Mori-Hiyama versus hay coupling for higher polyynes

Article abstract of DOI:10.1002/ejoc.201200554

Dimerizations of C₄ precursors RCa=CCa=CTMS [R = C ₆H₅ (1), p-CH₃C₆H₅, (2), 4-n-C₅H₁₁C₆H₄ (3), C ₆H₉ (4), p-CH₃O

Full text of DOI:10.1002/ejoc.201200554

Job/Unit: O20554
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FULL PAPER
DOI: 10.1002/ejoc.201200554
Mori–Hiyama versus Hay Coupling for Higher Polyynes
Nurbey Gulia,[a] Karolina Osowska,[a] Bartłomiej Pigulski,[a] Tadeusz Lis,[a]
Zbigniew Galewski,[a] and Sławomir Szafert*[a]
Keywords: Polyynes / Cross-coupling / X-ray diffraction / Topochemistry / Polymerization
Dimerizations of C4 precursors RCϵCCϵCTMS [R = C6H5
(1), p-CH3C6H5, (2), 4-n-C5H11C6H4 (3), C6H9 (4), p-
CH3OC6H4 (5), p-C6H5COC6H4 (6), p-NO2C6H4 (7), and p-
NCC6H4 (8)] by Hay coupling with in situ deprotection gave
stable octatetraynes R(CϵC)4R (1–8-C8-1–8) in 42–80%
yields as light yellow to brown powders. The same tetraynes
were next synthesized from the same C4 precursors by an
alternative Mori–Hiyama method that typically utilizes tri-
methylsilyl-substituted alkynes without prior deprotection.
The latter protocol proved useful and gave the expected
products but with lower yields of 8–74%. The resulting tet-
raynes were characterized by spectroscopic methods and in
some cases by X-ray crystallography. In the cases of 1-C8-1
and 3-C12-3, close analysis of the crystal data showed high
degrees of carbon chain linearity, with % contraction indexes
of 0.13% and 0.19%, respectively. The chains were more
strained in the cases of 6-C8-6 (0.34%) and 3-C8-3 (0.68%).
Deeper analysis of packing motifs revealed 3-C12-3 to be a
very promising candidate for topochemical 1,4-polymeriza-
tion.
elongation. For the latter step, the most commonly used
procedures include not only classical Glaser/Hay/Eglinton–
Galbraith,[8–10] or Cadiot–Chodkiewicz[8b,11] reactions
(shown in Scheme 1), but also other approaches/modifica-
tions that have been developed over the last years.[12]
Introduction
Over the last three decades, conjugated oligo- and po-
lyynes have continued to attract unabated attention. This
has been due to their salient application potential as car-
bon-rich building blocks both in organic syntheses and as
material precursors in different technological areas.[1] For
instance, organic polyynes (especially diynes) are important
precursors of numerous types of polymers, including those
that result from topochemical crystal-to-crystal polymeriza-
tion.[2] Thanks to the presence of redox-active end-groups,
organometallic and metal-containing polyynes are regarded
as extremely useful in molecular nanoelectronics as parts of
molecular-scale devices such as wires and switches.[3] This
group of compounds includes organometallic complexes of
type LmMCxMLm,[4] as well as metal-containing species in
which metal atoms are not bound directly to the carbon
atoms of polyyne chains. The latter group mostly includes
ferrocene derivatives,[5] although other types of compounds
are known.[6] Moreover, the polyyne motif is ubiquitous in
many natural organic products, which often show remark-
able biological activities.[7]
Scheme 1. Syntheses of diynes by (a) Glaser, (b) Eglinton–Gal-
braith, (c) Hay, and (d) Cadiot–Chodkiewicz couplings.
Most of the methods mentioned above utilize terminal
alkynes, which are often only of moderate stability towards
isolation and purification and tend to decompose under
ambient conditions.[13] This inexpedient “property”,
which also applies for long-chain disubstituted polyynes,
can be greatly mitigated by application of bulky end-
groups.[4e,4g,4h,12i,14]
Unlike the compounds with odd-carbon chains, symmet-
rical even-carbon chain polyynes of C2n type are quite
straightforward to synthesize. The typical pathway involves
the introduction of an acetylene moiety, followed by chain
Terminal alkynes are usually synthesized from much
more stable trialkylsilyl-substituted precursors by different
deprotection procedures, so in 2000 Mori and Hiyama (M–
H) successfully employed silyl-protected alkynes to test a
new coupling method that proceeded without the desil-
ylation step.[15] A while later, pathways with in situ depro-
[a] Department of Chemistry, University of Wrocław,
14 F. Joliot-Curie, 50–383 Wrocław, Poland
Fax: +48-71-328-23-48
E-mail: slawomir.szafert@chem.uni.wroc.pl
Homepage: http://zn1.stud.wchuwr.pl/Main/SlawomirSzafert
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejoc.201200554.
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N. Gulia, K. Osowska, B. Pigulski, T. Lis, Z. Galewski, S. Szafert
FULL PAPER
tection were introduced, although some of the reaction con- was obtained by the use of two different catalytic systems
ditions had to be chosen in a particularly astute manner.[16] (see Exp. Sect.), which gave nearly identical yields (49–
A number of butadiynes were obtained by the Mori–Hi- 51%).
yama method, which has proven to give good results for
Workup by column chromatography gave the targeted
different types of end-groups. Here we have extended this butadiynes, including the new 3-C4TMS (oil), 4-C4TMS
method for the synthesis of organic octatetraynes and com- (brown liquid), 6-C4TMS (beige solid), 7-C4TMS (light yel-
pared the Mori–Hiyama yields with those of Hay coupling low powder), and 8-C4TMS (yellow solid) in 49–80% yields.
with in situ deprotection. The resulting tetraynes were fully All of the compounds were soluble in common polar and
characterized by spectroscopic methods and in some cases nonpolar organic solvents such as CH2Cl2, acetone, THF,
by X-ray crystallography.
and hexanes.
1
All resulting diynes were characterized by H and 13C
NMR spectroscopy and gave correct elemental analysis. Al-
1
though the H and 13C NMR spectroscopic data were rou-
Results and Discussion
tine, we performed HMBC analysis for selected diynes in
order to assign the carbon signals unambiguously. The re-
sults are presented in Table 1 and the representative HMBC
spectrum for 3-C4TMS is shown in Figure 1.
Syntheses of Diacetylenes
Syntheses of the diacetylenic derivatives C6H5Cϵ
CCϵCTMS (1-C4TMS),[17] p-CH3C6H4CϵCCϵCTMS (2-
C4TMS),[18] 4-n-C5H11C6H4CϵCCϵCTMS (3-C4TMS),
C6H9CϵCCϵCTMS (4-C4TMS), p-CH3OC6H4CϵCCϵ
CTMS (5-C4TMS),[19] p-C6H5COC6H4CϵCCϵCTMS (6-
C4TMS), p-NO2C6H4CϵCCϵCTMS (7-C4TMS), and p-
NCC6H4CϵCCϵCTMS (8-C4TMS) was by the already
classical Cadiot–Chodkiewicz procedure[11] as shown in
Scheme 2. In the cases of the new 3-C4TMS, 4-C4TMS, and
8-C4TMS the reactions were performed by starting from
aryl- or cyclohexenyl-substituted terminal acetylenes, which
were treated with TMSCϵCBr or TMSCϵCI (Method I in
Scheme 2). In the cases of 6-C4TMS and 7-C4TMS the aryl-
substituted bromoalkynes p-C6H5COC6H4CϵCBr (6-
C2Br)[20] and p-NO2C6H4CϵCBr[21] were treated with
TMSCϵCH (Methods II and III in Scheme 2) in the pres-
ence of palladium(II)/CuI catalyst. Compound 6-C4TMS
Table 1. 13C NMR shifts for chain carbon atoms in diynes
RCϵCCϵCTMS.[a]
Compound
R
Yield
[%]
C(1) C(2) C(3) C(4)
[17]
1-C4TMS[17] C6H5
95
85[18b]
50
76.6 74.3 88.0 90.3
2-C4TMS[18] p-CH3C6H4
–
73.6 88.0 90.1
[18]
[18a]
3-C4TMS
4-C4TMS
5-C4TMS
6-C4TMS
7-C4TMS
8-C4TMS
4-n-C5H11C6H4
77.3 73.8 88.3 90.3
C6H9
80
36
51
52
79.2 71.9 88.4 89.4
[b][19]
p-CH3OC6H4
p-C6H5COC6H4
p-NO2C6H4
p-NϵCC6H4
–
73.2 88.3 90.1
77.1 75.8 87.6 92.7
79.2 74.4 87.1 94.4
78.4 74.6 87.1 93.9
53
[a] All spectra were measured in CDCl3. [b] The signal overlies with
the solvent signal.
Scheme 2. Syntheses of TMS end-capped diynes.
Figure 1. Partial HMBC spectrum for 3-C4TMS.
2
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Mori–Hiyama versus Hay Coupling for Higher Polyynes
As shown in Table 1, for all the compounds the most lyynes, for instance, form solid admixture with unique prop-
strongly downfield-shifted signal belongs to the C(4) car- erties with benzene.[22] Benzaldehyde-end-capped tetraynes
bon, which is α to the trimethylsilyl group. The next are the were used for the synthesis of tetraynic porphyrins.[23] It was
C(3) carbons, which lie in the narrow range between δ = noticed that some of the C8 and longer polyynes possess
87.1 and 88.4 ppm. This range becomes slightly wider for higher dipole moments, as well as first- and second-order
C(2) carbons (75.8–71.9 ppm; 3.9 ppm) as well as for C(1) hyperpolarizabilities.[24] The pharmaceutical potential of a
atoms (79.2–76.6 ppm; 2.6 ppm). The signals in C6D6 (mea- few natural tetraynes is also worth mentioning.[25]
sured for 3-C4TMS and 7-C4TMS) are shifted only slightly
relative to those in CDCl3, as shown in the Experimental series of symmetric tetraynes R(CϵC)4R (1–8-C8-1–8) di-
Section. rectly from TMS-end-capped diynes was a major goal of
A straightforward synthesis and characterization of the
Proton spectra revealed the signals of the TMS groups this research. For comparison, two synthetic strategies –
at 0.24 (3-C4TMS, 0.11 in C6D6), 0.20 (4-C4TMS), 0.25 (6- a) Hay coupling with in situ deprotection, and b) the Mori–
C4TMS), 0.25 (7-C4TMS, 0.11 in C6D6), and 0.24 (8- Hiyama approach – were tested. The latter, as mentioned
C4TMS) ppm. The signal of the carbonyl group carbon in already, has successfully been employed for the synthesis of
6-C4TMS was at δ = 195.8 ppm.
symmetrical diynes,[15] so we were curious as to whether or
not the protocol would work equally well for tetraynes as it
did for diynes, with which the yields exceeded 70%.
As shown in Scheme 3 the Hay coupling was performed
Synthesis of Tetraynes
Organic and organometallic tetraynes have been objects by the standard procedures, with wet TBAF as the depro-
of intense research over the last two decades. To date, nu- tecting agent, ClSiMe3 as the F– ion scavenger, and CuI/
merous aryl-end-capped organic C8 polyynes have been ob- TMEDA/acetone or CH3CN as the oxidation catalytic sys-
tained and characterized. The compounds are interesting tem. Workups on silica gel columns gave analytically pure
from different perspectives. Perfluorophenyl-substituted po- target tetraynes 1–8-C8-1–8 in 42–80% yields (see Table 2)
Scheme 3. Syntheses of tetraynes.
Table 2. Yields and spectroscopic data for 1–8-C8-1–8.[a]
Compound
1-C8-1
2-C8-2[18b]
3-C8-3
4-C8-4
5-C8-5
6-C8-6
7-C8-7
8-C8-8
Hay yield [%]
M–H yield [%]
IR [cm–1]
72
52
2202
2098
75
25
2198
2094
80
74
2198
2075
65
25
2192
2100
77
8
2197
2074
71
61
42
15
2205
2105
54
59
2202
2102
2200
(not observed)
13C NMR;
75.8
74.8
70.5
65.6
78.7
74.7
67.8
64.7
80.9
74.9
68.0
64.8
80.2
73.1
67.3
64.5
76.1
73.5
71.4
68.9
77.8
77.0
68.8
64.8
78.2
74.3
73.4
67.6
77.6
74.1
73.8
67.7
CϵCCϵCAr
13C NMR;
CϵCCϵCAr
13C NMR;
CϵCCϵCAr
13C NMR;
CϵCCϵCAr
[a] The chemical shifts are in ppm. Spectra were recorded in C6D6.
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as light yellow to brown solids readily soluble in most com- smart not to exclude the approach from a strategy for a
mon organic solvents. The compounds are stable in the so- longer chain synthesis.
lid state and in solution for extended periods (weeks to
months).
Although no thermal analysis was performed for the ma-
jority of the compounds, 2-C8-2 revealed interesting behav-
Compounds 1–8-C8-1–8 were characterized by IR and by ior. The compound melted without decomposition at
1H and 13C NMR spectroscopy and gave correct micro- 120 °C, giving a nematic phase, and then polymerized at
analyses. The IR spectra showed a set of two νCϵC absorp- 156 °C. Figure 3 shows the thermal transformations of 2-
tions for each compound at frequencies ranging from 2205 C8-2.
to 2192 cm–1 (vs) and from 2105 to 2074 cm–1 (variable in-
tensities). The latter band was not observed in the case of
6-C8-6.
Similarly as for C4 compounds, HMBC spectra were re-
corded for selected compounds in order to assign carbon
chain signals unambiguously. The spectrum of 3-C8-3 is
shown in part in Figure 2.
Figure 3. Melting and polymerization of 2-C8-2: crystalline phase
(top left), nematic phase (top right), disappearance of nematic
phase (bottom left), and polymerization (bottom right).
Crystal Structures of Tetraynes
The crystal structures of 1-C8-1, 3-C8-3, 3-C12-3, and 6-
C8-6 were determined as outlined in Tables 3 and 4 and
described in the Experimental Section.
Figure 2. Partial HMBC spectrum of 3-C8-3.
From these data, we assigned carbon chain signals for
each compound. The most strongly downfield-shifted sig-
nals, ranging from 75.8 ppm for 1-C8-1 to 80.9 ppm for 3-
C8-3, were assigned to carbons adjacent to end-groups.
Along the carbon chain towards its middle point the signals
for each compound moved upfield. The detail analysis is
presented in Table 2 and in the Experimental Section.
The Mori–Hiyama protocol was next tested. The reac-
tions were performed in DMF at 60 °C with the use of
CuCl as catalyst and C4TMS precursor as shown in
Scheme 3 (Method B). Workup gave the target tetraynes in
8–74% yields, showing the protocol to be useful. Neverthe-
less, as can easily be seen in Table 2, the yields achieved in
the Hay couplings substantially surpass the Mori–Hiyama
results. This is particularly apparent in the case of 5-C8-5,
but in some cases (3-C8-3, 6-C8-6, and 8-C8-8) Mori–Hi-
yama coupling gave similar yields. With this in mind and in
view of the simplicity of the method it would always be
Table 3. X-ray data for tetraynes 1-C8-1, 3-C8-3, and 6-C8-6 and
for hexayne 3-C12-3.
Complex
Formula
Formula weight 250.28
T [K]
Space group
a [Å]
1-C8-1
3-C8-3
3-C12-3
6-C8-6
C20H10
C30H30
390.54
100(2)
C34H30
438.58
100(2)
C34H18O2
458.51
100(2)
C2/c
51.66(2)
3.889(3)
100(2)
P21/n
10.808(6) 7.704(4)
3.871(3) 8.974(4)
¯
P1
¯
P1
4.936(4)
9.892(7)
b [Å]
c [Å]
16.768(9) 16.297(8) 13.545(9) 11.380(4)
α [o]
90.0
90.90(5)
87.91(4)
79.40(4)
82.78(4)
90.0
96.38(3)
90.0
β [o]
106.03(5) 91.21(5)
90.0
γ [o]
92.54(5)
V [Å3]
Z
674.3(7)
2
1.233
1125.2(9) 644.9(8)
2272(2)
4
1.340
2
1
ρ [gcm–3]
μ (Mo-Kα)
[mm–1]
R1 [%] (Ͼ2σ)
1.153
1.131
0.070
0.065
0.478
0.082
0.0636
0.1139
0.2389
0.0658
0.1769
0.0603
0.1507
wR2 [%] (Ͼ2σ) 0.1218
4
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Mori–Hiyama versus Hay Coupling for Higher Polyynes
Table 4. Interatomic distances and angles for 1-C8-1, 3-C8-3, 3-C12-
3, and 6-C8-6.
Crystals of hexayne 3-C12-3 were obtained by chance
when one of the 3-C8-3 mixtures (from Hay coupling) was
set for crystallization. It has been documented that longer
or shorter polyynes can spontaneously form in small quan-
tities during chain elongation processes.[27] Subsequent di-
merization of such mixture without prior separation gives
mixture of symmetrical polyynes. This method is sometimes
used for the formation of C4n+2 compounds.[28]
As depicted in Figure 4 the centrosymmetric molecule of
1-C8-1 is almost ideally planar. The two phenyl rings are
coplanar, which is a consequence of the fact that the mole-
cule lies at the symmetry center. The interatomic distances
in the carbon chain are 1.2072(19) and 1.213(2) Å for the
triple C(1)ϵC(2) and C(3)ϵC(4) bonds and 1.367(2) and
1.363(3) Å for the single C(2)–C(3) and C(4)–C(4a) bonds,
respectively, and are similar to those found for other tet-
raynes.[4a,4b] An analogous situation applies for centrosym-
metric 3-C12-3, which crystallizes in the C2/c space group.
Also in this case the terminal phenyl rings are coplanar, as
shown in Figure 5.
Complex
1-C8-1
3-C8-3
3-C12-3
6-C8-6
Interatomic distances [Å]
C(11)–C(1)
C(1)–C(2)
C(2)–C(3)
C(3)–C(4)
C(4)–C(4a)
C(4)–C(5)
C(5)–C(6)
C(6)–C(6a)
C(6)–C(7)
C(7)–C(8)
C(8)–C(21)
1.435(2)
1.2072(19) 1.196(6)
1.367(2)
1.213(2)
1.431(7)
1.4318(19) 1.4299(19)
1.2088(19) 1.2075(19)
1.3600(19) 1.363(2)
1.2168(19) 1.2107(19)
1.367(7)
1.217(7)
–
1.355(6)
1.202(6)
–
1.375(7)
1.202(6)
1.422(6)
1.363(3)
–
1.360(3)
–
–
–
–
–
–
1.3507(19)
1.2206(18)
1.350(3)
–
–
–
–
–
–
–
–
–
C(1)-C(X)[a] sum
C(1)–C(X)[a] dist
% contraction
8.937
8.934
0.03
11.807
11.792
0.13
8.914
8.878
0.41
11.767
11.688
0.68
14.0638
14.045
0.13
16.9275
16.895
0.19
8.9224
8.916
0.07
11.7822
11.742
0.34
C(11)–C(Y)[b] sum
C(11)–C(Y)[b] dist
% contraction
Interatomic angles [°]
C(11)–C(1)–C(2)
C(1)–C(2)–C(3)
C(2)–C(3)–C(4)
C(3)–C(4)–C(4a)
C(3)–C(4)–C(5)
C(4)–C(5)–C(6)
C(5)–C(6)–C(6a)
C(5)–C(6)–C(7)
C(6)–C(7)–C(8)
C(7)–C(8)–C(21)
176.69(15) 177.6(6)
177.87(16) 177.6(6)
177.84(16) 178.7(6)
178.02(14) 173.06(15)
178.24(15) 177.40(15)
178.22(15) 176.98(16)
179.3(2)
–
–
179.6(2)
–
–
–
–
–
–
176.2(6)
176.8(6)
–
177.8(6)
177.8(5)
177.2(5)
177.47(15)
178.05(15)
179.9(2)
–
–
–
–
–
–
–
–
–
av. Angle
177.93
177.46
178.32
176.76
Figure 4. ORTEP views of 1-C8-1.
[a] C(X) represents the last atom in carbon chain opposite to C(1).
[b] C(Y) represents the atom from the end-group that bounds to
the carbon chain.
Slightly lower degrees of planarity are observed for 3-C8-
3 and 6-C8-6, although in the latter case this is caused by
the bulky end-groups. The two molecules are shown in Fig-
ures 6 and 7, respectively, and the bottom views illustrate
their planarity.
In the case of the structure of 1-C8-1, data for two poly-
In 3-C8-3 the angle between the phenyl rings is 4.8°. In
morphs of this compound have already been published,[26] 6-C8-6 it is 0°, but the phenyl rings of the C6H5CO substitu-
but only space group and unit cell characteristics were re- ents form an angle of 49.2° with the rings that are adjacent
ported, with no interatomic angles or atomic coordinates. to the carbon chain. The value is almost identical with the
For that reason we decided to grow crystals of this com- analogous one in diyne C6H5COC6H4CϵCCϵCC6H4-
pound and to solve and refine its structure to fill out an COC6H5 (49.8°).[15] Each C=O group [defined by C(5),
important gap in the CCDC data and to provide additional C(14), C(21), and O(1) atoms] lies at an angle of 37.9° to
information for a future structural analysis.[4a,4b]
the terminal phenyl ring and of 16.2° to the C6H4 ring.
Figure 5. ORTEP views of 3-C12-3.
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group. As a consequence, molecules 1-C8-1 and 6-C8-6 are
packed to form two non-parallel sets of parallel chains.
These sets form angles of 14.0° in 1-C8-1 and 15.2° in 6-C8-
6. Figures 8 and 9 show packing diagrams for 1-C8-1 and
6-C8-6 with nearly perpendicular sets of molecules.
Figure 6. ORTEP views of 3-C8-3.
Figure 7. ORTEP views of 6-C8-6.
These values are also similar to the corresponding ones in
C6H5COC6H4CϵCCϵCC6H4COC6H5 (38.4° and 15.1°,
respectively).
Figure 8. Packing diagram for 1-C8-1 with the shortest chain–chain
distances for parallel and non-parallel neighbors. The distances [Å]
are: C(1B)–C(1D), C(2B)–C(2D), etc., 3.871; C(1)–C(1B) and
C(1)–C(1D), 5.119; C(1)–C(1G), 4.369. Symmetry operations for
related atoms are (B): 0.5 – x, 0.5 + y, 1.5 – z; (D): 0.5 – x, 0.5 +
y, 1.5 – z; (G): –x, 1 – y, 1 – z.
The interatomic distances and angles within carbon
chains (see Table 4) were next analyzed. The shortest CϵC
distances are 1.196(6) Å and 1.202(6) Å, both for 3-C8-3,
and they are shorter than the CϵC distances in ethyne[29]
(1.2033 Å) and butadiyne (1.217–1.20964 Å).[30] The long-
est CϵC distance of 1.2206(18) Å belongs to internal triple
bond in 3-C12-3 and is slightly longer than the average value
of this bond in the other crystallographically characterized
C8 compounds.[4a,4b]
Because C8 chains are long enough to exhibit distinctive
bending, we inspected the chains in order to estimate the
degree of deformation for each compound. As can be seen
from the top sections of Figures 4–7, compounds 1-C8-1, 3-
C12-3, and 6-C8-6 can be regarded as S-shaped, whereas 3-
C8-3 represents a slightly unsymmetrical bow. These easily
perceptible deformations from linearity are further sup-
ported by the non-zero % contraction values, which range
(those calculated for chain carbon-carbon bonds only) from
as low as 0.03 for 1-C8-1 through 0.07 and 0.013 for 6-C8-
6 and 3-C12-3, respectively, to the highest value of 0.41 for
3-C8-3. Interestingly, the average value for the C-C–C
angles is the lowest for 6-C8-6 and the highest for 3-C12-3.
The closest chain–chain separation was then analyzed.
As defined earlier,[4a,4b,16] we approximate the closest chain–
chain distance as the closest carbon-carbon distance from
two neighboring carbon chains. Accordingly, the nearest
chains with parallel orientation for 1-C8-1 are only 3.871 Å
apart and this separation is slightly larger than the sum of
the van der Waals radii (3.56 Å) and very similar to that
found for TMS(CϵC)4TMS (3.853 Å).[31]
Despite the bulkier end-group the distance is similarly
short for 6-C8-6 (3.889 Å), whereas for 3-C8-3, with less
bulky (relative to 6-C8-6) end-groups, it is longer (4.524 Å).
Additionally, for 6-C8-6 the chain–chain distance between
non-parallel chains is even shorter than that for parallel
chains and reaches 3.652 Å.
Not surprisingly, the value for 3-C12-3 (Figure 10) is
much shorter (3.484 Å), which can be attributed to the
longer chain. This value is even smaller than that for MeTe-
(CϵC)4TeMe (3.486 Å), which had previously been re-
garded as the one possessing the shortest carbon–carbon
chain distance out of all the X-ray-characterized com-
pounds.[4a,4b,32]
Packing Motifs and Reactivity Implications
The four structures crystallize in the monoclinic system
1,n-Topochemical polymerization is one of the most
in the P21/n (1-C8-1) and C2/c (6-C8-6) space groups and in widely recognized transformations that can take place in
the triclinic system in the P1 (3-C8-3 and 3-C12-3) space relation to organic polyynes.[2] The geometric requirements
¯
6
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Mori–Hiyama versus Hay Coupling for Higher Polyynes
Figure 9. Packing diagram for 6-C8-6 with the shortest chain–chain
distances for parallel and non-parallel neighbors. The distances [Å]
are: C(1)–C(1H), C(2)–C(2H), etc., 3.889; C(3H)–C(3AA), 3.652.
Symmetry operations for related atoms are (H): –x, –1 + y, z;
(AA): –x, –1 + y, 1.5 – z.
for such process for diynes (1,4-polymerization) are fulfilled
when the nearest parallel chains are separated by ca. 3.5 Å
and the angle φ is close to 45° (see Figure 11).
The corresponding values for triynes and tetraynes are
3.5 Å and 28° (1,6-polymerization) and 3.5 Å and 21° (1,8-
polymerization), respectively.[4a,4b] On searching for such
values, it can easily be seen (see Table 5) that there is no
good candidate for 1,8-polymerization. Although structures
1-C8-1 and 6-C8-6 present more ladder-type architectures (φ
= 83.0° and 82.4°; for ideal ladder type φ = 90°), compound
3-C12-3 seems as an ideal candidate for 1,4-polymerization.
Figure 10. Packing diagram for 3-C12-3 with the shortest chain–
chain distances. The distances [Å] are: C(1)–C(4D), 5.032; C(2)–
C(3D), 5.095; C(3)–C(6AA), 3.567; C(4)–C(6B), 3.625; C(5)–
C(5B), 3.625. Symmetry operations for related atoms are: (AA): 1
+ x, y, z; (B) 2 – x, 1 –y, 1 – z; (D): 2 – x, 2 – y, 1 – z.
Conclusions
In summary, we have demonstrated the utility of the
Mori–Hiyama protocol for the synthesis of longer polyynes.
Although the received yields were lower than those of more
“traditional” Hay coupling with in situ deprotection, the
simplicity of the procedure might in specific cases be more
useful than the resulting yield. The Mori–Hiyama approach
also seems advantageous in cases when one needs to avoid
isolation or even formation of terminal alkynes. The re-
sulting octatetraynes are stable solids that can be stored for
long periods (weeks to months) at reduced temperatures.
They were fully characterized by spectroscopic methods
and for some compounds HMBC experiments were con-
ducted in order to assign the signals of carbons from unsat-
Figure 11. Topochemical 1,4-polymerization of crystalline diynes.
urated chains unambiguously. Structural analysis of crystal- uct of 3-C8-3 synthesis, the insight into packing motifs
lographically characterized compounds showed high de- showed a great potential for topochemical (crystal-to-crys-
grees of chain linearity. In the case of 3-C12-3, a side prod- tal) 1,4-polymerization.
Eur. J. Org. Chem. 0000, 0–0
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N. Gulia, K. Osowska, B. Pigulski, T. Lis, Z. Galewski, S. Szafert
FULL PAPER
were evaporated under oil pump vacuum to give 1-C8-1 as a light
yellow crystalline solid in 72% yield (0.117 g, 0.467 mmol).
Table 5. Packing parameters for tetraynes 1-C8-1, 3-C8-3, 3-C12-3,
and 6-C8-6.
Complex
1-C8-1 3-C8-3 3-C12-3 6-C8-6
Method B: C6H5(CϵC)2TMS (0.250 g, 1.26 mmol) was added to a
suspension of CuCl (0.120 g, 1.21 mmol) in DMF (5 mL). The mix-
ture was heated to 60 °C and kept at this temperature for 3 h. HCl
(1 m, 30 mL) was then added to the warm solution. The water layer
was extracted with Et2O (5ϫ20 mL). The combined organic layers
were rinsed with saturated NaCl solution and dried with Na2SO4.
The solution was next filtered and reduced in volume to ca. 30 mL
under oil pump vacuum. It was chromatographed on a silica gel
column (25ϫ2.5 cm, hexanes) to give 1-C8-1 in 52% yield (0.082 g,
0.328 mmol) as a light yellow solid.
Chain–chain contact [Å, parallel] [°][33] 3.871 4.524
3.484
45.3
11.88
0.70
–
3.889
82.4
0.51
0.06
15.2
3.652
83.0
0.47
0.04
14.0
5.119
29.1
8.90
0.76
–
Offset distance [Å][33]
Fractional offset
Angle between nonparallel chains [°]
Chain–chain contact [Å, nonparallel]
–
–
Experimental Section
1H NMR (300 MHz, C6D6):
δ = 7.20–6.80 (m, 10 H of
General: All reactions were conducted under N2 with use of stan-
dard Schlenk techniques. Solvents were treated as follows: hexanes
and Et2O were distilled from Na, THF was predried with NaOH
and then distilled from Na/benzophenone, CH2Cl2 and acetone
were distilled from P2O5, and CH3CN (HPLC grade) and DMF
(Aldrich, 99.8% anhydrous) were used as received.
2ϫC6H5) ppm. 13C{1H} NMR (75 MHz, C6D6): δ = 133.1 (s, 4 C-
ortho of 2ϫC6H5), 129.6 (s, 4 C-meta of 2ϫC6H5), 128.0 (s, 2 C-
para of 2ϫC6H5), 120.9 (s, 2 C-ipso[36] of 2ϫC6H5), 75.8 (s, 2 C,
C6H5CϵCCϵC), 74.8 (s, 2 C, C6H5CϵCCϵC), 70.5 (2 C,
C H CϵCCϵC), 65.6 (2 C, C H CϵCCϵC) ppm. IR (KBr): ν =
˜
6
5
6
5
2202 (CϵC), 2098 (CϵC) cm–1. MS: m/z = 250 [M]+. C20H10
TMSCϵCH (98%, Aldrich), Pd(PPh3)2Cl2 (99%, Aldrich), CuI
(99.999%, Aldrich), CuCl (99.995%, Aldrich), BuLi (1.6 m in hex-
ane, Aldrich), N-bromosuccinimide (NBS, 99%, Aldrich), N-iodo-
succinimide (NIS, 97%, Fluka), AgF (99.9%, Aldrich), EtNH2
(2.0 m in THF, Aldrich), diisopropylamine (99.95%, Aldrich), eth-
ynylcyclohexene (99%, Aldrich), tetrabutylammonium fluoride
(TBAF, 1.0 m in THF, Aldrich), N,N,NЈ,NЈ-tetramethylethylenedi-
amine (TMEDA, 99%, distilled from KOH, Aldrich), phenylacetyl-
ene (98%, Aldrich), 4-ethynyltoluene (97%, Aldrich), 4-ethynyl-
benzonitrile (97%, Aldrich), 4-ethynylpentylbenzene (97%, Ald-
rich), PPh3 (99%, Merck), ClSiMe3 (97%, Riedel–de Haen),
Na2SO4 (POCh), NaCl (POCh), and MgSO4 (POCh) were used
without further purification unless stated otherwise.
(250.30): calcd. C 95.97, H 4.03; found C 96.13, H 4.08.
p-CH3C6H4(CϵC)4-p-C6H4CH3 (2-C8-2):[18b] A) As described in
ref.[18b] B) p-CH3C6H5(CϵC)2TMS (0.220 g, 1.04 mmol), CuCl
(0.101 g, 1.02 mmol), and DMF (5 mL) were combined in a pro-
cedure analogous to that used for 1-C8-1 (Method B) to give 2-C8-
2 as a light yellow powder in 25% yield (0.036 g. 0.129 mmol) with
NMR characteristics congruent with those reported. M.p. 120 °C.
p-C5H11C6H4(CϵC)2TMS (3-C4TMS):
A Schlenk flask was
charged with p-C5H11C6H4CϵCH (1.00 mL, 0.858 g, 4.98 mmol)
and THF (20 mL). The solution was cooled to –45 °C and nBuLi
(3.44 mL, 5.50 mmol, 1.1 equiv.) was added with stirring. After
15 min CuI (0.949 g, 4.98 mmol) was added. The temperature was
slowly raised to ca. –10 °C. After 10 min the solution was again
cooled to –45 °C and EtNH2 (3 mL) and TMSCϵCBr (0.863 g,
4.88 mmol) were added. After 15 min the cold bath was removed
and the mixture was stirred for 1 h at room temperature. The sol-
vent was removed under oil pump vacuum. The residue was passed
through a 5 cm silica gel plug (rinsed with hexanes/CH2Cl2, 1:1, v/
v) and solvent was removed under oil pump vacuum. The residue
was flash chromatographed (silica gel, hexanes) to give 3-C4TMS
as an oily liquid in 50% yield (0.666 g, 2.48 mmol). 1H NMR
(600 MHz, C6D6): δ = 7.30 (d, JH,H = 8.3 Hz, 2 H of C6H4), 6.73
(d, JH,H = 8.3 Hz, 2 H of C6H4), 2.27 (t, JH,H = 7.8 Hz, 2 H of
CH2), 1.31–1.38 (m, 2 H of CH2), 1.15–1.22 (m, 2 H of CH2), 1.06–
1.13 (m, 2 H of CH2), 0.83 (t, JH,H = 7.4 Hz, 3 H of CH3), 0.11 (s,
9 H, SiMe3) ppm. 13C{1H} NMR (150 MHz, C6D6): δ = 144.8 (s,
C-para of C6H4), 133.0 (s, 2 C-ortho of C6H4), 128.9 (s, 2 C-meta
of C6H4), 119.0 (s, C-ipso of C6H4), 90.5 (s, 1 C, CϵCCϵCTMS),
TMSCϵCI, TMSCϵCBr,[34] C6H5(CϵC)2TMS,[17] p-CH3C6H5-
(CϵC)2TMS,[18b] p-CH3OC6H4(CϵC)2TMS,[19] p-C6H5COC6-
H4CϵCTMS,[16] and p-NO2C6H4CϵCBr,[16,35] were prepared by
the known protocols.
Infrared spectra were recorded in a KBr cell with a Bruker 66/s
FTIR spectrophotometer. TG-DTA analyses were recorded with a
Setaram SETSYS 16/18 instrument. NMR spectra were obtained
with BRUKER ESP 300E and 500 spectrometers. GC–MS analyses
were recorded with
a gas chromatograph, a mass detector
(HP 5971A), and an infrared detector (HP5965B, Hewlett–Pack-
ard). Microanalyses were conducted with an ARL Model 3410 +
ICP spectrometer (Fisons Instruments) and a VarioEL III CHNS
(both in-house).
C6H5(CϵC)4C6H5 (1-C8-1)
Method A: A Schlenk flask was charged with CuCl (1.32 g,
13.3 mmol), acetone (5 mL), and TMEDA (0.781 mL, 5.21 mmol). 89.5 (s, 1 C, CϵCCϵCTMS), 77.9 (s, 1 C, CϵCCϵCTMS), 74.9
The mixture was stirred for 30 min and a blue supernatant formed
over a green solid. It was filtered off and the filtrate was kept under
N2. In a separate flask, C6H5(CϵC)2TMS[17] (0.258 g, 1.30 mmol)
was dissolved in acetone (10 mL). The solution was purged with
N2 for 10 min and TBAF (0.260 mL, 0.260 mmol, 20 mol-%) was
added. After 20 min, ClSiMe3 (0.168 mL, 1.33 mmol) was intro-
duced and after another 15 min O2 began to be bubbled through
the solution. The blue filtrate was then added to the solution in
several portions. After the last portion had been added, bubbling
of O2 was continued for an additional 3.5 h. After this time the
solvent was evaporated under oil pump vacuum. The residue was
dissolved in hexanes/CH2Cl2 (5 mL, 1:1, v/v) and passed through a
Al2O3 plug (10 cm) and then through a silica plug (3 cm). Solvents
(s, 1 C, CϵCCϵCTMS), 36.1 (s, 1 C, C6H4CH2CH2), 31.7 (s, 1 C,
CH2CH2CH3), 31.0 (s, 1 C, CH2CH2CH2CH3), 22.8 (s, 1 C,
CH2CH3), 14.2 (s, 1 C, CH3), –0.4 (s, 3 C, SiMe3) ppm. H NMR
(500 MHz, CDCl3): δ = 7.40 (d, JH,H = 8.3 Hz, 2 H of C6H4), 7.13
(d, JH,H = 8.3 Hz, 2 H of C6H4), 2.60 (t, JH,H = 7.8 Hz, 2 H of
CH2), 1.57–1.63 (m, 2 H of CH2), 1.30–1.35 (m, 4 H of CH2), 0.89
(t, JH,H = 7.4 Hz, 3 H of CH3), 0.24 (s, 9 H, SiMe3) ppm. 13C{1H}
NMR (125 MHz, CDCl3): δ = 144.9 (s, C-para of C6H4), 132.8 (s,
2 C-ortho of C6H4), 128.7 (s, 2 C-meta of C6H4), 118.6 (s, C-ipso
1
of C6H4), 90.3 (s,
1 C, CϵCCϵCTMS), 88.3 (s, 1 C,
CϵCCϵCTMS), 77.3 (s, 1 C, CϵCCϵCTMS), 73.8 (s, 1 C,
CϵCCϵCTMS), 36.2 (s, 1 C, C6H4CH2CH2), 31.6 (s, 1 C,
CH2CH2CH3), 31.0 (s, 1 C, CH2CH2CH2CH3), 22.7 (s, 1 C,
8
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Mori–Hiyama versus Hay Coupling for Higher Polyynes
CH2CH3), 14.2 (s, 1 C, CH3), –0.2 (s, 3 C, SiMe3) ppm. C18H24Si CH=CCH2CH2), 21.3 (s, 2 C, CH2CH2CH=C) ppm. IR (KBr):
(262.43): calcd. C 82.38, H 9.22; found C 82.46, H 9.16.
ν
= 2192 (vs), 2100 (s) cm–1. MS: m/z = 258 [M]+. C20H18
˜
CϵC
(258.36): calcd. C 92.98, H 7.02; found C 92.55, H 7.17.
p-C5H11C6H4(CϵC)4-p-C6H4C5H11 (3-C8-3)
p-CH3OC6H4(CϵC)4-p-C6H4OCH3 (5-C8-5)
Method A: Compound 3-C4TMS (0.212 g, 0.790 mmol), TBAF
(0.158 mL, 0.158 mmol), ClSiMe3 (0.102 mL, 0.790 mmol), CuCl
(0.799 g, 7.900 mmol), and TMEDA (0.474 mL, 3.16 mmol) were
combined in a procedure analogous to that used for 1-C8-1
(Method A). The analogous workup gave 3-C8-3 as a light yellow,
crystalline powder in 80% yield (0.123 g, 0.316 mmol).
Method A: p-CH3OC6H4(CϵC)2TMS[19] (0.070 g, 0.310 mmol),
TBAF (0.061 mL, 0.061 mmol), ClSiMe3 (0.040 mL, 0.309 mmol),
CuCl (0.030 g, 0.309 mmol), and TMEDA (0.018 mL, 0.12 mmol)
were combined in a procedure analogous to that used for 1-C8-1
(Method A). THF was used instead of acetone. The analogous
workup gave 7-C8-7 as a light yellow, crystalline powder in 77%
yield (0.037 g, 0.12 mmol).
Method B: Compound 3-C4TMS (0.200 g, 0.745 mmol), CuCl
(0.076 g, 0.745 mmol), and DMF (10 mL) were combined in a pro-
cedure analogous to that used for 1-C8-1 (Method B) to give 3-C8-
3 as a light yellow powder in 74% yield (0.107 g, 0.274 mmol).
1H NMR (600 MHz, C6D6): δ = 7.22 (d, JH,H = 8.3 Hz, 4 H of
2ϫC6H4), 6.73 (d, JH,H = 8.3 Hz, 4 H of 2ϫC6H4), 2.27 (t, JH,H
= 7.8 Hz, 4 H of 2ϫCH2), 1.31–1.38 (m, 4 H of 2ϫCH2), 1.16–
1.24 (m, 4 H of 2ϫCH2), 1.06–1.14 (m, 4 H of 2ϫCH2), 0.84 (t,
JH,H = 7.3 Hz, 6 H of 2ϫCH3) ppm. 13C{1H} NMR (150 MHz,
C6D6): δ = 145.6 (s, 2 C-para of 2ϫC6H4), 133.6 (s, 4 C-ortho of
2ϫC6H4), 128.9 (s, 4 C-meta of 2ϫC6H4), 118.0 (s, 2 C-ipso of
Method B: p-CH3OC6H4(CϵC)2TMS (0.054 g, 0.24 mmol), CuCl
(0.023 g, 0.23 mmol), and DMF (5 mL) were combined in a pro-
cedure analogous to that used for 1-C8-1 (Method B) to give 7-C8-
7 as a light yellow powder in 8% yield (0.008 g. 0.026 mmol).
1H NMR (500 MHz, C6D6): δ = 7.21 (d, JH,H = 8.9 Hz, 2 H of
C6H4), 6.40 (d, JH,H = 8.9 Hz, 2 H of C6H4), 3.08 (s, 3 H of
OCH3) ppm. 13C{1H} NMR (125 MHz, C6D6): δ = 160.9 [s, 2 C-
para (CH3OC) of 2ϫC6H4], 134.7 (s, 4 C-ortho of 2ϫC6H4), 114.4
(s, 4 C-meta of 2ϫC6H4), 113.2 (s, 2 C-ipso of 2ϫC6H4), 76.1 (s,
2 C, C6H4CϵCCϵC), 73.5 (s, 2 C, C6H4CϵCCϵC), 71.4 (s, 2 C,
C6H4CϵCCϵC), 68.9 (s, 2 C, C6H4CϵCCϵC), 54.6 (s, 1 C,
2ϫC6H4), 80.9 (s,
2 C, C6H4CϵCCϵC), 74.9 (s, 2 C,
C6H4CϵCCϵC), 68.0 (s, 2 C, C6H4CϵCCϵC), 64.8 (s, 2 C,
C6H4CϵCCϵC), 36.2 (s, 2 C, C6H4CH2CH2), 36.1 (s, 2 C,
CH2CH2CH3), 31.7 (s, 2 C, CH2CH2CH2CH3), 22.8 (s, 2 C,
OCH ) ppm. IR (KBr): ν = 2197 (CϵC), 2074 (CϵC) cm–1.
˜
3
C22H14O2 (310.35): calcd. C 85.14, H 4.55; found C 85.21, H 4.55.
CH CH ), 14.2 (s, 2 C, CH ) ppm. IR (KBr): ν = 2198 (vs),
˜
CϵC
2
3
3
2075 (w) cm–1. MS: m/z = 391 [M]+. C30H30 (390.57): calcd. C
p-C6H5COC6H4CϵCBr (6-C2Br): A 50 mL Schlenk flask was
charged with p-C6H5COC6H4CϵCTMS[16] (0.880 g, 3.16 mmol)
and acetonitrile (25 mL). It was wrapped with aluminum foil and
AgF (0.440 g, 3.47 mmol) was added. After 30 min NBS (0.720 g,
4.10 mmol) was added. The mixture was stirred for 28 h, after
which time a solid precipitated. It was filtered off and solvent was
evaporated from the filtrate. The crude product was extracted with
diethyl ether, which was then washed with water. The organic frac-
tion was dried with MgSO4. After removal of Et2O the product
was additionally purified by flash chromatography (silica gel,
92.26, H 7.74; found C 92.05, H 7.58.
C6H9(CϵC)2TMS
(4-C4TMS):
C6H9CϵCH
(0.200 mL,
1.701 mmol), nBuLi (0.828 mL, 1.87 mmol, 1.1 equiv.), CuI
(0.356 g, 1.87 mmol), EtNH2 (6 mL), and TMSCϵCI (0.287 mL,
1.87 mmol) were combined in a procedure analogous to that used
for 3-C4TMS. The analogous workup gave 4-C4TMS as a brown
liquid in 80% yield (0.275 g, 1.36 mmol). 1H NMR (500 MHz,
CDCl3): δ = 6.31–6.27 (m, 1 H, HC=), 2.13–2.03 (m, 4 H of C6H9),
1.65–1.55 (m, 4 H of C6H9), 0.20 (s, 9 H, SiMe3) ppm. 13C{1H}
NMR (125 MHz, CDCl3): δ = 139.6 (s, 1 C, CH=C), 119.6 (s, 1 C,
1
CH2Cl2) to yield 6-C2Br (0.612 g, 69%) as a beige solid. H NMR
(500 MHz, CDCl3): δ = 7.78 (d, JH,H = 7.5 Hz, 2 H of C6H5), 7.76
(d, JH,H = 8.6 Hz, 2 H of C6H4), 7.60 (t, JH,H = 7.5 Hz, 1 H of
C6H5), 7.55 (d, JH,H = 8.6 Hz, 2 H of C6H4), 7.49 (t, JH,H = 7.5 Hz,
2 H of C6H5) ppm. 13C{1H} NMR (125 MHz, CDCl3): δ = 196.0
(s, 1 C, C=O), 137.8 (s, 1 C-ipso of C6H5), 137.5 (s, 1 C-para of
C6H4), 132.8 (s, 1 C-para of C6H5), 132.1 (s, 2 C-ortho of C6H4),
130.2 (s, 2 C-ortho of C6H5), 130.1 (s, 2 C-meta of C6H4), 128.6 (s,
2 C-meta of C6H5), 127.0 [s, 1 C-ipso (CCϵCBr) of C6H4], 79.6
CH=C), 89.4 (s,
C6H9CϵCCϵC), 79.2 (s, 1 C, C6H9CϵCCϵC), 71.9 (s, 1 C,
C6H9CϵCCϵC), 28.7 (s,
CH=CCH2), 22.2 (s,
CH2CH2CH=C), –0.1 (s, 3 C, SiMe3) ppm. C13H18Si (202.37):
calcd. C 77.16, H 8.97; found C 77.24, H 9.06. GC–MS: m/z = 202
[M]+.
1
C, C6H9CϵCCϵC), 88.4 (s,
1
C,
1
C, CH2CH=C), 26.1 (s,
1
1
C,
C,
1
C, CH=CCH2CH2), 21.4 (s,
C6H9(CϵC)4C6H9 (4-C8-4)
(CϵCBr), 53.6 (ϵCBr) ppm. IR (KBr): ν = 2195 (CϵC), 1652
˜
(C=O) cm–1. HRMS (ESI): calcd. for C15H9OBrNa 306.9729 [M +
Na]+; found 306.9735. C15H9BrO (285.14): calcd. C 63.18, H 3.18;
found C 62.72, H 3.04.
Method A: Compound 4-C4TMS (0.337 g, 1.67 mmol), TBAF
(0.333 mL, 0.333 mmol), ClSiMe3 (0.216 mL, 1.67 mmol), CuCl
(1.65 g, 16.7 mmol), and TMEDA (0.999 mL, 6.66 mmol) were
combined in a procedure analogous to that used for 1-C8-1
(Method A). The analogous workup gave 4-C8-4 as a pale yellow-
brown powder in 65% yield (0.140 g, 0.541 mmol).
p-C6H5COC6H4(CϵC)2TMS (6-C4TMS):
Method A: A 50 mL Schlenk flask was charged with TMSCϵCH
(0.110 mL, 0.78 mmol) and THF (15 mL). The solution was cooled
to –45 °C and nBuLi (2.53 m solution in hexanes, 0.320 mL,
0.81 mmol) was added with stirring. After 15 min, CuCl (0.083 g,
0.84 mmol) was added. The cold bath was removed and after
10 min 6-C2Br (0.210 g, 0.736 mmol), EtNH2 (1 mL, 2.0 mmol),
Method B: Compound 4-C4TMS (0.150 g, 0.760 mmol), CuCl
(0.080 g, 0.812 mmol), and DMF (5 mL) were combined in a pro-
cedure analogous to that used for 1-C8-1 (Method B) to give 4-C8-4
as a pale yellow-brown powder in 25% yield (0.036 g. 0.128 mmol).
1H NMR (300 MHz, CDCl3): 6.38–6.33 (m, 4 H, =CH), 2.12–2.06 Pd(PPh3)2Cl2 (0.026 g, 0.037 mmol), and PPh3 (0.019 g,
(m, 8 H, C6H9), 1.66–1.54 (m, 8 H, C6H9) ppm. 13C{1H} NMR 0.072 mmol) were added with stirring. The mixture was left at room
(75 MHz, C6D6): δ = 141.8 (s, 2 C, CH=C), 119.3 (s, 2 C, CH=C), temperature for 10 min and the solvent was removed under oil
80.2 (s, 2 C, C6H9CϵCCϵC), 73.1 (s, 2 C, C6H9CϵCCϵC), 67.3 pump vacuum. The residue was flash chromatographed (CH2Cl2/
(s, 2 C, C6H9CϵCCϵC), 64.5 (s, 2 C, C6H9CϵCCϵC), 28.2 (s, 2 hexanes 2:1, v/v) to give 6-C4TMS as a beige solid in 49% yield
C, CH2CH=C), 25.8 (s,
2
C, CH=CCH2), 22.1 (s,
2
C,
(0.108 g, 0.36 mmol).
Eur. J. Org. Chem. 0000, 0–0
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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9

Job/Unit: O20554
/KAP1
Date: 18-07-12 17:38:48
Pages: 13
N. Gulia, K. Osowska, B. Pigulski, T. Lis, Z. Galewski, S. Szafert
FULL PAPER
Method B: A Schlenk flask was charged with 6-C2Br (0.776 g,
9.0 Hz, 2 H of C6H4), 7.62 (d, JH,H = 9.0 Hz, 2 H of C6H4), 0.25
2.72 mmol) and THF (30 mL). TMSCϵCH (0.580 mL, (s, 9 H of SiMe3) ppm. 13C{1H} NMR (125 MHz, CDCl3): δ =
4.10 mmol), CuI (0.010 g, 0.050 mmol), and Pd(PPh3)2Cl2 (0.038 g,
0.054 mmol) were added. Diisopropylamine (0.960 mL, 6.79 mmol)
was then added in portions over a period of a few min. The mixture
was stirred at room temperature for 20 h. It was then treated with
saturated NaCl (20 mL) and extracted with Et2O (3ϫ30 mL). The
organic layer was dried with MgSO4 and the solvent was removed
under oil pump vacuum. The residue was flash chromatographed
(silica gel, CH2Cl2/hexanes 2:1, v/v) to give 6-C4TMS as a beige
solid in 51% yield (0.422 g, 1.40 mmol). 1H NMR (500 MHz,
147.8 [s, 1 C, C-para (O2NC) from C6H4], 133.6 (s, 2 C-ortho of
C6H4), 128.6 (s, 1 C-ipso of C6H4), 123.9 (s, 2 C-meta of C6H4),
94.4 (s, 1 C, C6H4CϵCCϵC), 87.1 (s, 1 C, C6H4CϵCCϵC), 79.2
(s, 1 C, C6H4CϵCCϵC), 74.4 (s, 1 C, C6H4CϵCCϵC), –0.4 (s, 3
C, SiMe3) ppm. GC–MS: m/z = 243 [M]+. C13H13NO2Si (243.34):
calcd. C 64.17, H 5.38; found C 63.82, H 5.33.
p-NO2C6H4(CϵC)4-p-C6H4NO2 (7-C8-7)
Method A: Compound 7-C4TMS (0.062 g, 0.254 mmol), TBAF
(0.050 mL, 0.050 mmol), ClSiMe3 (0.032 mL, 0.25 mmol), CuCl
(0.025 g, 0.25 mmol), and TMEDA (0.015 mL, 0.10 mmol) were
combined in a procedure analogous to that used for 1-C8-1
(Method A). THF was used instead of acetone. The analogous
workup gave 7-C8-7 as a light yellow-brown, crystalline powder in
42% yield (0.018 g, 0.053 mmol).
CDCl3): δ = 7.77 (d, JH,H = 7.6 Hz, 2 H of C6H5), 7.75 (d, JH,H
=
8.6 Hz, 2 H of C6H4), 7.59 (t, JH,H = 7.6 Hz, 1 H of C6H5), 7.58
(d, JH,H = 8.6 Hz, 2 H of C6H4), 7.48 (t, JH,H = 7.6 Hz, 2 H of
C6H5), 0.25 (s, 9 H, SiMe3) ppm. 13C{1H} NMR (125 MHz,
CDCl3): δ = 195.8 (s, 1 C, C=O), 137.9 (s, 1 C-ipso of C6H5), 137.3
(s, 1 C-para of C6H4), 132.9 (s, 1 C-para of C6H5), 132.7 (s, 2 C-
ortho of C6H4), 130.1 (s, 2 C-ortho of C6H5), 130.1 (s, 2 C-meta of
C6H4), 128.6 (s, 2 C-meta of C6H5), 125.8 [s, 1 C-ipso (CCϵC) of
C6H4], 92.7 (s, 1 C, C6H4CϵCCϵC), 87.6 (s, 1 C, C6H4CϵCCϵC),
77.1 (s, 1 C, C6H4CϵCCϵC), 75.8 (s, 1 C, C6H4CϵCCϵC), –0.3
Method B: Compound 7-C4TMS (0.029 g, 0.12 mmol), CuCl
(0.012 g, 0.12 mmol), and DMF (5 mL) were combined in a pro-
cedure analogous to that used for 1-C8-1 (Method B) to give 7-C8-
7 as a light yellow solid in 15% yield (0.003 g. 0.009 mmol).
(s, 3 C, SiMe ) ppm. IR (Nujol mull): ν = 2204 (CϵC), 2104
˜
3
1H NMR (500 MHz, C6D6): δ = 7.45 (d, JH,H = 8.9 Hz, 2 H of
C6H4), 6.75 (d, JH,H = 8.90 Hz, 2 H of C6H4) ppm. 13C{1H} NMR
(125 MHz, C6D6): δ = 147.8 [s, 2 C-para (O2NC) from 2ϫC6H4],
133.2 (s, 4 C-ortho of 2ϫC6H4), 127.0 (s, 2 C-ipso of 2ϫC6H4),
123.4 (s, 4 C-meta of 2ϫC6H4), 78.2 (s, 2 C, C6H4CϵCCϵC), 74.3
(s, 2 C, C6H4CϵCCϵC), 73.4 (s, 2 C, C6H4CϵCCϵC), 67.6 (s, 2 C,
(CϵC), 1651 (C=O) cm–1. GC–MS: m/z = 302 [M]+. C20H18OSi
(302.45): calcd. C 79.42, H 6.00; found C 77.56, H 6.02.
p-C6H5COC6H4(CϵC)4-p-C6H4COC6H5 (6-C8-6)
Method A: Compound 6-C4TMS (0.073 g, 0.240 mmol), TBAF
(0.048 mL, 0.048 mmol), ClSiMe3 (0.031 mL, 0.24 mmol), CuCl
(0.024 g, 0.024 mmol), and TMEDA (0.014 mL, 0.09 mmol) were
combined in a procedure analogous to that used for 1-C8-1
(Method A). THF was used instead of acetone. The analogous
workup gave 6-C8-6 as a light yellow-brown, crystalline powder in
71% yield (0.039 g, 0.085 mmol).
C H CϵCCϵC) ppm. IR (KBr): ν
= 2205 (vs), 2105 (s) cm–1.
˜
CϵC
6
4
p-NCC6H4(CϵC)2TMS (8-C4TMS): 4-Ethynylbenzonitrile (0.294,
0.294 g, 2.24 mmol), THF (15 mL), nBuLi (2.53 m solution in THF,
0.975 mL, 1.1 equiv.), CuCl (0.222 g, 2.24 mmol), ICϵCTMS
(0.553 g, 2.467 mmol), and Et2NH (1.5 mL) were combined in a
procedure analogous to that used for 3-C4TMS. The analogous
workup gave 8-C4TMS as a yellow solid in 53% yield (0.268 g,
1.20 mmol). 1H NMR (500 MHz, CDCl3, 7.26 ppm): δ = 7.62–7.59
(m, 2 H of C6H4), 7.54–7.57 (m, 2 H of C6H4), 0.24 (s, 9 H of
SiMe3) ppm. 13C NMR (125 MHz, CDCl3): δ = 133.2 (s, 2 C-ortho
of C6H4), 132.2 (s, 2 C-meta of C6H4), 126.6 (s, 1 C-ipso of C6H4),
118.3 (s, 1 C, CϵN), 112.7 (s, 1 C-para of C6H4), 93.9 (s, 1 C,
C6H4CϵCCϵC), 87.1 (s, 1 C, C6H4CϵCCϵC), 78.4 (s, 1 C,
C6H4CϵCCϵC), 74.6 (s, 1 C, C6H4CϵCCϵC), –0.4 (s, 3 C,
Method B: Compound 6-C4TMS (0.028 g, 0.092 mmol), CuCl
(0.009 g, 0.091 mmol), and DMF (5 mL) were combined in a pro-
cedure analogous to that used for 1 (Method B) to give 6-C8-6 as
a light brown powder in 61% yield (0.013 g. 0.028 mmol).
1H NMR (500 MHz, C6D6): δ = 7.59 (d, JH,H = 7.7 Hz, 2 H, HAr),
7.38 (d, JH,H = 8.5 Hz, 2 H, C6H4), 7.12 (t, JH,H = 7.7 Hz, 1 H,
C6H5), 7.08 (d, JH,H = 8.5 Hz, 2 H, C6H5), 7.02 (t, JH,H = 7.7 Hz,
2 H, C6H5) ppm. 13C{1H} NMR (125 MHz, C6D6): δ = 194.5 (s, 2
C, 2 C=O), 138.8 (s, 2 C-ipso of 2ϫC6H5), 137.5 (s, 2 C-para of
2ϫC6H4), 133.2 (s, 2 C-para of 2ϫC6H5), 132.4 (s, 4 C-ortho of
2ϫC6H4), 130.1 (s, 4 C-ortho of 2ϫC6H5), 130.0 (s, 4 C-meta of
2ϫC6H4), 128.4 (s, 4 C-meta of 2ϫC6H5), 124.0 [s, 2 C-ipso
(CCϵC) of 2ϫC6H4], 77.8 (s, 2 C, C6H4CϵCCϵC), 77.0 (s, 2 C,
C6H4CϵCCϵC), 68.8 (s, 2 C, C6H4CϵCCϵC), 64.8 (s, 2 C,
SiMe ) ppm. IR (KBr): ν = 2106 (CϵC), 2108 (CϵC), 2231
˜
3
(CϵN) cm–1. GC–MS: m/z = 223 [M]+. C14H13NSi (223.35): calcd.
C 75.29, H 5.87; found C 75.30, H 6.02.
p-NCC6H4(CϵC)4-p-C6H4CN (8-C8-8)
Method A: Compound 8-C4TMS (0.046 g, 0.206 mmol), TBAF
(0.206 mL, 0.206 mmol), ClSiMe3 (0.027 mL, 0.207 mmol), CuCl
(0.020 g, 0.206 mmol), and TMEDA (0.012 mL, 0.080 mmol) were
combined in a procedure analogous to that used for 1-C8-1
(Method A). THF was used instead of acetone. The analogous
workup gave 8-C8-8 as a light yellow, crystalline powder in 54%
yield (0.017 g, 0.056 mmol).
C H CϵCCϵC) ppm. IR (KBr): ν
= 2200 (s) cm–1.
˜
CϵC
6
4
p-NO2C6H4(CϵC)2TMS (7-C4TMS): 1-(Bromoethynyl)-4-nitro-
benzene[16,35] (1.26 g, 5.57 mmol), TMSCϵCH (1.19 mL,
8.42 mmol), Pd(PPh3)2Cl2 (0.079 g, 0.11 mmol), CuI (0.021 g,
0.11 mmol), diisopropylamine (1.98 mL, 14.0 mmol), and THF
(80 mL) were combined in a procedure analogous to that used for
6-C4TMS (Method B). The analogous workup gave 7-C4TMS as a
light yellow, crystalline powder in 52% yield (0.714 g, 0.293 mmol).
1H NMR (500 MHz, C6D6): δ = 7.55 (d, JH,H = 9.0 Hz, 2 H of
C6H4), 6.88 (d, JH,H = 9.0 Hz, 2 H of C6H4), 0.11 (s, 9 H of
SiMe3) ppm. 13C{1H} NMR (125 MHz, C6D6): δ = 147.7 [s, 1 C,
Method B: Compound 8-C4TMS (0.038 g, 0.170 mmol), CuCl
(0.017 g, 0.172 mmol), and DMF (5 mL) were combined in a pro-
cedure analogous to that used for 1-C8-1 (Method B) to give 8-C8-
8 as a light yellow powder in 59% yield (0.015 g. 0.050 mmol).
C-para (O2NC) from C6H4], 133.2 (s, 2 C-ortho of C6H4), 127.6 1H NMR (500 MHz, C6D6): δ = 6.69–6.72 (m, 4 H of 2ϫC6H4),
(s, 1 C-ipso of C6H4), 123.5 (s, 2 C-meta of C6H4), 94.1 (s, 1 C,
C6H4CϵCCϵC), 88.0 (s, 1 C, C6H4CϵCCϵC), 79.2 (s, 1 C,
C6H4CϵCCϵC), 74.9 (s, 1 C, C6H4CϵCCϵC), –0.7 (s, 3 C,
6.59–6.62 (m, 4 H of 2ϫC6H4) ppm. 13C NMR (125 MHz, C6D6):
δ = 133.0 (s, 4 C-ortho of 2ϫC6H4), 131.9 (s, 4 C-meta of
2ϫC6H4), 125.2 (s, 2 C-ipso of 2ϫC6H4), 118.0 (s, 2 C, 2ϫCϵN),
113.3 (s, 2 C-para of 2ϫC6H4), 77.6 (s, 2 C, C6H4CϵCCϵC), 74.1
SiMe3) ppm. 1H NMR (500 MHz, CDCl3): δ = 8.19 (d, JH,H
=
10
www.eurjoc.org
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 0000, 0–0

Job/Unit: O20554
/KAP1
Date: 18-07-12 17:38:48
Pages: 13
Mori–Hiyama versus Hay Coupling for Higher Polyynes
ski, T. Bartik, B. Bartik, M. Jaeger, J. A. Gladysz, J. Am. Chem.
(s, 2 C, C6H4CϵCCϵC), 73.8 (s, 2 C, C6H4CϵCCϵC), 67.7 (s, 2 C,
C H CϵCCϵC) ppm. IR (KBr): ν
= 2202 (vs), 2102 (s) cm–1.
˜
CϵC
Soc. 2000, 122, 810–822; f) G.-Y. Xu, G. Zou, Y.-H. Ni, M. C.
DeRosa, R. J. Crutchley, T. Ren, J. Am. Chem. Soc. 2003, 125,
10057–10065; g) W. Mohr, J. Stahl, F. Hampel, J. A. Gladysz,
Chem. Eur. J. 2003, 9, 3324–3340; h) J. Stahl, J. C. Bohling,
E. B. Bauer, T. B. Peters, W. Mohr, J. M. Martín-Alvarez, F.
Hampel, J. A. Gladysz, Angew. Chem. 2002, 114, 1951; Angew.
Chem. Int. Ed. 2002, 41, 1871–1876; i) J. Stahl, W. Mohr, L.
de Quadras, T. B. Peters, J. C. Bohling, J. M. Martín-Alvarez,
G. R. Owen, F. Hampel, J. A. Gladysz, J. Am. Chem. Soc. 2007,
129, 8282–8295.
a) R. D. Adams, B. Qu, M. D. Smith, Organometallics 2002,
21, 3867–3872; b) J. T. Lin, J. J. Wu, C.-S. Li, Y. S. Wen, K.-J.
Lin, Organometallics 1996, 15, 5028–5034; c) K. Kowalski, S.
Domagała, J. Organomet. Chem. 2007, 692, 3100–3103.
a) J. Classen, R. Gleiter, F. Rominger, Eur. J. Inorg. Chem. 2002,
2040–2046; b) T. J. J. Müller, J. Blümel, J. Organomet. Chem.
2003, 683, 354–367.
a) F. Bohlmann, T. Burkhardt, C. Zdero, Naturally Occurring
Acetylenes, Academic Press, New York, NY, 1973; b) J. Lam,
H. Breteler, T. Arnason, L. Hansen (Eds.), Chemistry and Bio-
logy of Naturally Occurring Acetylenes and Related Compounds
(NOARC), Elsevier, New York, 1988; c) R. R. Tykwinski,
A. L. K. Shi Shun, Angew. Chem. 2006, 118, 1050; Angew.
Chem. Int. Ed. 2006, 45, 1034–1057; d) V. Fiandanese, D. Bot-
talico, G. Marchese, A. Punzi, Tetrahedron 2006, 63, 5126–
5132; e) Y.-L. Li, J. Li, N.-L. Wang, X.-S. Yao, Molecules 2008,
13, 1931–1941; f) J. W. Blunt, B. R. Copp, M. H. G. Munro,
P. T. Northcote, M. R. Prinsep, Nat. Prod. Rep. 2003, 20, 1–8;
g) S. López, F. Fernández-Trillo, L. Castedo, C. Saá, Org. Lett.
2003, 5, 3725–3728; h) B. W. Gung, G. Kumi, J. Org. Chem.
2004, 69, 3488–3492.
6
4
C22H8N2 (300.32): calcd. C 87.99, H 2.68; found C 87.81, H 2.74.
Details of X-ray Data Collection and Reduction: X-ray diffraction
data were collected with a KUMA KM4 CCD (ω scan technique)
diffractometer with an Oxford Cryosystem-Cryostream cooler.[37]
The space groups were determined from systematic absences and
subsequent least-squares refinement. Lorentz and polarization cor-
rections were applied. The structures were solved by direct methods
and refined by full-matrix, least-squares on F2 by use of the
SHELXTL Package.[38] Non-hydrogen atoms were refined with an-
isotropic thermal parameters. Hydrogen atom positions were calcu-
lated and added to the structure factor calculations, but were not
refined.
[5]
[6]
[7]
CCDC-876314 (for 1-C8-1), -876313 (for 3-C8-3), -876315 (for 3-
C12-3) and -876312 (for 6-C8-6) contain the supplementary crystal-
lographic data for this paper. These data can be obtained free of
charge from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
Supporting Information (see footnote on the first page of this arti-
cle): NMR spectra of the new butadiynes and octatetraynes.
Acknowledgments
The authors would like to thank the National Science Center
(Grant Nos. N204 136339 and N204 15138) for support of this
research.
[8]
a) C. Glaser, Ber. Dtsch. Chem. Ges. 1869, 2, 422–424; b) P.
Siemsen, R. C. Livingston, F. Diederich, Angew. Chem. 2000,
112, 2740; Angew. Chem. Int. Ed. 2000, 39, 2632–2657.
A. S. Hay, J. Org. Chem. 1962, 27, 3320–3321.
[1] a) M. M. Haley, R. R. Tykwinski (Eds.), From Molecules to
Materials, Wiley-VCH, Weinheim, 2005; b) F. Cataldo (Ed.),
Polyynes: Synthesis Properties and Applications, CRC Press
Taylor & Francis Group, Boca Raton, 2006.
[9]
[10]
a) G. Eglinton, A. R. Galbraith, Chem. Ind. 1956, 737–738; b)
G. Eglinton, A. R. Galbraith, J. Chem. Soc. 1959, 889–896.
a) W. Chodkiewicz, Ann. Agric. Sci. Ann. Chim. Paris 1957, 2,
819–869; b) P. Cadiot, W. Chodkiewicz in Chemistry of Acetyl-
enes (Ed.: H. G. Viehe), Marcel Dekker, New York, 1969, pp.
597–647; c) K. Sonogashira, Handbook of Organopalladium
Chemistry for Organic Synthesis (Ed.: E. Negishi), Wiley-VCH,
New York, 2002, pp. 493–529; d) A. de Meijere, F. Diederich
(Eds.), Metal-Catalyzed Cross-Coupling Reactions, 2nd ed.,
Wiley-VCH, Weinheim, 2004.
a) E. T. Chernick, S. Eisler, R. R. Tykwinski, Tetrahedron Lett.
2001, 42, 8575–8578; b) M. J. Dabdoub, V. B. Dabdoub, E. J.
Lenardão, Tetrahedron Lett. 2001, 42, 1807–1809; c) V. Fiand-
anese, D. Bottalico, G. Marchese, A. Punzi, Tetrahedron Lett.
2003, 44, 9087–9090; d) E.-i. Negishi, N. Okukado, S. F. Lov-
ich, F.-T. Luo, J. Org. Chem. 1984, 49, 2629–2632; e) J. Yan, J.
Wu, H. Jin, J. Organomet. Chem. 2007, 692, 3636–3639; f) Q.
Liu, D. J. Burton, Tetrahedron Lett. 1997, 37, 4371–4374; g) F.
Bellina, A. Carpita, L. Mannocci, R. Rossi, Eur. J. Org. Chem.
2004, 2610–2619; h) S. Wang, L. Yu, P. Li, L. Meng, L. Wang,
Synthesis 2011, 1541–1546; i) T. Gibtner, F. Hampel, J.-P. Gis-
selbrecht, A. Hirsch, Chem. Eur. J. 2002, 68, 408–432.
a) T. Morisaki, T. Luu, R. R. Tykwinski, Org. Lett. 2006, 8,
689–692; b) U. Niedballa in Methoden der Organischen Chemie
(Houben–Weyl) (Eds.: E. Müller), Thieme, Stuttgart, 1977, vol.
V/2a, p. 917; c) W. Hunsmann, Chem. Ber. 1950, 83, 213–217.
a) C. Klinger, O. Vostrowsky, A. Hiesch, Eur. J. Org. Chem.
2006, 1508–1524; b) Q. Zheng, J. C. Bohling, T. B. Peters, A. C.
Frisch, F. Hampel, J. A. Gladysz, Chem. Eur. J. 2006, 12, 6486–
6505; c) W. A. Chalifoux, M. J. Ferguson, R. R. Tykwinski,
Eur. J. Org. Chem. 2007, 1001–1006; d) W. A. Chalifoux, R. R.
Tykwinski, Nature Chem. 2010, 2, 967–971; e) K. West, C.
Wang, A. S. Batsanov, M. R. Bryce, J. Org. Chem. 2006, 71,
8541–8544; f) C. Wang, A. S. Batsanov, K. West, M. R. Bryce,
[2] a) G. Wegner, Z. Naturforsch. B 1969, 24, 824–832; b) U. H. F.
Bunz, Y. Rubin, Y. Tobe, Chem. Soc. Rev. 1999, 28, 107–119;
c) F. Diederich, Y. Rubin, Angew. Chem. 1992, 104, 1123; An-
gew. Chem. Int. Ed. Engl. 1992, 31, 1101–1123; d) R. R. Tyk-
winski, Y. Zhao, Synlett 2002, 1939–1953; e) Y. Xu, M. D.
Smith, M. F. Geer, P. J. Pellechia, J. C. Brown, A. C. Wibowo,
L. S. Shimizu, J. Am. Chem. Soc. 2010, 132, 5334–5335; f) J.
Xiao, M. Yang, J. W. Lauher, F. W. Fowler, Angew. Chem. 2000,
112, 2216; Angew. Chem. Int. Ed. 2000, 39, 2132–2135; g) Y.
Takeoka, K. Asai, M. Rikukawa, K. Sanui, Chem. Commun.
2001, 2592–2593; h) V. Enkelmann, Chem. Mater. 1994, 6,
1337–1340; i) V. Enkelmann, Adv. Polym. Sci. 1984, 63, 91–
136; j) J. L. Foley, L. Li, D. J. Sandman, M. J. Vela, B. M. Fox-
man, R. Albro, C. J. Eckhardt, J. Am. Chem. Soc. 1999, 121,
7262–7263 and references cited therein; k) F. Carré, N. De-
vylder, S. G. Dutremez, C. Guérin, B. J. L. Henner, A. Jolivet,
V. Tomberli, F. Dahan, Organometallics 2003, 22, 2014–2033;
l) H. Irngartinger, M. Skipinski, Tetrahedron 2000, 56, 6781–
6794; m) J. R. Neabo, K. I. S. Tohoundjona, J. F. Morin, Org.
Lett. 2011, 13, 1358–1361; n) S. R. Diegelmann, N. Hartman,
N. Markovic, J. D. Tovar, J. Am. Chem. Soc. 2012, 134, 2028–
2031; o) Y. Nemoto, M. Sano, J. Phys. Chem. B 2011, 115,
12744–12750; p) J. Nagasawa, M. Yoshida, N. Tamaoki, Eur.
J. Org. Chem. 2011, 2247–2255.
[11]
[12]
[13]
[14]
[3] J. Cornil, D. Beljonne, J.-P. Calbert, J.-L. Brédas, Adv. Mater.
2001, 13, 1053–1119.
[4] a) S. Szafert, J. A. Gladysz, Chem. Rev. 2003, 103, 4175–4205;
b) S. Szafert, J. A. Gladysz, Chem. Rev. 2006, 106, PR1–PR33;
c) A. Sakurai, M. Akita, Y. Moro-oka, Organometallics 1999,
18, 3241–3249; d) A. B. Antonova, M. I. Bruce, B. G. Ellis, M.
Gaudio, P. A. Humphrey, M. Jevric, G. Melino, B. K. Nichol-
son, G. J. Perkins, B. W. Skelton, B. Stapleton, A. H. White,
N. N. Zaitseva, Chem. Commun. 2004, 960–961; e) R. Dembin-
Eur. J. Org. Chem. 0000, 0–0
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Job/Unit: O20554
/KAP1
Date: 18-07-12 17:38:48
Pages: 13
N. Gulia, K. Osowska, B. Pigulski, T. Lis, Z. Galewski, S. Szafert
FULL PAPER
Org. Lett. 2008, 10, 3069–3072; g) S. M. E. Simpkins, M. D.
Weller, L. R. Cox, Chem. Commun. 2007, 4035–4037.
[15] Y. Nishihara, K. Ikegashira, K. Hirabayashi, J.-i. Ando, A.
Mori, T. Hiyama, J. Org. Chem. 2000, 65, 1780–1787.
[16] K. Osowska, T. Lis, S. Szafert, Eur. J. Org. Chem. 2008, 4598–
4606.
[17] P. A. A. Klusener, J. C. Hanekamp, L. Brandsma, P.
von Ragué Schleyer, J. Org. Chem. 1990, 55, 1311–1321.
[18] a) G. C. M. Lee, B. Tobias, J. M. Holmes, D. A. Harcourt,
M. E. Garst, J. Am. Chem. Soc. 1990, 112, 9330–9336; b) I.
Deperasin´ska, A. Szemik-Hojniak, K. Osowska, M. F. Rode,
A. Szczepanik, Ł. Wis´niewski, T. Lis, S. Szafert, J. Photochem.
Photobiol., A: Chem. 2011, 217, 299–307.
[19] a) A. Hirsch, O. Vostrowsky, Science Synthesis 2008, 43, 37–
117; b) W. B. Wan, M. M. Haley, J. Org. Chem. 2001, 66, 3893–
3901; c) T. Luu, B. J. Medos, E. R. Graham, D. M. Vallee, R.
McDonald, M. J. Ferguson, R. R. Tykwinski, J. Org. Chem.
2010, 75, 8498–8507; d) P. Bichler, W. A. Chalifoux, S. Eisler,
A. L. K. Shi Shun, E. T. Chernick, R. R. Tykwinski, Org. Lett.
2009, 11, 519–522; e) G. C. M. Lee, B. Tobias, J. M. Holmes,
D. A. Harcourt, M. E. Garst, J. Am. Chem. Soc. 1990, 112,
9330–9336; f) A. L. K. Shi Shun, E. T. Chernick, S. Eisler,
R. R. Tykwinski, J. Org. Chem. 2003, 68, 1339–1347.
[20] In ref.[16] we reported difficulties with the synthesis of 6-C2Br.
The use of a fresh batch of NBS and high-purity solvents al-
lowed the compound to be obtained in good yield.
Kusumi, I. Ohtani, K. Nishiyama, H. Kakisawa, Tetrahedron
Lett. 1987, 28, 3981–3984.
a) I. Nitta, Acta Crystallogr. 1960, 13, 1035–1035; b) T. Wat-
anabé, I. Taguchi, N. Masaki, Acta Crystallogr. 1959, 12, 347–
348.
N. Weisbach, PhD Thesis, Department Chemie und Pharmazie,
University of Erlangen-Nürnberg, Germany, 2011, p. 160.
R. Dembinski, T. Bartik, B. Bartik, M. Jaeger, J. A. Gladysz,
[26]
[27]
[28]
[29]
J. Am. Chem. Soc. 2000, 122, 810–822.
a) H. Fast, H. L. Welsh, J. Mol. Spectrosc. 1972, 41, 203–221;
b) R. K. McMullan, Å. Kvick, P. Popelier, Acta Crystallogr.,
Sect. B 1992, 48, 726–731.
a) M. Tanimoto, K. Kuchitsu, Y. Morino, Bull. Chem. Soc.
Jpn. 1971, 44, 386–391; b) R. Tay, G. F. Metha, F. Shanks, D.
McNaughton, Struct. Chem. 1995, 6, 47–55.
B. F. Coles, P. B. Hitchcock, D. R. M. Walton, J. Chem. Soc.,
Dalton Trans. 1975, 442–445.
D. B. Werz, R. Gleiter, F. Rominger, Organometallics 2003, 22,
843–849.
[30]
[31]
[32]
[33] a) φ is the angle (°) between the line connecting two atoms
(each from one end-group) adjacent to the carbon chain and
the line coming through carbon chain midpoints of the two
neighboring, parallel molecules. b) Offset is defined as a dis-
tance (in Å) by which one of the neighboring, parallel mole-
cules is shifted with regard to the other.
[34] R. Dembinski, T. Lis, S. Szafert, C. L. Mayne, T. Bartik, J. A.
Gladysz, J. Organomet. Chem. 1999, 578, 229–246.
[35] G. Vives, J. M. Guerrero, J. Godoy, S. Khatua, Y.-P. Wang, J. L.
Kiappes, S. Link, J. M. Tour, J. Org. Chem. 2010, 75, 6631–
6643.
[36] Although in some cases it was against the nomenclature rules
we have continued to name the carbon atom (in the phenyl
substituent) directly bound to the alkyne chain as ipso.
[37] Oxford Diffraction (1995–2004), CrysAlisRED Software, Ox-
ford Diffraction, Wrocław, Poland.
[21] a) A. Arcadi, S. Cacchi, G. Fabrizi, F. Marinelli, L. M. Parisi,
J. Org. Chem. 2005, 70, 6213–6217; b) H. Abe, H. Suzuki, Bull.
Chem. Soc. Jpn. 1999, 72, 787–798; c) M. S. Baird, M. Mitra,
J. Chem. Soc., Chem. Commun. 1979, 13, 563–564; d) Z. Chen,
H. Jiang, Y. Li, Ch. Qi, Chem. Commun. 2010, 46, 8049–8051.
[22] a) C. R. Patrick, G. S. Prosser, Nature 1960, 187, 1021–1021;
b) J. Kendall, R. McDonald, M. J. Ferguson, R. R. Tykwinski,
Org. Lett. 2008, 10, 2163–2166.
[23] K. Maruyama, S. Kawabata, Bull. Chem. Soc. Jpn. 1990, 63,
170–175.
[24] N. Matsuzawa, D. A. Dixon, Int. J. Quantum Chem. 1992, 44,
497–515.
[25] a) H. B. Rasmussen, S. B. Christensen, L. P. Kvist, A. Khar-
azmi, A. G. Hanusi, J. Nat. Prod. 2000, 63, 1295–1296; b) T.
[38] G. M. Sheldrick, Acta Crystallogr., Sect. A 2008, 64, 112–122.
Received: April 26, 2012
Published Online: ᭿
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Eur. J. Org. Chem. 0000, 0–0

Job/Unit: O20554
/KAP1
Date: 18-07-12 17:38:48
Pages: 13
Mori–Hiyama versus Hay Coupling for Higher Polyynes
Topochemical 1,n-Polymerization
A series of diaryloctatetraynes was synthe-
sized by Mori–Hiyama and Hay protocols.
Target compounds were isolated and spec-
troscopically characterized. Crystalline
samples were analyzed by X-ray diffraction
methods and the structures were closely
scrutinized to reveal potential for topoch-
emical 1,n-polymerization.
N. Gulia, K. Osowska, B. Pigulski, T. Lis,
Z. Galewski, S. Szafert* ................. 1–13
Mori–Hiyama versus Hay Coupling for
Higher Polyynes
Keywords: Polyynes / Cross-coupling / X-
ray diffraction / Topochemistry / Poly-
merization
Eur. J. Org. Chem. 0000, 0–0
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
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