.0 (2 =CH), 146.7 (=C), 146.8 (=CH).
IR (neat): 3018, 2956, 2929, 2871, 2858, 2837, 1602, 1508, 1463,
1440, 1290, 1247, 1172, 1035, 831 cm–1.
EI-MS: m/z (%) = 229 (49, [M+]), 186 (17), 174 (11), 173 (100),
154 (13), 153 (12), 143 (12), 140 (17), 139 (28), 127 (13), 115 (12).
HRMS (EI): m/z calcd for C14H15NO2 [M+]: 229.1103; found:
229.1084.
1H NMR (500 MHz, CDCl3): d = 0.93 (t, J = 7.3 Hz, 3 H), 1.34–
1.47 (m, 4 H), 2.37–2.42 (m, 2 H), 3.79 (s, 3 H), 5.65 (d, J = 10.6
Hz, 1 H), 5.92 (dt, J = 10.6, 7.3 Hz, 1 H), 6.81–6.86 (m, 2 H), 7.35–
7.40 (m, 2 H).
(Z)-1-(4-Bromophenyl)oct-3-en-1-yne (5fg)
Eluent: pentane.
13C NMR (125 MHz, CDCl3): d = 13.9 (CH3), 22.2 (CH2), 30.0
(CH2), 31.0 (CH2), 55.2 (OCH3), 85.1 (≡C), 93.3 (≡C), 109.1
(=CH), 113.9 (2 =CH), 115.8 (=C), 132.7 (2 =CH), 143.5 (=CH),
159.3 (=C).
IR (neat): 3020, 2956, 2927, 2869, 2858, 1485, 1465, 1394, 1070,
1010, 823 cm–1.
EI-MS: m/z (%) = 214 (84, [M+]), 186 (11), 185 (64), 172 (20), 171
(100), 170 (16), 158 (28), 153 (12), 145 (10), 141 (14), 128 (44),
127 (12), 121 (18), 115 (22), 102 (12).
HRMS (EI): m/z calcd for C15H18O [M+]: 214.1358; found:
214.1359.
1H NMR (500 MHz, CDCl3): d = 0.92 (t, J = 7.3 Hz, 3 H), 1.35–
1.47 (m, 4 H), 2.35–2.41 (m, 2 H), 5.64 (dt, J = 10.6, 1.5 Hz, 1 H),
5.99 (dt, J = 10.6, 7.3 Hz, 1 H), 7.26–7.31 (m, 2 H), 7.41–7.46 (m,
2 H).
13C NMR (125 MHz, CDCl3): d = 13.9 (CH3), 22.2 (CH2), 30.1
(CH2), 30.9 (CH2), 87.6 (≡C), 92.2 (≡C), 108.7 (=CH), 122.1 (=C),
122.6 (=C), 131.5 (2 =CH), 132.7 (2 =CH), 144.9 (=CH).
(Z)-1-(Aminophenyl)oct-3-en-1-yne (5fd)
Eluent: pentane–Et2O (7:3).
EI-MS: m/z (%) = 264 (51, [M+]), 262 (53, [M+]), 221 (38), 219
(39), 208 (64), 206 (67), 195 (10), 193 (11), 168 (15), 155 (22), 154
(100), 153 (34), 152 (24), 141 (32), 140 (70), 139 (74), 128 (11),
127 (34), 126 (13), 115 (15), 114 (21), 113 (18), 87 (10), 77 (10), 75
(12), 63 (16).
HRMS (EI): m/z calcd for C14H1581Br [M+]: 264.0338; found:
264.0259.
IR (neat): 3473, 3382, 3016, 2956, 2927, 2869, 2856, 2185, 1622,
1602, 1512, 1292, 1176, 827 cm–1.
1H NMR (500 MHz, CDCl3): d = 0.93 (t, J = 7.3 Hz, 3 H), 1.35–
1.48 (m, 4 H), 2.36–2.41 (m, 2 H), 3.77 (br s, 2 H), 5.65 (d, J = 10.7
Hz, 1 H), 5.88 (dt, J = 10.7, 7.3 Hz, 1 H), 6.57–6.61 (m, 2 H), 7.22–
7.26 (m, 2 H).
13C NMR (125 MHz, CDCl3): d = 13.9 (CH3), 22.2 (CH2), 29.9
(CH2), 31.0 (CH2), 84.4 (≡C), 94.0 (≡C), 109.2 (=CH), 113.1 (=C),
114.7 (2 =CH), 132.6 (2 =CH), 142.8 (=CH), 146.3 (=C).
HRMS (EI): m/z calcd for C14H1579Br [M+]: 262.0357; found:
262.0344.
(Z)-1-(2-Thienyl)oct-3-en-1-yne (5fi)
Eluent: pentane.
EI-MS: m/z (%) = 199 (73, [M+]), 171 (11), 170 (76), 157 (23), 156
(100), 154 (13), 143 (20), 141 (12), 130 (20), 128 (19), 117 (13),
115 (13), 106 (14).
IR (neat): 3018, 2956, 2927, 2869, 2858, 1186, 848, 827, 731, 698
cm–1.
Synthesis 2005, No. 12, 1991–2007 © Thieme Stuttgart · New York

2004
M. Hoshi et al.
PAPER
1H NMR (500 MHz, CDCl3): d = 0.93 (t, J = 7.3 Hz, 3 H), 1.33–
1.47 (m, 4 H), 2.35–2.4 (m, 2 H), 5.66 (dt, J = 10.7, 1.2 Hz, 1 H),
5.97 (dt, J = 10.7, 7.3 Hz, 1 H), 6.96 (dd, J = 5.1, 3.6 Hz, 1 H), 7.17
(dd, J = 3.6, 0.9 Hz, 1 H), 7.23 (dd, J = 5.1, 1.2 Hz, 1 H).
13C NMR (125 MHz, CDCl3): d = 13.9 (CH3), 22.2 (CH2), 30.1
(CH2), 30.9 (CH2), 86.3 (≡C), 90.3 (≡C), 108.7 (=CH), 123.7 (=C),
126.8 (=CH), 127.0 (=CH), 131.2 (=CH), 144.5 (=CH).
EI-MS: m/z (%) = 234 (100, [M+]), 206 (11), 205 (57), 203 (20),
202 (18), 192 (16), 191 (80), 190 (64), 189 (78), 179 (15), 178 (54),
176 (16), 165 (34), 164 (10), 163 (18), 152 (29).
HRMS (EI): m/z calcd for C18H18 [M+]: 234.1409; found: 234.1422.
(Z)-1-(2-Isopropylphenyl)oct-3-en-1-yne (5fm)
Eluent: pentane.
EI-MS: m/z (%) = 190 (78, [M+]), 162 (11), 161 (60), 148 (16), 147
(100), 135 (10), 134 (62), 128 (22), 121 (21), 115 (19), 103 (14), 97
(13), 77 (13).
HRMS (EI): m/z calcd for C12H14S [M+]: 190.0816; found:
190.0813.
IR (neat): 3022, 2958, 2927, 2869, 1483, 1463, 1444, 756, 732 cm–1.
1H NMR (500 MHz, CDCl3): d = 0.93 (t, J = 7.3 Hz, 3 H), 1.27 (d,
J = 6.8 Hz, 6 H), 1.34–1.48 (m, 4 H), 2.38–2.45 (m, 2 H), 3.49 (hept,
J = 6.8 Hz, 1 H), 5.71 (d, J = 10.7 Hz, 1 H), 5.97 (dt, J = 10.7, 7.3
Hz, 1 H), 7.1–7.15 (m, 1 H), 7.25–7.28 (m, 2 H), 7.4–7.43 (m, 1 H).
13C NMR (125 MHz, CDCl3): d = 13.9 (CH3), 22.4 (CH2), 23.1
[CH(CH3)2], 30.2 (CH2), 31.1 (CH2), 31.5 [CH(CH3)2], 90.1 (≡C),
92.1 (≡C), 109.3 (=CH), 122.4 (=C), 124.8 (=CH), 125.5 (=CH),
128.3 (=CH), 132.2 (=CH), 143.8 (=CH), 150.0 (=C).
EI-MS: m/z (%) = 226 (100, [M+]), 184 (11), 183 (77), 170 (10),
169 (28), 168 (25), 167 (22), 166 (10), 165 (26), 156 (25), 155 (83),
154 (14), 153 (31), 152 (26), 144 (14), 143 (50), 142 (24), 141 (53),
129 (43), 128 (34), 127 (11), 115 (31), 91 (15), 55 (16), 42 (15).
(Z)-1-(3-Pyridyl)oct-3-en-1-yne (5fj)
Eluent: pentane–Et2O (7:3).
IR (neat): 3024, 2956, 2927, 2871, 2858, 1475, 1407, 1022, 802,
732, 704 cm–1.
1H NMR (500 MHz, CDCl3): d = 0.93 (t, J = 7.0 Hz, 3 H), 1.35–
1.48 (m, 4 H), 2.38–2.43 (m, 2 H), 5.68 (dt, J = 10.7, 1.5 Hz, 1 H),
6.04 (dt, J = 10.7, 7.6 Hz, 1 H), 7.24 (ddd, J = 7.9, 4.9, 0.6 Hz, 1 H),
7.71 (dt, J = 7.9, 1.8 Hz, 1 H), 8.50 (dd, J = 4.9, 1.5 Hz, 1 H), 8.67
(d, J = 1.2 Hz, 1 H).
HRMS (EI): m/z calcd for C17H22 [M+]: 226.1722; found: 226.1698.
13C NMR (125 MHz, CDCl3): d = 13.9 (CH3), 22.2 (CH2), 30.2
(CH2), 30.9 (CH2), 89.7 (≡C), 89.8 (≡C), 108.4 (=CH), 120.8 (=C),
122.9 (=CH), 138.2 (=CH), 145.6 (=CH), 148.2 (=CH), 150.2
(=CH).
EI-MS: m/z (%) = 185 (58, [M+]), 156 (30), 143 (10), 142 (40), 141
(17), 130 (13), 129 (100), 128 (11), 116 (12), 115 (13).
(5E,9E)-Tetradeca-5,9-dien-7-yne (8fa)
Eluent: pentane.
IR (neat): 3020, 2956, 2927, 2871, 2860, 1465, 954 cm–1.
1H NMR (500 MHz, CDCl3): d = 0.88 (t, J = 7.3 Hz, 6 H), 1.25–1.4
(m, 8 H), 2.05–2.15 (m, 4 H), 5.56 (d, J = 15.3 Hz, 2 H), 6.10 (dt,
J = 15.3, 7.3 Hz, 2 H).
13C NMR (125 MHz, CDCl3): d = 13.8 (2 CH3), 22.1 (2 CH2), 30.8
(2 CH2), 32.8 (2 CH2), 86.7 (2 ≡C), 109.6 (2 =CH), 144.3 (2 =CH).
HRMS (EI): m/z calcd for C13H15N [M+]: 185.1204; found:
185.1202.
EI-MS: m/z (%) = 190 (76, [M+]), 147 (26), 134 (19), 119 (21), 105
(50), 103 (11), 93 (10), 92 (13), 91 (100), 79 (25), 78 (67), 77 (17),
67 (12), 65 (14).
(Z)-1-(2-Methylphenyl)oct-3-en-1-yne (5fk)
Eluent: pentane.
IR (neat): 3020, 2956, 2927, 2871, 2858, 1485, 1456, 756, 715 cm–1.
HRMS (EI): m/z calcd for C14H22 [M+]: 190.1722; found: 190.1680.
1H NMR (500 MHz, CDCl3): d = 0.92 (t, J = 7.3 Hz, 3 H), 1.36–
1.49 (m, 4 H), 2.39–2.46 (m, 2 H), 2.45 (s, 3 H), 5.72 (dt, J = 10.7,
1.5 Hz, 1 H), 5.97 (dt, J = 10.7, 7.3 Hz, 1 H), 7.11–7.17 (m, 1 H),
7.18–7.21 (m, 2 H), 7.39–7.42 (m, 1 H).
13C NMR (125 MHz, CDCl3): d = 13.9 (CH3), 20.8 (ArCH3), 22.3
(CH2), 30.1 (CH2), 31.0 (CH2), 90.4 (≡C), 92.3 (≡C), 109.2 (=CH),
123.5 (=C), 125.5 (=CH), 127.9 (=CH), 129.3 (=CH), 131.7 (=CH),
139.8 (=C), 143.9 (=CH).
EI-MS: m/z (%) = 198 (100, [M+]), 169 (47), 156 (12), 155 (68),
154 (41), 153 (43), 152 (28), 143 (13), 142 (69), 141 (66), 139 (12),
129 (34), 128 (51), 127 (24), 116 (12), 115 (53), 105 (10), 91 (10),
77 (16).
(3E,7E)-2,2-Dimethyldodeca-3,7-dien-5-yne (8ba)
Eluent: pentane.
IR (neat): 3024, 2960, 2929, 2869, 1475, 1463, 1363, 1265, 956
cm–1.
1H NMR (500 MHz, CDCl3): d = 0.89 (t, J = 7.3 Hz, 3 H), 1.02 (s,
9 H), 1.28–1.41 (m, 4 H), 2.08–2.13 (m, 2 H), 5.51 (dd, J = 16.1, 2.1
Hz, 1 H), 5.55–5.6 (m, 1 H), 6.10 (dt, J = 15.8, 7.3 Hz, 1 H), 6.15
(d, J = 16.1 Hz, 1 H).
13C NMR (125 MHz, CDCl3): d = 13.8 (CH3), 22.1 (CH2), 29.0 (3
CH3), 30.9 (CH2), 32.8 (CH2), 33.9 (C), 86.9 (≡C), 87.2 (≡C), 105.1
(=CH), 109.6 (=CH), 144.2 (=CH), 154.4 (=CH).
EI-MS: m/z (%) = 190 (77, [M+]), 175 (16), 147 (46), 133 (22), 119
(64), 117 (19), 115 (14), 107 (11), 106 (10), 105 (100), 93 (13), 91
(52), 79 (13), 77 (16), 55 (13).
HRMS (EI): m/z calcd for C15H18 [M+]: 198.1409; found: 198.1429.
(Z)-1-(1-Naphthyl)oct-3-en-1-yne (5fl)
Eluent: pentane–CH2Cl2 (9:1).
IR (neat): 2956, 2927, 2869, 2858, 1404, 798, 773, 732 cm–1.
HRMS (EI): m/z calcd for C14H22 [M+]: 190.1722; found: 190.1727.
1H NMR (500 MHz, CDCl3): d = 0.95 (t, J = 7.3 Hz, 3 H), 1.4–1.54
(m, 4 H), 2.49–2.55 (m, 2 H), 5.82 (dt, J = 10.7, 1.5 Hz, 1 H), 6.04
(dt, J = 10.7, 7.3 Hz, 1 H), 7.41–7.44 (m, 1 H), 7.48–7.58 (m, 2 H),
7.65–7.68 (m, 1 H), 7.78–7.81 (m, 1 H), 7.82–7.85 (m, 1 H), 8.34–
8.38 (m, 1 H).
13C NMR (125 MHz, CDCl3): d = 13.9 (CH3), 22.3 (CH2), 30.3
(CH2), 31.0 (CH2), 91.4 (≡C), 91.5 (≡C), 109.2 (=CH), 121.4
(=CH), 125.2 (=C), 126.2 (=CH), 126.3 (=C), 126.6 (=CH), 128.2
(=CH), 128.4 (=CH), 130.1 (=CH), 133.1 (=C), 133.1 (=CH), 144.4
(=CH).
(1E,5E)-1-(Cyclohex-1-enyl)deca-1,5-dien-3-yne (8da)
Eluent: pentane.
IR (neat): 3024, 2954, 2927, 2858, 2837, 1624, 1448, 1434, 1201,
950, 790 cm–1.
1H NMR (500 MHz, CDCl3): d = 0.89 (t, J = 7.3 Hz, 3 H), 1.28–
1.42 (m, 4 H), 1.55–1.7 (m, 4 H), 2.07–2.18 (m, 6 H), 5.5–5.63 (m,
1 H), 5.82 (s, 1 H), 6.11 (dt, J = 15.6, 7.3 Hz, 1 H), 6.55 (d, J = 15.6
Hz, 1 H).
Synthesis 2005, No. 12, 1991–2007 © Thieme Stuttgart · New York

PAPER
Stereoselective Synthesis of 1-Arylalk-3-en-1-ynes and Alka-1,5-dien-3-ynes
2005
13C NMR (125 MHz, CDCl3): d = 13.8 (CH3), 22.1 (CH2), 22.2
(CH2), 22.3 (CH2), 23.8 (CH2), 26.1 (CH2), 30.9 (CH2), 32.8 (CH2),
88.0 (≡C), 89.5 (≡C), 104.2 (=CH), 109.8 (=CH), 132.2 (=C), 135.6
(=C), 144.2 (=CH), 144.3 (=CH).
EI-MS: m/z (%) = 214 (72, [M+]), 185 (18), 171 (20), 157 (16), 144
(13), 143 (38), 142 (15), 141 (21), 131 (20), 129 (100), 128 (48),
127 (13), 117 (38), 116 (13), 115 (48), 105 (15), 95 (35), 92 (10), 91
(55), 79 (16), 77 (19), 67 (14), 65 (13).
IR (neat): 3026, 2954, 2923, 2854, 1456, 950, 746, 690 cm–1.
1H NMR (500 MHz, CDCl3): d = 0.90 (t, J = 7.0 Hz, 3 H), 1.27–
1.42 (m, 4 H), 2.12–2.17 (m, 2 H), 5.65 (d, J = 15.8 Hz, 1 H), 6.18
(dt, J = 15.8, 7.0 Hz, 1 H), 6.27 (dd, J = 16.1, 2.1 Hz, 1 H), 6.90 (d,
J = 16.1 Hz, 1 H), 7.23–7.38 (m, 5 H).
13C NMR (125 MHz, CDCl3): d = 13.8 (CH3), 22.1 (CH2), 30.8
(CH2), 32.9 (CH2), 87.4 (≡C), 90.9 (≡C), 108.4 (=CH), 109.6
(=CH), 126.1 (2 =CH), 128.4 (=CH), 128.6 (2 =CH), 136.4 (=C),
140.4 (=CH), 145.1 (=CH).
HRMS (EI): m/z [M+] calcd for C16H22 [M+]: 214.1722; found:
214.1703.
EI-MS: m/z (%) = 210 (85, [M+]), 181 (22), 168 (13), 167 (76), 166
(50), 165 (100), 154 (24), 153 (57), 152 (72), 151 (11), 141 (17),
139 (21), 128 (23), 116 (10), 115 (48), 95 (38), 91 (11), 89 (10).
(4E,8E)-5-Propyltrideca-4,8-dien-6-yne (8ea)
Eluent: pentane.
IR (neat): 3018, 2958, 2929, 2871, 1458, 1377, 952, 894 cm–1.
HRMS (EI): m/z calcd for C16H18 [M+]: 210.1409; found: 210.1378.
1H NMR (500 MHz, CDCl3): d = 0.89 (t, J = 7.3 Hz, 3 H), 0.91 (t,
J = 7.3 Hz, 3 H), 0.91 (t, J = 7.3 Hz, 3 H), 1.28–1.43 (m, 4 H), 1.5–
1.57 (m, 2 H), 2.05–2.14 (m, 4 H), 5.58 (d, J = 15.6 Hz, 1 H), 5.84
(t, J = 7.3 Hz, 1 H), 6.09 (dt, J = 15.6, 7.3 Hz, 1 H).
13C NMR (125 MHz, CDCl3): d = 13.7 (CH3), 13.8 (CH3), 13.8
(CH3), 21.6 (CH2), 22.1 (CH2), 22.5 (CH2), 30.4 (CH2), 30.9 (CH2),
32.7 (CH2), 32.8 (CH2), 85.3 (≡C), 90.2 (≡C), 109.8 (=CH), 123.2
(=C), 137.7 (=CH), 143.7 (=CH).
EI-MS: m/z (%) = 218 (74, [M+]), 190 (13), 189 (68), 175 (28), 161
(12), 148 (13), 147 (17), 133 (38), 131 (14), 128 (11), 120 (10), 119
(46), 117 (29), 116 (10), 115 (27), 106 (10), 105 (70), 103 (14), 95
(10), 93 (18), 92 (24), 91 (100), 81 (14), 79 (29), 78 (11), 77 (26),
69 (10), 67 (14), 65 (14), 55 (20).
(1E,5Z)-1-Phenyldeca-1,5-dien-3-yne (9fb = 10ca)
Eluent: pentane.
IR (neat): 3024, 2956, 2925, 2869, 2856, 1448, 948, 746, 690 cm–1.
1H NMR (500 MHz, CDCl3): d = 0.93 (t, J = 7.3 Hz, 3 H), 1.32–
1.47 (m, 4 H), 2.35–2.4 (m, 2 H), 5.63 (d, J = 10.6 Hz, 1 H), 5.93
(dt, J = 10.6, 7.3 Hz, 1 H), 6.33 (dd, J = 16.1, 2.1 Hz, 1 H), 6.92 (d,
J = 16.1 Hz, 1 H), 7.23–7.43 (m, 5 H).
13C NMR (125 MHz, CDCl3): d = 13.9 (CH3), 22.3 (CH2), 30.1
(CH2), 31.0 (CH2), 89.0 (≡C), 92.9 (≡C), 108.5 (=CH), 109.0
(=CH), 126.2 (2 =CH), 128.4 (=CH), 128.6 (2 =CH), 136.4 (=C),
140.4 (=CH), 144.2 (=CH).
EI-MS: m/z (%) = 210 (69, [M+]), 181 (28), 179 (10), 168 (15), 167
(72), 166 (52), 165 (100), 154 (24), 153 (57), 152 (69), 151 (10),
141 (17), 139 (21), 128 (24), 116 (11), 115 (46), 95 (38), 91 (12), 77
(11).
HRMS (EI): m/z calcd for C16H26 [M+]: 218.2035; found: 218.2035.
(5Z,9E)-Tetradeca-5,9-dien-7-yne (9fa = 10fa)
Eluent: pentane.
HRMS (EI): m/z calcd for C16H18 [M+]: 210.1409; found: 210.1458.
IR (neat): 3020, 2956, 2929, 2871, 2860, 1465, 954, 731 cm–1.
(1Z,5E)-1-Phenyldeca-1,5-dien-3-yne (10fb = 9ca)
Eluent: pentane.
IR (neat): 3018, 2954, 2925, 2869, 2854, 1448, 954, 785, 690 cm–1.
1H NMR (500 MHz, CDCl3): d = 0.89 (t, J = 7.3 Hz, 3 H), 0.91 (t,
J = 7.3 Hz, 3 H), 1.3–1.5 (m, 8 H), 2.1–2.15 (m, 2 H), 2.3–2.35 (m,
2 H), 5.55 (d, J = 10.7 Hz, 1 H), 5.62 (d, J = 15.8 Hz, 1 H), 5.86 (dt,
J = 10.7, 7.3 Hz, 1 H), 6.12 (dt, J = 15.8, 7.3 Hz, 1 H).
13C NMR (125 MHz, CDCl3): d = 13.8 (CH3), 13.9 (CH3), 22.1
(CH2), 22.2 (CH2), 29.9 (CH2), 30.9 (CH2), 31.0 (CH2), 32.8 (CH2),
84.9 (≡C), 92.4 (≡C), 109.1 (=CH), 109.7 (=CH), 143.3 (=CH),
144.3 (=CH).
1H NMR (500 MHz, CDCl3): d = 0.90 (t, J = 7.0 Hz, 3 H), 1.3–1.45
(m, 4 H), 2.14–2.19 (m, 2 H), 5.71 (dt, J = 15.8, 1.2 Hz, 1 H), 5.80
(dd, J = 11.9, 2.4 Hz, 1 H), 6.20 (dt, J = 15.8, 7.0 Hz, 1 H), 6.58 (d,
J = 11.9 Hz, 1 H), 7.23–7.37 (m, 3 H), 7.83–7.87 (m, 2 H).
13C NMR (125 MHz, CDCl3): d = 13.8 (CH3), 22.2 (CH2), 30.8
(CH2), 32.9 (CH2), 86.7 (≡C), 95.3 (≡C), 107.6 (=CH), 109.8
(=CH), 128.2 (2 =CH), 128.2 (=CH), 128.5 (2 =CH), 136.6 (=C),
137.6 (=CH), 145.5 (=CH).
EI-MS: m/z (%) = 190 (77, [M+]), 147 (17), 134 (20), 133 (11), 119
(22), 117 (11), 105 (57), 103 (12), 93 (11), 92 (13), 91 (100), 79
(27), 78 (66), 77 (20), 67 (13), 65 (15).
EI-MS: m/z (%) = 210 (60, [M+]), 181 (29), 179 (10), 168 (18), 167
(75), 166 (49), 165 (100), 154 (22), 153 (53), 152 (65), 151 (10),
141 (17), 139 (19), 128 (23), 116 (13), 115 (45), 95 (60), 91 (11).
HRMS (EI): m/z calcd for C14H22 [M+]: 190.1722; found: 190.1726.
(5Z,9Z)-Tetradeca-5,9-dien-7-yne (11fa)
Eluent: pentane.
HRMS (EI): m/z calcd for C16H18 [M+]: 210.1409; found: 210.1419.
IR (neat): 3020, 2956, 2929, 2871, 2858, 1465, 732 cm–1.
(1Z,5Z)-1-Phenyldeca-1,5-dien-3-yne (11fb = 11ca)
Eluent: pentane.
IR (neat): 3020, 2956, 2925, 2869, 2856, 1448, 783, 731, 690 cm–1.
1H NMR (500 MHz, CDCl3): d = 0.91 (t, J = 7.3 Hz, 6 H), 1.3–1.45
(m, 8 H), 2.3–2.4 (m, 4 H), 5.60 (d, J = 10.0 Hz, 2 H), 5.89 (dt,
J = 10.0, 7.3 Hz, 2 H).
13C NMR (125 MHz, CDCl3): d = 13.9 (2 CH3), 22.3 (2 CH2), 30.0
(2 CH2), 31.0 (2 CH2), 90.5 (2 ≡C), 109.2 (2 = CH), 143.4 (2 =CH).
EI-MS: m/z (%) = 190 (75, [M+]), 147 (13), 134 (21), 133 (13), 119
(32), 117 (13), 115 (10), 106 (13), 105 (70), 103 (12), 93 (12), 92
(14), 91 (100), 79 (32), 78 (62), 77 (20), 67 (12), 65 (14).
1H NMR (500 MHz, CDCl3): d = 0.91 (t, J = 7.3 Hz, 3 H), 1.3–1.47
(m, 4 H), 2.36–2.42 (m, 2 H), 5.68 (dt, J = 10.6, 1.2 Hz, 1 H), 5.86
(dd, J = 11.9, 2.7 Hz, 1 H), 5.95 (dt, J = 10.6, 7.3 Hz, 1 H), 6.60 (d,
J = 11.9 Hz, 1 H), 7.23–7.37 (m, 3 H), 7.85–7.9 (m, 2 H).
13C NMR (125 MHz, CDCl3): d = 13.9 (CH3), 22.3 (CH2), 30.3
(CH2), 31.1 (CH2), 92.0 (≡C), 93.5 (≡C), 107.7 (=CH), 109.1
(=CH), 128.2 (2 =CH), 128.3 (=CH), 128.5 (2 =CH), 136.5 (=C),
137.6 (=CH), 144.5 (=CH).
HRMS (EI): m/z calcd for C14H22 [M+]: 190.1722; found: 190.1741.
(1E,5E)-1-Phenyldeca-1,5-dien-3-yne (8fb = 8ca)
Eluent: pentane.
Synthesis 2005, No. 12, 1991–2007 © Thieme Stuttgart · New York

2006
M. Hoshi et al.
PAPER
(2) (a) Nicolaou, K. C.; Dai, W.-M. Angew. Chem., Int. Ed.
EI-MS: m/z (%) = 210 (64, [M+]), 181 (24), 168 (16), 167 (76), 166
(47), 165 (100), 154 (21), 153 (56), 152 (72), 141 (15), 139 (21),
128 (25), 116 (13), 115 (44), 95 (54), 89 (10).
Engl. 1991, 30, 1387; and references cited therein.
(b) Maier, M. E. Synlett 1995, 13; and references cited
therein. (c) Grissom, J. W.; Gunawardena, G. U.; Klingberg,
D.; Huang, D. Tetrahedron 1996, 52, 6453; and references
cited therein. (d) Maier, M. E.; Bobe, F.; Niestroj, A. J. Eur.
J. Org. Chem. 1999, 1.
HRMS (EI): m/z calcd for C16H18 [M+]: 210.1409; found: 210.1452.
(1E,5E)-1,6-Diphenylhexa-1,5-dien-3-yne (8cb)
Eluent: pentane–CH2Cl2 (9:1).
(3) (a) Martin, R. E.; Diederich, F. Angew. Chem. Int. Ed. 1999,
38, 1350; and references cited therein. (b) Hynd, G.; Jones,
G. B.; Plourde, G. W. II; Wright, J. M. Tetrahedron Lett.
1999, 40, 4481. (c) Tour, J. M. Acc. Chem. Res. 2000, 33,
791; and references cited therein. (d) Bunz, U. H. F. Chem.
Rev. 2000, 100, 1605; and references cited therein.
(e) Siemsen, P.; Livingston, R. C.; Diederich, F. Angew.
Chem. Int. Ed. 2000, 39, 2632; and references cited therein.
(f) Shimada, S.; Masaki, A.; Hayamizu, K.; Matsuda, H.;
Okada, S.; Nakanishi, H. Chem. Lett. 2000, 1128.
(g) Collins, S. K.; Yap, G. P. A.; Fallis, A. G. Org. Lett.
2000, 2, 3189. (h) Ciulei, S. C.; Tykwinski, R. R. Org. Lett.
2000, 2, 3607. (i) Schmittel, M.; Michel, C.; Wiegrefe, A.;
Kalsani, V. Synthesis 2001, 1561. (j) Heuft, M. A.; Collins,
S. K.; Yap, G. P. A.; Fallis, A. G. Org. Lett. 2001, 3, 2883.
(k) Nielsen, M. B.; Moonen, N. N. P.; Boudon, C.;
Gisselbrecht, J.-P.; Seiler, P.; Gross, M.; Diederich, F.
Chem. Commun. 2001, 1848. (l) Rodriguez, J. G.; Tejedor,
J. L. J. Org. Chem. 2002, 67, 7631. (m) Rodriguez, J. G.;
Tejedor, J. L. Tetrahedron Lett. 2003, 44, 2691.
(n) Kaafarani, B. R.; Wex, B.; Wang, F.; Catanescu, O.;
Chien, L. C.; Neckers, D. C. J. Org. Chem. 2003, 68, 5377.
(o) Rodriguez, J. G.; Esquivias, J.; Lafuente, A.; Diaz, C. J.
Org. Chem. 2003, 68, 8120. (p) Chanteau, S. H.; Tour, J. M.
J. Org. Chem. 2003, 68, 8750. (q) Takayama, Y.; Delas, C.;
Muraoka, K.; Uemura, M.; Sato, F. J. Am. Chem. Soc. 2003,
125, 14163. (r) Wilson, J. N.; Josowicz, M.; Wang, Y.;
Bunz, U. H. F. Chem. Commun. 2003, 2962. (s) Kozaki,
M.; Okada, K. Org. Lett. 2004, 6, 485. (t) Shirai, Y.; Zhao,
Y.; Cheng, L.; Tour, J. M. Org. Lett. 2004, 6, 2129.
(4) Nagata, T.; Ando, Y.; Hirota, A. Biosci. Biotechnol.
Biochem. 1992, 56, 810.
IR (neat): 954, 792, 746, 688 cm–1.
1H NMR (500 MHz, CDCl3): d = 6.34 (dd, J = 15.8, 1.8 Hz, 2 H),
6.97 (d, J = 15.8 Hz, 2 H), 7.23–7.42 (m, 10 H).
13C NMR (125 MHz, CDCl3): d = 91.5 (2 ≡C), 108.2 (2 =CH),
126.2 (4 =CH), 128.6 (2 =CH), 128.7 (4 =CH), 136.3 (2 = C), 141.1
(2 = CH).
EI-MS: m/z (%) = 230 (51, [M+]), 229 (34), 228 (30), 227 (10), 226
(16), 215 (14), 202 (10), 115 (100).
(1Z,5E)-1,6-Diphenylhexa-1,5-dien-3-yne (9cb = 10cb)31
Eluent: pentane–CH2Cl2 (9:1).
IR (neat): 950, 790, 761, 690 cm–1.
1H NMR (500 MHz, CDCl3): d = 5.88 (dd, J = 11.9, 2.7 Hz, 1 H),
6.40 (dd, J = 16.1, 2.7 Hz, 1 H), 6.65 (d, J = 11.9 Hz, 1 H), 6.98 (d,
J = 16.1 Hz, 1 H), 7.23–7.42 (m, 8 H), 7.83–7.85 (m, 2 H).
13C NMR (125 MHz, CDCl3): d = 90.6 (≡C), 95.6 (≡C), 107.5
(=CH), 108.2 (=CH), 126.2 (2 =CH), 128.3 (2 =CH), 128.3 (=CH),
128.4 (2 =CH), 128.6 (=CH), 128.7 (2 =CH), 136.2 (=C), 136.5
(=C), 138.3 (=CH), 141.4 (=CH).
EI-MS: m/z (%) = 230 (52, [M+]), 229 (42), 228 (32), 227 (11), 226
(17), 215 (16), 202 (10), 116 (12), 115 (100).
(1Z,5Z)-1,6-Diphenylhexa-1,5-dien-3-yne (11cb)31
Eluent: pentane–CH2Cl2 (9:1).
IR (neat): 783, 746, 688 cm–1.
1H NMR (500 MHz, CDCl3): d = 5.82–5.96 (m, 2 H), 6.64–6.82 (m,
2 H), 7.23–7.41 (m, 6 H), 7.82–7.85 (m, 4 H).
13C NMR (125 MHz, CDCl3): d = 94.6 (2 ≡C), 107.5 (2 =CH),
128.3 (2 =CH), 128.4 (4 =CH), 128.5 (4 =CH), 136.4 (2 =C), 138.5
(2 =CH).
(5) Garlaschelli, L.; Magistrali, E.; Vidari, G.; Zuffardi, O.
Tetrahedron Lett. 1995, 36, 5633.
(6) Müller, H.; Schmidt, C.; Kehr, S.; Hagedorn, M. Macromol.
Rapid Commun. 2000, 21, 449.
EI-MS: m/z (%) = 230 (46, [M+]), 229 (37), 228 (32), 227 (10), 226
(7) Sonoda, M.; Itahashi, K.; Tobe, Y. Tetrahedron Lett. 2002,
(17), 215 (17), 202 (11), 116 (10), 115 (100).
43, 5269.
(8) (a) Metal-Catalyzed Cross-Coupling Reactions; Diederich,
F.; Stang, P. J., Eds.; Wiley-VCH: Weinheim, 1998.
(b) Tsuji, J. Transition Metal Reagents and Catalysts:
Innovations in Organic Synthesis; Wiley: Chichester, 2000.
(9) (a) Miyaura, N.; Suzuki, A. Chem. Rev. 1995, 95, 2457.
(b) Suzuki, A. In Metal-Catalyzed Cross-Coupling
Reactions; Diederich, F.; Stang, P. J., Eds.; Wiley-VCH:
Weinheim, 1998. (c) Suzuki, A. J. Organomet. Chem. 1999,
576, 147.
(10) (a) Sonogashira, K.; Tohda, Y.; Hagihara, N. Tetrahedron
Lett. 1975, 16, 4467. (b) Sonogashira, K. In Metal-
Catalyzed Cross-Coupling Reactions; Diederich, F.; Stang,
P. J., Eds.; Wiley-VCH: Weinheim, 1998. (c) Sonogashira,
K. J. Organomet. Chem. 2002, 653, 46.
Acknowledgment
This work was partially supported by Grant-in-Aid for Scientific
Research (C) (KAKENHI 13650898) from Japan Society for the
Promotion of Science.
References
(1) (a) Kusumi, T.; Ohtani, I.; Nishiyama, K.; Kakisawa, H.
Tetrahedron Lett. 1987, 28, 3981. (b) Graham, A. E.;
McKerrecher, D.; Davies, D. H.; Taylor, R. J. K.
Tetrahedron Lett. 1996, 37, 7445. (c) Miller, M. W.;
Johnson, C. R. J. Org. Chem. 1997, 62, 1582.
(d) Yoshimura, F.; Kawata, S.; Hirama, M. Tetrahedron
Lett. 1999, 40, 8281. (e) Ohta, T.; Uwai, K.; Kikuchi, R.;
Nozoe, S.; Oshima, Y.; Sasaki, K.; Yoshizaki, F.
Tetrahedron 1999, 55, 12087. (f) Paterson, I.; Davies, R. D.
M.; Marquez, R. Angew. Chem. Int. Ed. 2001, 40, 603.
(g) Organ, M. G.; Ghasemi, H. J. Org. Chem. 2004, 69, 695.
(11) Hoshi, M.; Shirakawa, K. Synlett 2002, 1101.
(12) A part of the results have been described previously.11
(13) The amount of 1 M NaOMe could be reduced to three-
quarters with about the same yield of product as the previous
report: Hoshi, M.; Nakayabu, H.; Shirakawa, K. unpublished
results.
Synthesis 2005, No. 12, 1991–2007 © Thieme Stuttgart · New York

PAPER
Stereoselective Synthesis of 1-Arylalk-3-en-1-ynes and Alka-1,5-dien-3-ynes
2007
(14) (a) Mori, A.; Mohamed Ahmed, M. S.; Sekiguchi, A.;
Masui, K.; Koike, T. Chem. Lett. 2002, 756. (b) Mori, A.;
Shimada, T.; Kondo, T.; Sekiguchi, A. Synlett 2001, 649.
(15) For examples, see: (a) Jun, C.-H.; Lu, Z.; Crabtree, R. H.
Tetrahedron Lett. 1992, 33, 7119. (b) Yi, C. S.; Liu, N.
Organometallics 1996, 15, 3968. (c) Slugovc, C.; Mereiter,
K.; Zobetz, E.; Schmid, R.; Kirchner, K. Organometallics
1996, 15, 5275. (d) Yi, C. S.; Liu, N.; Rheingold, A. L.;
Liable-Sands, L. M. Organometallics 1997, 16, 3910.
(e) Ohmura, T.; Yorozuya, S.; Yamamoto, Y.; Miyaura, N.
Organometallics 2000, 19, 365. (f) Rubina, M.; Gevorgyan,
V. J. Am. Chem. Soc. 2001, 123, 11107. (g) Yang, C.;
Nolan, S. P. J. Org. Chem. 2002, 67, 591. (h) Nishiura, M.;
Hou, Z.; Wakatsuki, Y.; Yamaki, T.; Miyamoto, T. J. Am.
Chem. Soc. 2003, 125, 1184. (i) Wang, C.-Y.; Su, H.; Yang,
D.-Y. Synlett 2004, 561. (j) Tazelaar, C. G. J.; Bambirra, S.;
Van Leusen, D.; Meetsma, A.; Hessen, B.; Teuben, J. H.
Organometallics 2004, 23, 936. (k) Komeyama, K.;
Takehira, K.; Takaki, K. Synthesis 2004, 1062.
(18) Johnson, C. R.; Braun, M. P. J. Am. Chem. Soc. 1993, 115,
11014.
(19) Hayashi, T.; Konishi, M.; Kobori, Y.; Kumada, M.; Higuchi,
T.; Hirotsu, K. J. Am. Chem. Soc. 1984, 106, 158.
(20) Negishi, E.; Williams, R. M.; Lew, G.; Yoshida, T. J.
Organomet. Chem. 1975, 92, C4.
(21) (a) Amatore, C.; Azzabi, M.; Jutand, A. J. Organomet.
Chem. 1989, 363, C41. (b) Amatore, C.; Azzabi, M.; Jutand,
A. J. Am. Chem. Soc. 1991, 113, 8375.
(22) (a) Negishi, E.; Takahashi, T.; Akiyoshi, K. J. Chem. Soc.,
Chem. Commun. 1986, 1338. (b) Scott, W. J.; Stille, J. K. J.
Am. Chem. Soc. 1986, 108, 3033.
(23) Hatanaka, Y.; Matsui, K.; Hiyama, T. Tetrahedron Lett.
1989, 30, 2403.
(24) (a) Carpita, A.; Neri, D.; Rossi, R. Gazz. Chim. Ital. 1987,
117, 481. (b) Andreint, B. P.; Benetti, M.; Carpita, A.; Rossi,
R. Tetrahedron 1987, 43, 4591.
(25) Tellier, F.; Descoins, C.; Sauvêtre, R. Tetrahedron 1991, 47,
7767.
(16) (a) Akita, M.; Yasuda, H.; Nakamura, A. Bull. Chem. Soc.
Jpn. 1984, 57, 480. (b) Trost, B. M.; Sorum, M. T.; Chan,
C.; Harms, A. E.; Rühter, G. J. Am. Chem. Soc. 1997, 119,
698. (c) Chen, L.; Li, C.-J. Tetrahedron Lett. 2004, 45, 2771.
(17) For examples, see: (a) Miyaura, N.; Yamada, K.; Suginome,
H.; Suzuki, A. J. Am. Chem. Soc. 1985, 107, 972.
(26) Hofmeister, H.; Annen, K.; Laurent, H.; Wiechert, R.
Angew. Chem., Int. Ed. Engl. 1984, 23, 727.
(27) Southwick, P. L.; Kirchiner, J. R. J. Org. Chem. 1962, 27,
3305.
(28) (a) Zweifel, G.; Whitney, C. C. J. Am. Chem. Soc. 1967, 89,
2753. (b) Hoshi, M.; Shirakawa, K. Chem. Commun. 2002,
2146.
(29) Hoshi, M.; Arase, A. Synth. Commun. 1997, 27, 567.
(30) (a) Zweifel, G.; Brown, H. C. Org. React. 1963, 13, 1.
(b) Brown, H. C. Organic Syntheses via Boranes; Wiley-
Interscience: New York, 1975.
(31) The work-up procedure should be carried out at or below
room temperature in order to avoid any decomposition of the
product.
(b) Hoshi, M.; Masuda, Y.; Arase, A. Bull. Chem. Soc. Jpn.
1983, 56, 2855. (c) Hara, R.; Liu, Y.; Sun, W.-H.;
Takahashi, T. Tetrahedron Lett. 1997, 38, 4103.
(d) Masuda, Y.; Murata, M.; Sato, K.; Watanabe, S. Chem.
Commun. 1998, 807. (e) Zeni, G.; Alves, D.; Pena, J. M.;
Braga, A. L.; Stefani, H. A.; Nogueira, C. W. Org. Biomol.
Chem. 2004, 2, 803. (f) Raminelli, C.; Prechtl, M. H. G.;
Santos, L. S.; Eberlin, M. N.; Comasseto, J. V.
Organometallics 2004, 23, 3990. (g) Raminelli, C.;
Gargalaka, J. Jr.; Silveira, C. C.; Comasseto, J. V.
Tetrahedron Lett. 2004, 45, 4927. (h) Alami, M.;
Ramiandrasoa, P.; Cahiez, G. Synlett 1998, 325.
(i) Choukroun, R.; Zhao, J.; Lorber, C.; Cassoux, P.;
Donnadieu, B. Chem. Commun. 2000, 1511. (j) Kleijn, H.;
Tigchelaar, M.; Meijer, J.; Vermeer, P. Recl. Trav. Chim.
Pays-Bas 1981, 100, 337. (k) Yoshimatsu, M.; Yamada, H.;
Shimizu, H.; Kataoka, T. J. Chem. Soc., Chem. Commun.
1994, 2107.
Synthesis 2005, No. 12, 1991–2007 © Thieme Stuttgart · New York