Studies on the synthesis of macrocyclic allenes by ring closing metathesis and Doering-Moore-Skattebol reaction

Article abstract of DOI:10.1002/ejoc.200500096

Several efficient synthetic approaches to allenic cyclophanes of the general structure 2/3, which are of interest as chiral ligands or host molecules, are described. The combination of the ruthenium-catalyzed ring-closing metathesis and the Doering-Moore-

Full text of DOI:10.1002/ejoc.200500096

FULL PAPER
Studies on the Synthesis of Macrocyclic Allenes by Ring Closing Metathesis
and Doering–Moore–Skattebøl Reaction
Christian E. Janßen[a] and Norbert Krause*[a]
Keywords: Allenes / Cyclophanes / Doering–Moore–Skattebøl synthesis / Macrocycles / Ring-closing metathesis
Several efficient synthetic approaches to allenic cyclophanes
of the general structure 2/3, which are of interest as chiral
ligands or host molecules, are described. The combination
of the ruthenium-catalyzed ring-closing metathesis and the
Doering–Moore–Skattebøl (DMS) reaction using the Seyferth
reagent PhHgCBr3 provided a straightforward access to the
allenic cyclophane 8. The macrocycles 13 and 17 with the
allenic bridge between the aromatic units were also obtained
efficiently by copper-promoted SN2Ј-substitution of propar-
gylic acetates and ring-closing metathesis. Alternatively,
macrocyclic allenes can be synthesized by ring-closing me-
tathesis of α,ω-bisallenes, as was demonstrated by the forma-
tion of the products 20, 21, and 23.
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2005)
Introduction
Due to their unique steric and electronic properties and
high reactivity, allenes have emerged has highly interesting
target molecules in organic synthesis.[1] Among the different
structural types, cyclic allenes have been studied mainly in
terms of their physical properties[2] and their participation
in biological systems, e.g., the neocarzinostatin chromo-
phore.[3] In contrast, the use of (macro)cyclic allenes as chi-
ral ligand or host molecule has found only limited interest
so far.[4,5] Recently, we have reported the synthesis of the
first macrocyclic allene incorporating alternating aromatic
rings and allenic bridges (allenophane 1)[5] which represents
a novel, highly promising type of ligand for transition metal
chemistry. However, due to the rather long linear sequence
of addition and substitution steps used, it is not suitable for
the generation of larger amounts of the allenophane. We
now report the results of a study on shorter, more efficient
routes to allenic cyclophanes of the general structure 2/3
(Figure 1), taking advantage of the ruthenium-catalyzed
ring closing metathesis (RCM) with Grubbs catalyst[6] and
the Doering–Moore–Skattebøl (DMS) reaction (the ad-
dition of a dihalocarbene to an alkene, followed by base-
mediated allene formation).[7]
Figure 1. Allenophane 1 and macrocyclic allenes 2/3.
Results and Discussion
magnesiumoct-1-ene to furnish the desired hydrocarbon 5
with excellent yield (Scheme 1). Ring closing metathesis
with the Grubbs-I catalyst under high dilution conditions
also proceeded with high efficiency to give a 3:2 mixture of
the cyclophanes 6 and 7.[8] The configuration of the newly
formed double bond of these symmetrical molecules was
The first route towards the target molecules 2/3 starts
out from (Z)-4,4Ј-dibromostilbene (4) which was subjected
to a nickel-catalyzed Kumada cross coupling with 8-bromo-
[a] Organic Chemistry II, University of Dortmund,
44221 Dortmund, Germany
3
determined by measurement of the vicinal JHH coupling
Fax: +49-231-755-3884
1
E-mail: norbert.krause@uni-dortmund.de
constant using long-range H,13C correlation with inverse
2322
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
DOI: 10.1002/ejoc.200500096
Eur. J. Org. Chem. 2005, 2322–2329

Macrocyclic Allenes by Ring Closing Metathesis and Doering–Moore–Skattebøl Reaction
FULL PAPER
Scheme 1. Synthesis of macrocyclic allene 8.
detection,[9] which gave values of 11 Hz and 17 Hz for 6 and of the electronic properties and steric accessibility of the
7, respectively. different C–C double bonds. It seems reasonable to assume
Since the reactivity of the bisolefins 6/7 under the usual that the “aliphatic” C–C double bond of 6/7 is more elec-
cyclopropanation conditions (bromoform or chloroform, tron-rich and sterically less hindered, compared to the “aro-
aqueous NaOH, phase-transfer catalyst[7]) was very low, we matic” double bond, and both factors favor the attack of
[10]
treated the mixture with the Seyferth reagent PhHgCBr3
and obtained the desired dibromocyclopropanes as a 3:2
the dibromocarbene at this position.
In order to synthesize macrocycles of type 3 with the
cis/trans mixture which was converted into the 25-mem- allenic bridge between the aromatic units,[7] we used the
bered allene 8[11] by treatment with methyllithium. Remark- well-established copper-promoted SN2Ј-substitution of pro-
ably, a completely regioselective cyclopropanation of the pargyl electrophiles[13,14] as the key step for the generation
“aliphatic” C–C double bond of the bisolefins 6/7 was ob- of the allene moiety (Scheme 2). Addition of the lithium
served. Regioselective dihalocyclopropanations of unsym- acetylide of alkyne 9 to the aldehyde 10 furnished the pro-
metrical, non-conjugated bisolefins have been reported oc- pargylic alcohol 11, which was converted into the corre-
casionally in the literature[12] and were explained in terms sponding acetate with acetanhydride and lithium chloride.
Scheme 2. Synthesis of macrocyclic allene 13.
Eur. J. Org. Chem. 2005, 2322–2329
www.eurjoc.org
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
2323

C. E. Janßen, N. Krause
FULL PAPER
Scheme 3. Synthesis of macrocyclic allene 17.
The SN2Ј-substitution with the magnesium cuprate formed seems to be no precedent for the ring-closing metathesis of
from tBuMgCl and CuI in the presence of LiBr[15] pro- bisallenes. As reference substrates, we first prepared the
ceeded as expected to give the desired allene 12 with 74% α,ω-bisallenes 18 and 19 (by DMS synthesis of hexa-
yield over both steps. Finally, the Grubbs-I catalyst again deca-1,15-diene and octadeca-1,17-diene, respectively)
induced a highly efficient ring-closing metathesis to the and treated them with the Grubbs-I catalyst
macrocyclic allene 13. To the best of our knowledge, this is Cl2(Cy3P)Ru=CHPh under high-dilution conditions
the first example of a ruthenium-catalyzed olefin metathesis (Scheme 4). Gratifyingly, the desired 15- and 17-membered
in the presence of an allenic moiety; gratifyingly, the latter allenes 20 and 21 were isolated with reasonably high yields
turned out to be inert under these conditions. The spectro- of 29% and 57%, respectively. In contrast to this, the analo-
scopic data of 13 indicate the presence of a single isomer gous reaction of bisallene 22 bearing an aromatic spacer
with regard to the olefinic double bond, probably the less (formed from 1,4-dibromobenzene by Kumada coupling
strained (Z) isomer.
with 8-bromomagnesiumoct-1-ene and subsequent DMS
In a similar fashion, we synthesized the allenic macrocy- synthesis with CHBr3/NaOH/MeLi) provided the allenic
cle 17 incorporating a tetrasubstituted allene bridge cyclophane 23 with only 9% yield (besides large amounts of
(Scheme 3). Again, the propargylic alcohol 14 (obtained by polymeric products). Future experiments will have to show
oxidation of the corresponding secondary alcohol and ad- whether this yield difference reflects a dependence on the
dition of phenyllithium) was converted into the allene 15
by esterification and SN2Ј-substitution with a magnesium
cuprate.[15] Double Kumada coupling with 8-bromomagne-
siumoct-1-ene set the stage for the final ring closing metath-
esis of bisolefin 16 which, once more, furnished the desired
allenic cyclophane 17 with high yield, as a 2:1 mixture of
E/Z isomers. The spectroscopic data of the mixture did not
allow an unambiguous assignment of the configuration of
the olefinic double bond. It should be noted that all
attempts to carry out a regioselective DMS synthesis by
treating olefins 13 or 17 with the Seyferth reagent
[10]
PhHgCBr3
failed since only complex mixtures of cyclo-
propanated products were formed.
In order to gain even more flexibility in the introduction
of allenic groups into (functionalized) macrocycles and cy-
clophanes, we also examined the ring-closing metathesis of
α,ω-bisallenes. Whereas a single report on the cross-metath-
esis of mono-substituted allenes (giving symmetrical 1,3-di-
substituted allenes with low to moderate yield in the pres-
ence of the Grubbs-I catalyst)[16,17] has appeared, there Scheme 4. Ring-closing metathesis of bisallenes 18, 19, and 22.
2324
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
Eur. J. Org. Chem. 2005, 2322–2329

Macrocyclic Allenes by Ring Closing Metathesis and Doering–Moore–Skattebøl Reaction
FULL PAPER
and 0.008 mbar to furnish 5.71 g (44%) of (Z)-4,4Ј-dibromostil-
bene (4) as a colorless solid (m.p. 49 °C). The residue was recrys-
tallized from ethanol to provide 4.99 g (39%) of (E)-4,4Ј-dibro-
mostilbene as a colorless solid (m.p. 210 °C).
ring strain of the allenic macrocycle formed in the ring-
closing metathesis.
1
(E)-4,4Ј-Dibromostilbene: H NMR: δ = 7.48 (d, J = 8.5 Hz, 4 H,
Conclusions
Ar-H), 7.36 (d, J = 8.5 Hz, 4 H, Ar-H), 7.02 (s, 2 H). 13C NMR:
Three different approaches to allenic cyclophanes of the δ = 137.4 (×), 133.3 (+), 129.6 (+), 129.5 (+), 123.0 (×). IR (KBr):
ν = 3013, 1585 cm–1. EI-MS: m/z (%) = 338 (100) [M+], 178 (97).
HR-EI-MS: calcd. for C14H10Br2: 335.9149, found 335.9112.
˜
general structure 2/3 are described in this paper. By combi-
nation of the ruthenium-catalyzed ring-closing metathesis
and the Doering–Moore–Skattebøl (DMS) reaction using
the Seyferth reagent PhHgCBr3, the allenic cyclophane 8
was assembled in a straightforward manner. The second ap-
proach to the macrocycles 13 and 17 with the allenic bridge
between the aromatic units took advantage of the copper-
promoted SN2Ј-substitution of propargylic acetates and
ring-closing metathesis. A third alternative, which might be
particular useful for accessing functionalized allenic macro-
cycles, involves the ring-closing metathesis of α,ω-bisallenes;
by using simple test substrates, the products 20, 21, and 23
were obtained with low to average yields. Current studies
are devoted towards the improvement of the efficiency of
the allene ring-closing metathesis, the stereoselective syn-
thesis of allenic macrocycles of the structure 2/3, and their
use as ligands in the formation of transition metal com-
plexes.
1
(Z)-4,4Ј-Dibromostilbene (4): H NMR: δ = 7.36 (d, J = 7.7 Hz, 4
H, Ar-H), 7.09 (d, J = 7.7 Hz, 4 H, Ar-H), 6.55 (s, 2 H). 13C NMR:
δ = 135.6 (×), 131.5 (+), 130.4 (+), 129.7 (+), 121.2 (×). IR (KBr):
ν = 3005, 1636 cm–1. EI-MS: m/z (%) = 338 (78) [M+], 178 (100).
˜
HR-EI-MS: calcd. for C14H10Br2: 335.9149, found 335. 9137.
(Z)-4,4Ј-Bis(oct-7-en-1-yl)stilbene (5): A solution of 8-bromooct-1-
ene[20] (9.20 g, 45.0 mmol) in THF (15 mL) was added dropwise to
magnesium turnings (1.27 g, 52.2 mmol) in THF (30 mL). After the
exothermic reaction had ceased, the mixture was heated at reflux
for 90 min. It was then cooled to room temperature and added
dropwise to a suspension of 4 (6.25 g, 18.5 mmol) and 1,3-bis(di-
phenylphosphanyl)propanenickel(ii) chloride (260 mg, 0.48 mmol)
in diethyl ether (40 mL). After the exothermic reaction, the solution
was heated at reflux for 3 h and stirred at room temperature for
another 10 h. Addition of pentane (40 mL) was followed by stirring
of the mixture under air for 2 h and filtration through silica gel
(elution with pentane). The filtrate was concentrated in vacuo, and
the crude product was purified by dry column chromatography (cy-
clohexane/ethyl acetate, 20:1) to give 6.80 g (91%) of 5 as a color-
1
less oil. H NMR: δ = 7.21 (d, J = 8.3 Hz, 4 H, Ar-H), 7.05 (d, J
Experimental Section
= 8.3 Hz, 4 H, Ar-H), 6.53 (s, 2 H), 5.87 (ddt, J = 16.9/10.3/6.8 Hz,
2 H), 5.02 (dd, J = 16.9/2.0 Hz, 2 H, C=CH2), 4.97 (dd, J = 10.1/
2.0 Hz, 2 H, C=CH2), 2.58 (t, J = 7.5 Hz, 4 H), 2.09–2.00 (m, 4
H), 1.66–1.55 (m, 4 H), 1.43–1.25 (m, 12 H). 13C NMR: δ = 141.9
(×), 139.3 (+), 134.1 (×), 129.7 (+), 128.9 (+), 128.3 (+), 114.4 (–),
General Remarks: All reactions were carried out under an argon
atmosphere using oven-dried glassware. THF and diethyl ether
were distilled from sodium benzophenone ketyl. Lithium bromide
was dried in vacuo at 120 °C and stored under an argon atmo-
sphere. All other commercially available starting materials were
used without further purification. The products were purified by
column chromatography with Macherey&Nagel silica gel 60 (230–
400 mesh) or by radial chromatography using a Harrison Research
8924 Chromatotron. Melting points were determined with a Büchi
510 capillary melting point apparatus and are uncorrected. 1H and
proton-decoupled 13C NMR spectra were recorded with a Bruker
DRX-400 spectrometer (400 MHz for protons, 100 MHz for car-
bon atoms) at room temperature in CDCl3. Chemicals shifts were
determined relative to the residual solvent peaks (CHCl3: δ = 7.26
for protons, δ = 77.0 for carbon atoms). Carbon atoms were as-
signed with DEPT experiments [symbols used: (+) for CH3,CH;
(–) for CH2; (×) for Cquat.]. Peaks for the major isomer of a mixture
are marked with an asterisk (*). IR spectra were obtained with a
Bruker IFS66 FT-IR spectrometer using KBr pellets or thin films
between KBr plates. EI mass spectra (70 eV) and high-resolution
mass spectra (HRMS) were measured with a Finnigan MAT 8230
or a Jeol SX102A spectrometer.
35.8 (–), 33.9 (–), 31.41 (–), 29.3 (–), 29.1 (–), 29.0 (–). IR (neat): ν
˜
= 3012, 2928, 1640, 1463 cm–1. EI-MS: m/z (%) = 400 (100) [M+],
111 (25). HR-EI-MS: calcd. for C30H40: 400.3130, found 400.3134.
(Z,Z)- and (1Z,15E)-[2.14]Paracyclophan-1,15-diene (6/7): To a re-
fluxing suspension of benzylidenedichlorobis(tricyclohexylphos-
phanyl)ruthenium (0.15 g, 0.18 mmol) in CH2Cl2 (400 mL) was
added dropwise within 6 h a solution of 5 (2.03 g, 5.03 mmol) in
CH2Cl2 (600 mL). During the reaction, the Grubbs-I catalyst
(4×100 mg) was added after 2, 4, 6, and 8 h. After 10 h reaction
time, the mixture was cooled to room temperature, silica gel (5 g)
was added, and the solvent was removed in vacuo. The remaining
loaded silica gel was used in dry column chromatography (pentane/
diethyl ether, 1:1, then CH2Cl2) to give 1.10 g (58%) of 6 and 0.65 g
(34%) of 7 as colorless oils.
1
(Z,Z)-[2.14]Paracyclophan-1,15-diene (6): H NMR: δ = 7.19 (d, J
= 8.3 Hz, 4 H, Ar-H), 7.04 (d, J = 8.3 Hz, 4 H, Ar-H), 6.52 (s, 2
H, 1-H, 2-H), 5.38 (m, 2 H, 15-H, 16-H), 2.56 (t, J = 7.7 Hz, 4 H),
2.05–1.91 (m, 4 H), 1.65–1.52 (m, 4 H), 1.40–1.20 (m, 12 H). 13C
NMR: δ = 141.8 (×), 134.7 (×), 130.3 (+), 129.5 (+), 128.7 (+),
128.2 (+), 35.7 (–), 32.6 (–), 31.3 (–), 29.5 (–), 29.2 (–), 29.0 (–). IR
(E)- and (Z)-4,4Ј-Dibromostilbene:[18] Sodium hydride (5.88 g, 0.147
mol) was added at 0 °C to a suspension of (4-bromobenzyl)tri-
phenylphosphonium bromide[18,19] (20.0 g, 38.3 mmol) in THF
(100 mL). The suspension was heated at reflux for 1 h and then
cooled to room temperature. A solution of 4-bromobenzaldehyde
(7.08 g, 38.2 mmol) in THF (50 mL) was added dropwise, and the
mixture was stirred for 6 h at room temperature, followed by ad-
dition of water (50 mL). After extraction with pentane (150 mL),
the organic layer was dried with Na2SO4 and concentrated in
vacuo; the residue was subjected to a vacuum sublimation at 90 °C
(neat): ν = 3017, 2926, 1652 cm–1. EI-MS: m/z (%) = 372 (100)
˜
[M+], 97 (45). HR-EI-MS: calcd. for C28H36: 372.2817, found
372.2825.
(1Z,15E)-[2.14]Paracyclophan-1,15-diene (7): 1H NMR: δ = 7.04 (d,
J = 8.0 Hz, 4 H, Ar-H), 7.00 (d, J = 8.0 Hz, Ar-H), 6.64 (s, 2 H,
1-H, 2-H), 5.40 (m, 2 H, 15-H, 16-H), 2.59 (t, J = 6.9 Hz, 4 H),
2.06–1.92 (m, 4 H), 1.65–1.54 (m, 4 H), 1.40–1.15 (m, 12 H). 13C
Eur. J. Org. Chem. 2005, 2322–2329
www.eurjoc.org
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
2325

C. E. Janßen, N. Krause
FULL PAPER
NMR: δ = 141.3 (×), 135.0 (×), 130.6 (+), 130.3 (+), 128.7 (+),
17.0 Hz, 1 H, C=CH2), 4.95 (d, J = 10.2 Hz, 1 H, C=CH2), 2.59
128.3 (+), 34.6 (–), 32.2 (–), 30.5 (–), 29.3 (–), 27.9 (–), 27.5 (–). IR (t, J = 7.5 Hz, 2 H), 2.05 (m, 2 H), 1.65–1.55 (m, 2 H), 1.42–1.27
(neat): ν = 3013, 2925, 2853, 1652 cm–1. EI-MS: m/z (%) = 372 (m, 6 H), 0.26 (s, 9 H). 13C NMR: δ = 143.5 (×), 139.0 (+), 131.9
˜
(100) [M+], 97 (40). HR-EI-MS: calcd. for C28H36: 372.2817, found
372.2788.
(+), 128.3 (+), 120.3 (×), 114.2 (–), 105.4 (×), 93.2 (×), 35.8 (–),
33.7 (–), 31.1 (–), 29.0 (–), 28.9 (–), 28.8 (–), 0.0 (+). IR (neat): ν =
˜
2928, 2158, 1641 cm–1. EI-MS: m/z (%) = 284 (100) [M+], 269 (90).
(Z)-[2.15]Paracyclophan-1,15,16-triene (8): To a solution of the 3:2
mixture of 6/7 (200 mg, 0.54 mmol) in benzene (3 mL) was added
HR-EI-MS: calcd. for C19H28Si: 284.1960, found 284.1955.
[10]
PhHgCBr3 (454 mg, 0.86 mmol), and the mixture was heated at
1-Ethynyl-4-(oct-7-en-1-yl)benzene (9): A solution of 1-(trimethylsi-
lylethynyl)-4-(oct-7-en-1-yl)benzene (1.89 g, 6.64 mmol) in meth-
anol (10 mL) was treated with K2CO3 (500 mg) and stirred for 1 h.
reflux for 6 h. The solvent was removed at 40 °C under reduced
pressure, and the residue was treated with petroleum ether and
CH2Cl2 (20:1). Filtration was followed by removal of the solvent After addition of brine (100 mL) and diethyl ether (100 mL), the
in vacuo and purification of the crude product by radial
chromatography (petroleum ether/CH2Cl2, 20:1). The resulting di-
bromocyclopropane (90 mg) was dissolved in diethyl ether (10 mL),
and to the cooled solution (–78 °C) was added MeLi (0.14 mL,
0.2 mmol, 1.39 m solution in diethyl ether) dropwise within 10 min.
After warming to 0 °C, water (10 mL) was added, and the mixture
was washed with diethyl ether (2×20 mL). The combined organic
layers were dried with Na2SO4 and the solvent was removed in
vacuo. The crude product was purified by radial chromatography
(petroleum ether/CH2Cl2, 20:1) to yield 43 mg (21% over both
steps) of 8 as a colorless solid (m.p. 104 °C). 1H NMR: δ = 7.07
(d, J = 8.3 Hz, 4 H, Ar-H), 7.00 (d, J = 8.3 Hz, 4 H, Ar-H), 6.60
organic layer was separated and washed with water (2×50 mL) and
brine (2×50 mL). Drying with Na2SO4 was followed by concentra-
tion to 20 mL under reduced pressure, filtration through a short
plug of silica gel, and removal of the solvent under reduced pres-
sure, affording 1.37 g (97%) of 9 as a reddish oil. 1H NMR: δ =
7.41 (d, J = 8.0 Hz, 2 H, Ar-H), 7.13 (d, J = 8.0 Hz, 2 H Ar-H),
5.81 (ddt, J = 17.1/10.3/6.8 Hz, 1 H), 5.00 (d, J = 17.1 Hz, 1 H,
C=CH2), 4.94 (d, J = 10.3 Hz, 1 H, C=CH2), 3.04 (s, 1 H), 2.61 (t,
J = 7.4 Hz, 2 H), 2.05 (m, 2 H), 1.63–1.54 (m, 2 H), 1.41–1.23 (m,
6 H). 13C NMR: δ = 143.9 (×), 139.1 (+), 132.0 (+), 128.4 (+),
119.2 (×), 114.2 (–), 83.8 (×), 76.4 (+), 35.8 (–), 33.7 (–), 31.1 (–),
29.0 (–), 28.9 (–), 28.8 (–). IR (neat): ν = 3299, 2927, 2109,
˜
(s, 2 H, 1-H, 2-H), 5.38 (qi, J = 4.7 Hz, 2 H, 15-H, 17-H), 2.59 (t, 1641 cm–1. EI-MS: m/z (%) = 212 (17) [M+], 115 (100). HR-EI-MS:
J = 6.9 Hz, 4 H), 1.96–1.80 (m, 4 H), 1.59 (tt, J = 7.1/7.3 Hz, 4 H),
1.40–1.15 (m, 12 H). 13C NMR: δ = 203.6 (×, C-16), 141.3 (×),
134.9 (×). 130.1 (+), 128.8 (+), 128.3 (+), 91.5 (+, C-15, C-17), 34.9
calcd. for C16H20: 212.1565, found 212.1565.
4-(Oct-7-en-1-yl)benzaldehyde (10): To a stirred solution of 1-
bromo-4-(oct-7-en-1-yl)benzene (6.00 g, 22.5 mmol) in THF
(25 mL) was added dropwise nBuLi (22 mL, 33 mmol, 1.5 m solu-
tion in hexane) at –78 °C. Stirring at this temperature was contin-
ued for 1 h before addition of N,N-dimethylformamide (6.56 g,
89.8 mmol) in THF (20 mL). After warming up to room tempera-
ture the mixture was hydrolyzed with 6 n hydrochloric acid (50 mL)
and diluted with diethyl ether (100 mL). The mixture was then neu-
tralized with a satd. NaHCO3 solution. The organic layer was sepa-
rated, washed with water (4×50 mL), and dried with Na2SO4. The
solvent was removed under reduced pressure to furnish 4.10 g
(–), 30.4 (–), 28.5 (–), 28.9 (–), 28.7 (–), 27.7 (–). IR (KBr): ν =
˜
3018, 2925, 1957, 1606 cm–1. EI-MS: m/z (%) = 384 (100) [M+], 219
(78). HR-EI-MS: calcd. for C29H36: 384.2817, found 384.2818.
1-Bromo-4-(oct-7-en-1-yl)benzene:
From
8-bromooct-1-ene[20]
(6.90 g, 36.0 mmol) in diethyl ether (40 mL), magnesium turnings
(0.88 g, 36.0 mmol) in diethyl ether (20 mL), 1,1Ј-bis(diphenylphos-
phanyl)ferrocenepalladium(ii) chloride (386 mg, 0.45 mmol) and
1,4-dibromobenzene (7.10 g, 30.4 mmol) in THF (10 mL) accord-
ing to the synthesis of 5. The crude product was purified by dry
column chromatography (pentane); yield: 6.90 g (87%) of 1-bromo-
1
(84%) of 10 as a colorless oil. H NMR: δ = 9.96 (s, 1 H, CHO),
1
4-(oct-7-en-1-yl)benzene as a colorless oil. H NMR: δ = 7.40 (d,
7.79 (d, J = 8.0 Hz, 2 H, Ar-H), 7.33 (d, J = 8.0 Hz, 2 H, Ar-H),
5.80 (ddt, J = 17.0/10.2/6.2 Hz, 1 H), 4.98 (d, J = 17.0 Hz, 1 H,
C=CH2), 4.93 (d, J = 10.2 Hz, 1 H, C=CH2), 2.68 (t, J = 8.2 Hz,
2 H), 2.07–1.95 (m, 2 H,), 1.64–1.47 (m, 2 H), 1.36–1.21 (m, 6 H).
J = 8.2 Hz, 2 H, Ar-H), 7.06 (d, J = 8.2 Hz, 2 H, Ar-H), 5.83 (ddt,
J = 17.1/10.1/6.5 Hz, 1 H), 5.02 (dd, J = 17.1/1.5 Hz, 1 H, C=CH2),
4.96 (dd, J = 10.1/1.5 Hz, 1 H, C=CH2), 2.57 (t, J = 8.0 Hz, 2 H),
2.06 (td, J = 7.2/6.5 Hz, 2 H), 1.61 (m, 2 H), 1.36 (m, 6 H). 13C 13C NMR: δ = 191.9 (+, CHO), 150.3 (×), 138.9 (+), 134.4 (×),
NMR: δ = 141.7 (×), 139.2 (+), 131.2 (+), 130.1 (+), 119.3 (×),
129.8 (+), 129.0 (+), 114.2 (–), 36.1 (-,), 33.6 (–), 30.9 (–), 29.0 (–),
114.2 (–), 35.3 (–), 33.7 (–), 31.2 (–), 29.0 (–), 28.9 (–), 28.8 (–). IR
28.8 (–), 28.7 (–). IR (neat): ν = 2928, 1702, 1640 cm–1. EI-MS:
˜
(neat): ν = 2927, 1640, 1073 cm–1. EI-MS: m/z (%) = 266/268 (33) m/z (%) = 216 [M+, 97], 132 (100). HR-EI-MS: calcd. for C15H20O:
˜
[M+], 182 (62), 171 (100). HR-EI-MS: calcd. for C14H19Br:
266.0670, found 266.0653.
216.1514, found 216.1515.
1,3-Bis[(4-oct-7-en-1-yl)phenyl]prop-2-yn-1-ol (11): To
a stirred
1-(Trimethylsilylethynyl)-4-(oct-7-en-1-yl)benzene:
bis(diphenylphosphanyl)palladium(ii) chloride
0.29 mmol), 1,3-dimesityl-4,5-dihydro-1H-imidazolium chloride
(256 mg, 0.75 mmol) and diisopropylamine (15 mL) was heated at
reflux for 1 h. To this suspension were added copper(i) iodide
(142 mg, 0.75 mmol) and 1-bromo-4-(oct-7-en-1-yl)benzene
A
mixture of
(210 mg,
solution of 9 (647 mg, 3.05 mmol) in THF (5 mL) was added drop-
wise LDA (1.68 mL, 3.36 mmol, 2 m suspension in hexane) at
–78 °C. The mixture stirred for 1 h at –50 °C, followed by addition
of 10 (660 mg, 3.05 mmol) in THF (2 mL). After stirring for 12 h
at room temperature, the mixture was hydrolyzed with water
(50 mL) and washed with diethyl ether (3×50 mL). The combined
(3.28 g, 12.3 mmol). Then trimethylsilylacetylene (2.21 g, organic layers were dried with Na2SO4 and the solvent was re-
22.4 mmol) was added dropwise within 10 min, and the mixture
was heated at reflux for 2 h. After cooling to room temperature
moved under reduced pressure. The crude product was purified by
radial chromatography (pentane/CH2Cl2), providing 887 mg (60%)
and removal of the solvent in vacuo, cyclohexane (200 mL) was of 11 as a colorless oil. 1H NMR: δ = 7.53 (d, J = 8.0 Hz, 2 H,
added, and the mixture was filtered through a short pad of silica
gel. The solvent was removed in vacuo to give 3.48 g (99%) of 1-
(trimethylsilylethynyl)-4-(oct-7-en-1-yl)benzene as a pale yellow oil.
Ar-H), 7.39 (d, J = 8.0 Hz, 2 H, Ar-H), 7.22 (d, J = 8.0 Hz, 2 H,
Ar-H), 7.13 (d, J = 8.0 Hz, 2 H, Ar-H), 5.81 (m, 2 H), 5.65 (d, J
= 6.1 Hz, 1 H), 5.00 (d, J = 17.1 Hz, 2 H), 4.94 (d, J = 10.3 Hz, 2
1H NMR: δ = 7.39 (d, J = 7.9 Hz, 2 H, Ar-H), 7.11 (d, J = 7.9 Hz, H), 2.61 (m, 4 H,), 2.27 (d, J = 6.1 Hz, 1 H), 2.05 (m, 4 H), 1.65–
2 H, Ar-H), 5.81 (ddt, J = 17.0/10.2/6.6 Hz, 1 H), 5.00 (d, J = 1.54 (m, 4 H), 1.42–1.26 (m, 12 H). 13C NMR: δ = 143.6 (×), 143.2
2326
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
Eur. J. Org. Chem. 2005, 2322–2329

Macrocyclic Allenes by Ring Closing Metathesis and Doering–Moore–Skattebøl Reaction
FULL PAPER
(×), 139.1 (+), 139.0 (+), 138.1 (×), 131.6 (+), 128.7 (+), 128.4 (+), 128.3 (+), 123.1 (×), 122.5 (×), 121.0 (×), 89.3 (×), 85.8 (×), 64.4
126.7 (+), 119.6 (×), 114.2 (–), 114.1 (–), 88.2 (×), 86.7 (×), 65.0 (+). IR (neat): ν = 3390, 3084, 2201 cm–1. EI-MS: m/z (%) = 285/
˜
(+), 35.8 (–), 35.6 (–), 33.8 (–), 33,7 (–), 31.4 (–), 31.1 (–), 29.1 (–),
287 (3, M+-Br), 77 (100). HR-EI-MS: calcd. for C15H10Br2O:
29.0 (–), 28.9 (–), 28.8 (–), 28.7 (–), 28.6 (–). IR (neat): ν = 3408, 363.9098, found 363.9068.
˜
2928, 2159, 1640 cm–1. EI-MS: m/z (%) = 428 (6) [M+], 411 (100).
HR-EI-MS: calcd. for C31H40O: 428.3079, found 428.3107.
1,3-Bis(4-bromophenyl)-1-phenylprop-2-yn-1-ol (14): A mixture of
1,3-bis(4-bromophenyl)prop-2-yn-1-ol (4.00 g, 10.9 mmol) and IBX
(4.59 g, 16.4 mmol) in DMSO (15 mL) was stirred for 3 h at room
1-{1-(1,1-Dimethylethyl)-3-[4-(oct-7-en-1-yl)phenyl]propa-1,2-dienyl}-
4-(oct-7-en-1-yl)benzene (12): A mixture of 11 (177 mg, 0.41 mmol), temperature. Addition of water (100 mL) was followed by extrac-
LiCl (150 mg, 3.5 mmol) and acetanhydride (10.1 g, 97.9 mmol) tion with diethyl ether (3×50 mL), washing of the combined or-
was stirred for 12 h at room temperature. Hydrolysis with a satd.
NaHCO3 solution (200 mL) was followed by extraction with di-
ethyl ether (3×50 mL). The combined organic layers were dried
with Na2SO4 and the solvent was in vacuo. The crude product was
purified by radial chromatography (cyclohexane/ethyl acetate, 4:1),
affording the acetate of 11 (157 mg, 82%) as a colorless oil. To a
solution of LiBr (443 mg, 5.1 mmol) and CuI (974 mg, 5.1 mmol)
in THF (8 mL) was added dropwise at 0 °C tBuMgCl (3.2 mL,
5.1 mmol, 1.6 m solution in diethyl ether). After stirring for 10 min
at 0 °C, the above mentioned acetate (401 mg, 0.81 mmol) in THF
(2 mL) was added dropwise. The mixture was stirred for 30 min at
0 °C. A satd. NH4Cl solution (containing 15% conc. ammonia)
and diethyl ether (40 mL) were added, the organic phase was sepa-
rated and washed with the NH4Cl/NH3 solution until the aqueous
layer remained colorless. The organic layer was dried with Na2SO4
and the solvent was removed under reduced pressure. The crude
product was purified by flash chromatography (cyclohexane/ ethyl
acetate, 5:1), providing 361 mg (90%) of 12 as a colorless oil. 1H
NMR: δ = 7.22 (m, 4 H,), 7.09 (m, 4 H), 6.18 (s, 1 H), 5.79 (m, 2
H), 4.98 (m, 2 H), 4.92 (m, 2 H), 2.56 (t, J = 7.7 Hz, 2 H, 2.03 (m,
4 H), 1.63–1.54 (m, 4 H), 1.41–1.28 (m, 12 H), 1.21, (s, 9 H,
(CH3)3C). 13C NMR: δ = 209.7 (×), 141.4, 141.3(×), 139.1 (+),
134.5 (×), 132.7 (×), 129.0 (+), 128.7 (+), 127.9 (+), 126.3 (+), 119.5
(×), 114.2 (–), 94.8 (+), 35.6 (–), 35.5 (–), 35.2 (×), 33.8 (–), 31.4
(–), 31.3 (–), 30.0 (+), 29.2 (–), 29.1 (–), 29.0 (–), 28.8 (–). IR (neat):
ganic layers with brine (4×50 mL) and filtration through a plug of
silica gel and Na2SO4. The solvent was removed under reduced
pressure and the residue was crystallized from ethanol to furnish
1,3-bis(4-bromophenyl)prop2-yn-1one (2.51 g, 64%) as a pale
brown solid (m.p. 178 °C). To a solution of 1,3-bis(4-bromophenyl)
prop2-yn-1one (0.31 g, 0.82 mmol) in THF (3 mL) was added
dropwise at –50 °C PhLi (0.47 mL, 0.94 mmol, 2 m in cyclohexane/
diethyl ether). The mixture was stirred for 2 h at –50 °C and then
warmed up to room temperature. It was hydrolyzed with a satd.
NH4Cl solution and washed with diethyl ether (3×50 mL). The
combined organic layers were washed with brine (2×30 mL) and
dried with Na2SO4. The solvent was removed in vacuo affording
0.35 g (96%) of 14 as a pale yellow oil. 1H NMR: δ = 7.64–7.30
(m, 13 H), 2.94 (s, 1 H, OH). 13C NMR: δ = 144.2 (×), 143.9 (×),
133.1 (+), 131.6 (+), 131.3 (+), 128.4 (+), 128.0 (+), 127.7 (+), 125.8
(+), 123.1 (×), 121.9 (×), 121.0 (×), 92.1 (×), 86.3 (×), 74.3 (×). IR
(neat): ν = 3407, 3060, 2223 cm–1. EI-MS: m/z (%) = 442 (1) [M+],
˜
363 (3), 98 (100). HR-EI-MS: calcd. for C21H14Br2O: 439.9411,
found 439.9448.
1-Bromo-4-[3-(4-bromophenyl)-1-(1,1-dimethylethyl)-3-phenylpropa-
1,2-dienyl]benzene (15): To
a
mixture of acetyl bromide
(0.15 g,1.2 mmol), triethylamine (0.15 g, 1.4 mmol) and 4-(N,N-di-
methylamino)pyridine (8 mg, 0.07 mmol) in CH2Cl2 (5 mL) was
added 14 (0.29 g, 0.65 mmol). After stirring for 12 h at room tem-
perature, water (5 mL) was added, and the mixture was washed
with diethyl ether (3×50 mL). The combined organic layers were
washed with brine and dried with Na2SO4. The solvent was re-
moved under reduced pressure and the crude product was purified
by flash chromatography (cyclohexane/ethyl acetate, 5:1) to furnish
0.19 g (60%) of the acetate of 14 as a reddish oil. According to the
synthesis of 12, the acetate (0.34 g, 0.70 mmol) was treated with
LiBr (0.37 g, 4.2 mmol) and CuI (0.80 g (4.2 mmol) in THF (8 mL),
tBuMgCl (2.6 mL, 4.2 mmol, 1.6 m solution in diethyl ether). The
crude product was purified by flash chromatography (cyclohexane/
ethyl acetate, 4:1); yield: 0.23 g (68%) of 15 as a pale yellow oil. 1H
ν = 2928, 1942, 1641 cm–1. EI-MS: m/z (%) = 468 (13) [M+], 411
˜
(100). HR-EI-MS: calcd. for C35H48: 468.3756, found 468.3743.
1-(1,1-Dimethylethyl)[3.14]paracyclophan-1,2,16-triene (13): To a re-
fluxing solution of 12 (100 mg, 0.21 mmol) in CH2Cl2 (70 mL) was
added benzylidenedichlorobis(tricyclohexylphosphanyl)ruthenium
(27 mg, 0.03 mmol), and refluxing was continued for 6 h. After
cooling to room temperature, the solvent was removed under re-
duced pressure and the crude product was purified by flash
chromatography (hexane/ethyl acetate, 25:1) to give 78 mg (84%)
of 13 as a colorless oil. 1H NMR: δ = 7.20 (m, 4 H), 7.07 (m, 4
H,), 6.17 (s, 1 H), 5.34 (m, 2 H), 2.53, (t, J = 7.6 Hz, 4 H), 1.93 NMR: δ = 7.64–7.15 (m, 13 H, Ar-H), 1.22 (s, 9 H, (CH3)3C). 13C
(m, 4 H), 1.56 (m, 4 H) 1.35–1.24 (m, 12 H), 1.19 (s, 9 H, NMR: δ = 202.6 (×), 136.6 (×), 136.3 (×), 135.8 (×), 131.4 (+),
(CH3)3C). 13C NMR: δ = 202.9 (×), 141.3 (×), 141.2 (×), 134.4 (×),
131.0 (+), 130.9 (+), 129.6 (+), 128.6 (+), 128.4 (+), 127.9 (+), 121.0
(×), 120.8 (×), 118.1 (×), 109.1 (×), 35.7 (×), 29.6 (+). IR (neat): ν
132.6 (×), 130.2 (+), 128.9 (+), 128.6 (+), 127.8 (+), 126.2 (+), 119.4
˜
(×), 94.7 (+), 35.6 (–), 35.5 (–), 35.1 (×), 32.5 (–), 31.4, 31.3 (–), = 3059, 1939 cm–1. EI-MS: m/z (%) = 482 (12) [M+], 425 (100).
29.9 (+), 29.5 (–), 29.1 (–), 29.0 (–), 28.9 (–). IR (neat): ν = 2970,
HR-EI-MS: calcd. for C25H22Br2: 480.0088, found 480.0086.
˜
2928, 1937 cm–1. EI-MS: m/z (%) = 440 (32) [M+], 383 (100). HR-
1-{1-(1,1-Dimethylethyl)-3-[4-(oct-7-en-1-yl)phenyl]-3-phenylpropa-
1,2-dienyl}-4-(oct-7-en-1-yl)benzene (16): According to the synthesis
of 5, 15 (0.11 g, 0.26 mmol) and 1,3-bis(diphenylphosphanyl)pro-
panenickel(ii) chloride (4.2 mg, 7.7 μmol) in diethyl ether (1 mL)
was treated with 8-bromomagnesiumoct-1-ene (0.8 mL, 0.8 mmol,
1 m solution in diethyl ether). The crude product was purified by
flash chromatography (cyclohexane/ethyl acetate, 10:1); yield:
EI-MS: calcd. for C33H44: 440.3443, found 440.3412.
1,3-Bis(4-bromophenyl)prop-2-yn-1-ol: From diisopropylamine
(2.75 g, 27.1 mmol) in THF (20 mL), nBuLi (10.1 mL, 25.3 mmol,
2.5 m solution in hexane), 1-bromo-4-ethynylbenzene[21] (3.28 g,
18.1 mmol) in THF (5 mL) and 4-bromobenzaldehyde (3.35 g,
18.0 mmol) in THF (20 mL) according to the preparation of 11.
Yield: 5.04 g (76%) of 1,3-bis(4-bromophenyl)prop-2-yn-1-ol as a
1
0.12 g (87%) of 16 as a colorless oil. H NMR: δ = 7.37–7.05 (m,
1
brownish solid (m.p. 60 °C). H NMR: δ = 7.53 (d, J = 8.5 Hz, 2
13 H), 5.80 (ddt, J = 17.0/10.2/6.7 Hz, 2 H), 4.98 (d, J = 17.0 Hz,
2 H), 4.91 (d, J = 10.2 Hz 2 H), 2.58 (m, 4 H), 2.03 (m, 4 H), 1.66–
1.55 (m, 4 H), 1.40–1.24 (m, 12 H), 1.21 (s, 9 H, (CH3)3C). 13C
NMR: δ = 203.0 (×), 141.4 (×), 141.3 (×), 139.1 (+), 137.9 (×),
H, Ar-H), 7.46 (d, J = 8.5 Hz, 2 H, Ar-H), 7.45 (d, J = 8.5 Hz, 2
H, Ar-H), 7.31 (d, J = 8.5 Hz, 2 H, Ar-H), 5.63 (s, 1 H), 2.54 (s, 1
H, OH). 13C NMR: δ = 139.4 (×), 133.1 (+), 131.8 (+), 131.6 (+),
Eur. J. Org. Chem. 2005, 2322–2329
www.eurjoc.org
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
2327

C. E. Janßen, N. Krause
FULL PAPER
134.8 (×), 134.5 (×), 129.2 (+), 128.3 (+), 128.2 (+), 128.1 (+), 128.0
(+), 127.8 (+), 126.6 (+), 118.3 (×), 114.2 (–), 109.2 (×), 35.8 (×),
35.6 (–), 33.8 (–), 31.4 (–), 29.9 (+), 29.2 (–), 29.0 (–), 28.8 (–). IR
29.7 (–), 29.6 (–), 29.5 (–), 29.1 (–), 29.1 (–), 28.3 (–). IR (neat): ν
˜
= 2927, 1956, 1464 cm–1. EI-MS: m/z (%) = 274 (14) [M+], 259 (8),
81 (100). HR-EI-MS: calcd. for C20H34: 274.2661, found 274.2607.
(neat): ν = 3077, 2926, 1940, 1641 cm–1. EI-MS: m/z (%) = 544 (9)
˜
Cyclopentadeca-1,2-diene (20): To a refluxing solution of 18
(201 mg, 0.81 mmol) in CH2Cl2 (165 mL) was added benzyl-
[M+], 487 (100). HR-EI-MS: calcd. for C41H52: 544.4069, found
544.4049.
idenedichlorobis(tricyclohexylphosphanyl)ruthenium
(100 mg,
0.12 mmol), and refluxing was continued for 18 h. After cooling to
room temperature, cyclohexane (100 mL) was added, the solvent
was removed under reduced pressure and the crude product was
purified by flash chromatography (cyclohexane) to give 48 mg
1-(1,1-Dimethylethyl)-3-phenyl[3.14]paracyclophan-1,2,16-triene (17):
To a refluxing solution of 16 (110 mg, 0.20 mmol) in CH2Cl2
(100 mL)
was
added
benzylidenedichlorobis(tricyclohexyl-
phosphanyl)ruthenium (25 mg, 0.03 mmol), and refluxing was con-
tinued for 3 h. After cooling to room temperature, cyclohexane
(50 mL) was added, the solvent was removed under reduced pres-
sure and the crude product was purified by flash chromatography
(cyclohexane/ethyl acetate, 20:1) to give 90 mg (85%) of 17 (2:1
mixture of E/Z isomers) as a colorless oil. 1H NMR: δ = 7.49–7.05
(m, 13 H), 5.37/5.32 (2m, 2 H), 2.63 (m, 4 H), 2.08–1.93 (m, 4 H),
1.68–1.54 (m, 4 H), 1.49–1.25 (m, 12 H), 1.30 (s, 9 H, (CH3)3C).
13C NMR: δ = 204.5*/203.0 (2×), 141.2 (×), 140.1 (×), 140.9 (×),
140.7 (×), 137.9/137.4* (2×), 134.7 (×), 134.6 (×), 134.5 (×), 134.4
(×), 131.6 (+), 130.3 (+), 130.0 (+), 129.2 (+), 128.9 (+), 128.7 (+),
128.4 (+), 128.3 (+), 128.2 (+), 128.0 (+), 127.5 (+), 126.7 (+), 118.7
(×), 118.3 (×), 109.4*/109.2 (2×), 35.8 (×), 35.7 (–) 35.4 (×), 30.1
(+), 29.9 (+); numerous additional peaks between 29.9 and 22.6
1
(29%) of 20 as a colorless oil. H NMR: δ = 5.08 (m, 2 H), 1.99
(m, 4 H), 1.45–1.10 (m, 20 H). 13C NMR: δ = 204.4 (×), 91.2 (+),
28.3 (–), 28.2 (–), 27.6 (–), 27.2 (–), 27.1 (–), 26.5 (–). IR (neat): ν
˜
= 2924, 1959, 1465 cm–1. EI-MS: m/z (%) = 206 (2) [M+], 81 (100).
HR-EI-MS: calcd. for C15H26: 206.2035, found 206.2051.
Cycloheptadeca-1,2-diene (21): To a refluxing solution of 19
(200 mg, 0.73 mmol) in CH2Cl2 (145 mL) was added benzyl-
idenedichlorobis(tricyclohexylphosphanyl)ruthenium
(90 mg,
0.12 mmol), and refluxing was continued for 18 h. After cooling to
room temperature, cyclohexane (100 mL) was added, the solvent
was removed under reduced pressure and the crude product was
purified by flash chromatography (cyclohexane) to give 98 mg
1
(57%) of 21 as a colorless oil. H NMR: δ = 5.09 (m, 2 H), 1.99
could not be assigned. IR (neat): ν = 3058, 2926, 1938, 1646 cm–1.
(m, 4 H), 1.45–1.20 (m, 2 H). 13C NMR: δ = 204.1 (×), 91.1 (+),
˜
EI-MS: m/z (%) = 516 (19) [M+], 459 (77), 57 (100). HR-EI-MS:
28.7 (–), 28.3 (–), 28.1 (–), 27.9 (–), 27.5 (–), 27.1 (–), 27.0 (–). IR
(neat): ν = 2925, 1957, 1458 cm–1. EI-MS: m/z (%) = 234 (27) [M+],
calcd. for C39H48: 516.3756, found 516.3777.
˜
81 (100). HR-EI-MS: calcd. for C17H30: 234.2348, found 234.2343.
Octadeca-1,2,16,17-tetraene (18): To a solution of hexadeca-1,15-
diene[22] (10.2 g, 45.9 mmol) in CH2Cl2 (40 mL) was added CHBr3
(41.4 g, 0.17 mol), triethylbenzylammonium chloride (1.10 g,
4.8 mmol) and 50% aqueous NaOH (30 mL). The mixture was
stirred for 8 h with an Ultra Turrax stirrer and then diluted with
pentane (300 mL) and brine (250 mL). The organic layer was sepa-
rated, washed with brine (3×100 mL), dried with Na2SO4, and the
solvent was removed under reduced pressure. The crude product
was purified by dry column chromatography (pentane) to furnish
22.6 g (87%) of the α,ω-bis(dibromocyclopropane) as a colorless
waxy solid. To a solution of the α,ω-bis(dibromocyclopropane)
(3.50 g, 6.2 mmol) in diethyl ether (25 mL) was added dropwise at
–65 °C MeLi (8.5 mL, 13.6 mmol, 1.6 m solution in diethyl ether).
The mixture was warmed to 0 °C and poured into ice water. The
organic layer was separated and the aqueous layer was washed with
pentane (3×30 mL). The combined organic layers were dried with
Na2SO4, and the solvent was removed in vacuo. The crude product
was purified by flash chromatography (pentane), affording 1.24 g
1,4-Di(oct-7-en-1-yl)benzene: According to the synthesis of 5, 1,4-
dibromobenzene (6.02 g, 25.5 mmol) and 1,3-bis(diphenylphos-
phanyl)propanenickel(ii) chloride (276 mg, 0.51 mmol) in diethyl
ether (20 mL) was treated with the Grignard reagent prepared from
8-bromooct-1-ene (13.1 g, 68.5 mmol) and magnesium turnings
(1.67 g, 68.7 mmol) in diethyl ether (70 mL). The crude product
was purified by kugelrohr distillation (40–90 °C, 0.01 mbar); yield:
1
4.90 g (65%) of 1,4-di(oct-7-en-1-yl)benzene as a colorless oil. H
NMR: δ = 7.11 (s, 4 H, Ar-H), 5.83 (ddt, J = 17.2/10.1/6.7 Hz, 2
H), 5.02 (d, J = 17.2 Hz, 2 H), 4.96 (d, J = 10.1 Hz, 2 H), 2.60 (t,
J = 7.7 Hz, 4 H), 2.07 (q, J = 6.7 Hz, 4 H), 1.63 (m, 4 H), 1.38 (m,
12 H). 13C NMR: δ = 140.0 (×), 139.1 (+), 128.2 (+), 114.1 (–),
35.5 (–), 33.8 (–), 31.5 (–), 29.2 (–), 29.0 (–), 28.8 (–). IR (neat): ν
˜
= 2927, 1640 cm–1. EI-MS: m/z (%) = 298 (74) [M+], 129 (87), 117
(100). HR-EI-MS: calcd. for C22H34: 298.2661, found 298.2661.
1,4-Di(nona-7,8-dien-1-yl)benzene (22): According to the prepara-
tion of 18, 1,4-di(oct-7-en-1-yl)benzene (1.08 g, 3.7 mmol) in
CH2Cl2 (20 mL) was treated with CHBr3 (3.01 g, 11.9 mmol), tri-
ethylbenzylammonium chloride (105 mg, 0.46 mmol) and 50%
aqueous NaOH (20 mL). Yield: 2.14 g (91%) of the bis(dibromocy-
clopropane) as a yellow oil. The bis(dibromocyclopropane) (1.50 g,
3.26 mmol) was treated with MeLi (3.3 mL, 5.2 mmol, 1.6 m solu-
tion in diethyl ether) to give 698 mg (90%) of 22 as a reddish oil.
1H NMR: δ = 7.10 (s, 4 H, Ar-H), 5.10 (qi, J = 6.7 Hz, 4 H), 4.66
(dt, J = 6.7/3.3 Hz, 4 H), 2.59 (t, J = 7.5 Hz, 4 H), 2.00 (m, 4 H),
1.68–1.55 (m, 4 H), 1.50–1.32 (m, 12 H). 13C NMR: δ = 208.5 (×),
140.0 (×), 128.2 (+), 90.0 (+), 74.5 (–), 35.5 (–), 31.5 (–), 29.1 (–),
1
(81%) of 18 as a colorless oil. H NMR: δ = 5.09 (qi, J = 6.7 Hz
2 H), 4.65 (dt, J = 6.7/3.2 Hz, 4 H), 2.00 (m, 4 H), 1.45–1.38 (m,
4 H), 1.35–1.23 (m, 16 H). 13C NMR: δ = 208.5 (×), 90.1 (+), 74.5
(–), 29.6 (–), 29.6 (–), 29.4 (–), 29.2 (–), 29.1 (–), 28.3 (–). IR (neat):
ν = 2926, 1956, 1464 cm–1. EI-MS: m/z (%) = 246 (23) [M+], 231
˜
(28), 81 (100). HR-EI-MS: calcd. for C18H30: 246.2348, found
246.2327.
Eicosa-1,2,18,19-tetraene (19): According to the preparation of 18,
octadeca-1,17-diene[22] (11.0 g, 43.9 mmol) in CH2Cl2 (40 mL) was
treated with CHBr3 (33.4 g, 0.13 mol), triethylbenzylammonium
chloride (1.05 g, 4.6 mmol) and 50% aqueous NaOH (50 mL).
Yield: 21.9 g (84%) of the α,ω-bis(dibromocyclopropane) as a pale
yellow solid (m.p. 42–46 °C). The α,ω-bis(dibromocyclopropane
(3.53 g, 5.94 mmol) was treated with MeLi (8.6 mL, 13.7 mmol,
29.0 (–), 28.9 (–), 28.2 (–). IR (neat): ν = 3044, 2928, 1956,
˜
1458 cm–1. EI-MS: m/z (%) = 322 (44) [M+], 199 (46), 117 (100).
HR-EI-MS: calcd. for C24H34: 322.2661, found 322.2642.
[15]Paracyclophan-7,8-diene (23): To a refluxing solution of 22
1.6 m solution in diethyl ether) to give 1.04 g (64%) of 19 as a
colorless oil. H NMR: δ = 5.09 (qi, J = 6.7 Hz 2 H), 4.65 (dt, J ichlorobis(tricyclohexylphosphanyl)ruthenium (76 mg, 0.09 mmol),
(200 mg, 0.62 mmol) in CH2Cl2 (125 mL) was added benzylidened-
1
= 6.7/3.3 Hz, 4 H), 2.00 (m, 4 H), 1.45–1.38 (m, 4 H), 1.35–1.23
and refluxing was continued for 18 h. After cooling to room tem-
perature, cyclohexane (100 mL) was added, the solvent was re-
(m, 20 H). 13C NMR: δ = 208.5 (×), 90.1 (+), 74.5 (–), 29.7 (–),
2328
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
Eur. J. Org. Chem. 2005, 2322–2329

Macrocyclic Allenes by Ring Closing Metathesis and Doering–Moore–Skattebøl Reaction
FULL PAPER
[7] a) W. v. E. Doering, P. M. La Flamme, Tetrahedron 1958, 2, 75–
79; b) W. R. Moore, H. R. Ward, J. Org. Chem. 1960, 25, 2073;
c) L. Skattebøl, Tetrahedron Lett. 1961, 2, 167–172.
[8] Treatment of (E)-5 (obtained by Kumada coupling of (E)-4 or
by photochemical isomerization of (Z)-5) with Grubbs-I cata-
lyst under the same conditions only furnished polymeric prod-
ucts.
moved under reduced pressure and the crude product was purified
by flash chromatography (cyclohexane) to give 19 mg (9%) of 23
as a colorless oil. 1H NMR: δ = 7.05 (s, 4 H, Ar-H), 5.08 (m, 2 H),
2.66–2.53 (m, 4 H), 2.09–1.91 (m, 4 H), 1.45–1.24 (m, 16 H). 13C
NMR: δ = 203.6 (×), 139.5 (×), 128.6 (+), 90.8 (+), 35.0 (–), 30.3
(–), 28.5 (–), 28.0 (–), 27.7 (–), 26.8 (–). IR (neat): ν = 3044, 2925,
˜
1959, 1458 cm–1. EI-MS: m/z (%) = 282 (60) [M+], 117 (100). HR-
[9] A. Mucci, F. Parenti, L. Schenetti, Eur. J. Org. Chem. 2002,
EI-MS: calcd. for C21H30: 282.2348, found 282.2344.
938–940.
[10] a) D. Seyferth, R. L. Lambert Jr., J. Organomet. Chem. 1969,
16, 21–26; b) D. Seyferth, Acc. Chem. Res. 1972, 5, 65–74.
[11] Cf.: a) K.-L. Noble, H. Hopf, L. Ernst, Chem. Ber. 1984, 117,
474–488; b) D. Cao, H. Kolshorn, H. Meier, Tetrahedron Lett.
1995, 36, 7069–7072.
Acknowledgments
[12] a) E. Vogel, W. Klug, A. Breuer, Org. Synth., Coll. Vol. VI
1988, 731–736; b) W. Tochtermann, T. Panitzsch, M. Petroll,
T. Habeck, A. Schlenger, C. Wolff, E.-M. Peters, K. Peters,
H. G. v. Schnering, Eur. J. Org. Chem. 1998, 2651–2657.
[13] A. Hoffmann-Röder, N. Krause, in: Modern Allene Chemistry
(Eds.: N. Krause, A. S. K. Hashmi), Wiley-VCH, Weinheim,
2004, pp. 51–92.
Generous support of this work by the Deutsche Forschungsgemein-
schaft and the Fonds der Chemischen Industrie is gratefully ac-
knowledged.
[1] N. Krause, A. S. K. Hashmi (Eds.), Modern Allene Chemistry,
Wiley-VCH, Weinheim, 2004.
[14] N. Krause, A. Hoffmann-Röder, Tetrahedron 2004, 60, 11671–
11694.
[2] a) R. D. Johnson, Chem. Rev. 1989, 89, 1111–1124; b) M. Balci, [15] a) T. L. MacDonald, D. R. Reagan, J. Org. Chem. 1980, 45,
Y. Taskesenligil, in: Advances in Strained and Interesting Or-
ganic Molecules, Vol. 8 (Ed.: B. Halton), Jai Press, Stamford,
2000, pp. 43–81; c) M. Christl, in: Modern Allene Chemistry
(Eds.: N. Krause, A. S. K. Hashmi), Wiley-VCH, Weinheim,
2004, pp. 243–358; d) C. Zelder, N. Krause, Eur. J. Org. Chem.
2004, 3968–3971.
4740–4747; b) A. Jansen, N. Krause, Synthesis 2002, 1987–
1992.
[16] M. Ahmed, T. Arnauld, A. G. M. Barrett, D. C. Braddock, K.
Flack, P. A. Procopiou, Org. Lett. 2000, 2, 551–553.
[17] Treatment of 1,2-nonadiene with the Grubbs-II catalyst or
Fürstner’s catalyst (A. Fürstner, O. Guth, A. Düffels, G. Seidel,
M. Liebl, B. Gabor, R. Mynott, Chem. Eur. J. 2001, 7, 4811–
4820) furnished only polymeric products: J. Averbeck, unpub-
lished results.
[18] a) J. A. Mata, E. Falomir, R. Llusar, E. Peris, J. Organomet.
Chem. 2000, 616, 80- 88; b) T. Bosanac, C. S. Wilcox, Org.
Lett. 2004, 6, 2321–2324.
[19] R. Broos, M. Anteunis, Synth. Commun. 1976, 6, 53–57.
[20] M.-C. Roux, R. Paugam, G. Rousseau, J. Org. Chem. 2001, 66,
4306–4310.
[21] a) M. Schmittel, H. Ammon, Synlett 1999, 750–752; b) J. Wet-
tergren, A. B. E. Minidis, Tetrahedron Lett. 2003, 44, 7611–
7612.
[3] a) J. W. Grissom, G. U. Gunawardena, D. Klingberg, D. Hu-
ang, Tetrahedron 1996, 52, 6453–6518; b) K. K. Wang, Chem.
Rev. 1996, 96, 207–222; c) K. K. Wang, in: Modern Allene
Chemistry (Eds.: N. Krause, A. S. K. Hashmi), Wiley-VCH,
Weinheim, 2004, pp. 1091–1126.
[4] M. S. Brody, R. M. Williams, M. G. Finn, J. Am. Chem. Soc.
1997, 119, 3429–3433.
[5] a) S. Thorand, F. Vögtle, N. Krause, Angew. Chem. 1999, 111,
3929–3931; Angew. Chem. Int. Ed. 1999, 38, 3721–3723; b) See
also: A. G. Fallis, Synlett 2004, 2249- 2267.
[6] a) T. M. Trnka, R. H. Grubbs, Acc. Chem. Res. 2001, 34, 18–
29; b) R. H. Grubbs, T. M. Trnka, in: Ruthenium in Organic
Synthesis (Ed.: S.-I. Murahashi), Wiley-VCH, Weinheim, 2004,
pp. 153–178.
[22] M. Schlosser, H. Bossert, Tetrahedron 1991, 47, 6287–6292.
Received: February 04, 2005
Eur. J. Org. Chem. 2005, 2322–2329
www.eurjoc.org
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
2329