Six- and eightfold palladium-catalyzed gross-coupling reactions of hexa- and octabromoarenes

Article abstract of DOI:10.1002/chem.200400723

Palladium-catalyzed sixfold coupling of hexabromobenzene (20) with a variety of alkenylboronates and alkenylstannanes provided hexaalkenylbenzenes 1 in up to 73% and 16 to 41% yields, respectively. In some cases pentaalkenylbenzenes 21 were isolated as the main products (up to 75%). Some functionally substituted hexaalkenylbenzene derivatives containing oxygen or sulfur atoms in each of their six arms have also been prepared (16 to 24% yield). The sixfold coupling of the less sterically encumbered 2, 3, 6, 7, 10, 11-hexabromotriphenylene (24) gave the desired hexakis(3,3-dimethyl-1-butenyl) triphenylene (25) in 93% yield. The first successful cross-coupling reaction of octabromonaphthalene (26) gave octakis-(3,3-dimethyl-1-butenyl)naphthalene (27) in 21% yield. Crystal structure analyses disclose that, depending on the nature of the substituents, the six arms are positioned either all on the same side of the central benzene ring as in 1a and 1i, making them nicely cup-shaped molecules, or alternatingly above and below the central plane las in 1h and 23. In 27, the four arms at C-1, 4, 6, 7 are down, while the others are up, or vice versa. Upon catalytic hydrogenation, 1a yielded 89% of hexakis(tert-butylethyl)benzene (23). Some efficient accesses to alkynes with sterically demanding substituents are also described. Elimination of phosphoric acid from the enol phosphate derived from the corresponding methyl ketones gave 1-ethynyladamantane (3b, 62% yield), 1-ethynyl-1-methylcyclohexane (3c, 85%) and 3,3-dimethylpentyne (3e, 65%). 1-(Trimethylsilyl)ethynylcyclopropane (7) was used to prepare 1-ethynyl-1-methylcyclopropane (3d) (two steps, 64% overall yield). The functionally substituted alkynes 3 f-h were synthesized in multistep sequences starting from the propargyl chloride 11, which was prepared in high yields from the dimethylpropargyl alcohol 10 (94%). The alkenylstannanes 19 were prepared by hydrostannation of the corresponding alkynes in moderate to high yields (42-97%), and the alkenylboronates 2 and 4 by hydroboration with catecholborane (27-96% yield) or pinacolborane (26-69% yield).

Full text of DOI:10.1002/chem.200400723

Six- and Eightfold Palladium-Catalyzed Cross-Coupling Reactions of
Hexa- and Octabromoarenes
[
a]
[a]
[b]
[a]
[b]
Baldur Stulgies, Peter Prinz, Jçrg Magull, Karsten Rauch, Kathrin Meindl,
[
b]
[a]
Stephan Rühl, and Armin de Meijere*
Dedicated to Professor Josef Michl on the occasion of his 65th birthday
Abstract: Palladium-catalyzed sixfold
coupling of hexabromobenzene (20)
with a variety of alkenylboronates and
alkenylstannanes provided hexaalke-
nylbenzenes 1 in up to 73% and 16 to
yield. Crystal structure analyses dis-
the corresponding methyl ketones gave
1-ethynyladamantane (3b, 62% yield),
close that, depending on the nature of
the substituents, the six arms are posi-
tioned either all on the same side of
the central benzene ring as in 1a and
1i, making them nicely cup-shaped
molecules, or alternatingly above and
below the central plane as in 1h and
23. In 27, the four arms at C-1,4,6,7 are
down, while the others are up, or vice
versa. Upon catalytic hydrogenation,
1a yielded 89% of hexakis(tert-butyl-
ethyl)benzene (23). Some efficient ac-
cesses to alkynes with sterically de-
manding substituents are also de-
scribed. Elimination of phosphoric acid
from the enol phosphate derived from
1-ethynyl-1-methylcyclohexane
(3c,
85%) and 3,3-dimethylpentyne (3e,
65%). 1-(Trimethylsilyl)ethynylcyclo-
propane (7) was used to prepare 1-eth-
ynyl-1-methylcyclopropane (3d) (two
steps, 64% overall yield). The function-
ally substituted alkynes 3 f–h were syn-
thesized in multistep sequences starting
from the propargyl chloride 11, which
was prepared in high yields from the
dimethylpropargyl alcohol 10 (94%).
The alkenylstannanes 19 were prepared
by hydrostannation of the correspond-
ing alkynes in moderate to high yields
(42–97%), and the alkenylboronates 2
and 4 by hydroboration with catechol-
borane (27–96% yield) or pinacolbor-
ane (26–69% yield).
41% yields, respectively. In some cases
pentaalkenylbenzenes 21 were isolated
as the main products (up to 75%).
Some functionally substituted hexaal-
kenylbenzene derivatives containing
oxygen or sulfur atoms in each of their
six arms have also been prepared (16
to 24% yield). The sixfold coupling of
the
,3,6,7,10,11-hexabromotriphenylene
24) gave the desired hexakis(3,3-di-
methyl-1-butenyl)triphenylene (25) in
3% yield. The first successful cross-
less
sterically
encumbered
2
(
9
coupling reaction of octabromonaph-
thalene (26) gave octakis-(3,3-dimeth-
yl-1-butenyl)naphthalene (27) in 2 1%
Keywords: alkynes · bromoarenes ·
cross-coupling · palladium
Introduction
Disk- and star-shaped molecules like hexasubstituted ben-
zene derivatives with six functional side chains have re-
ceived considerable attention over the last two decades due
to their interesting properties such as being discotic liquid
[
a] Dr. B. Stulgies, Dr. P. Prinz, K. Rauch, Prof. Dr. A. de Meijere
Institut für Organische Chemie
Georg-August-Universität Gçttingen
Tammannstrasse 2, 37077 Gçttingen (Germany)
Fax : (+49)551-39-9475
E-mail: armin.demeijere@chemie.uni-goettingen.de
[1]
[2]
crystals, nonlinear optical materials, core structures for
[
3]
[4]
dendritic as well as light-harvesting materials. Suitably
hexasubstituted benzene derivatives have been designed as
hosts and complex-forming ligands with considerable poten-
[
b] Prof. Dr. J. Magull, K. Meindl, Dr. S. Rühl
Institut für Anorganische Chemie
Georg-August-Universität Gçttingen
Tammannstrasse 4, 37077 Gçttingen (Germany)
[5]
tial. An elegant route to hexaalkylbenzenes is by sixfold
alkylation of hexamethylbenzene activated as a cationic cy-
clopentadienyliron complex under basic conditions as devel-
Supporting information for this article is available on the WWW
under http://www.chemeurj.org/ or from the author and include 18
pages of preparative procedures for starting materials and intermedi-
ates.
[6]
oped by Astruc et al. The sixfold coupling of hexahaloben-
zenes with alkynes and alkenes under palladium catalysis
308
ꢀ 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
DOI: 10.1002/chem.200400723
Chem. Eur. J. 2005, 11, 308 – 320

FULL PAPER
offers another interesting access to a group of aesthetically
[7]
appealing molecules. Vollhardt et al. reported the first suc-
[8]
cessful sixfold Sonogashira–Hagihara coupling of hexabro-
mobenzene with terminal alkynes to yield hexakis(trimethyl-
silylethynyl)- and hexakis(trimethylsilylbutadiynyl)benzene.
[9]
Sixfold Heck coupling of hexabromobenzene with styrene
and substituted styrenes under conditions of the Jeffery pro-
[10]
tocol readily occurred, and gave very good yields of prod-
ucts showing the correct relative molecular masses, but
NMR spectroscopy disclosed that these products were
multi-component mixtures of different isomers, apparently
formed by additional intramolecular 5-exo-trig-cyclizations
during the consecutive palladium-catalyzed alkenylation of
Scheme 1. Hydroboration of terminal alkynes 3. For details see Table 1.
[11]
an intermediate o-bromostilbene unit on the central ben-
Table 1. Hydroboration of terminal alkynes 3 to catechol boronates 2
and pinacol boronates 4 (see Scheme 1).
[9b,c,12]
zene ring.
Since pure hexastyrylbenzene derivatives 1
(
R = Ar) could never be isolated from these mixtures, and
3
R
2 [%]
4 [%]
[13]
since such side reactions cannot occur in Suzuki
Stille couplings, we turned our attention to the latter cou-
pling protocols to access C -symmetric hexaalkenylbenzene
derivatives 1. Herein we report convenient syntheses of sev-
eral of these molecules and an extension of this approach to
compounds with larger aromatic cores.
and
a
b
c
d
e
f
tert-butyl
1-adamantyl
91
96
61
31
29
–
37
–
–
[14]
1-methylcyclohexyl
1-methylcyclopropyl
tert-pentyl
1,1-dimethyl-4-methoxybutyl
1,1-dimethyl-3-thiomethylpropyl
1,1-dimethyl-3-methoxypropyl
6
–
26
36
69
68
g
h
–
27
formed via the enol phosphate into the alkyne 3b (overall
[19]
yield for the two operations 60%, Scheme 2). The same
sequence was applied to prepare (1’-methylcyclohexyl)-
ethyne (3c) from 1-methylcyclohexanecarboxylic acid (5c)
in 76% overall yield.
Results and Discussion
Preparation of various alkenylboronates and alkenylstan-
nanes: In order to be able to test the possibilities of carrying
out sixfold Suzuki- and Stille-type couplings with hexabro-
mobenzene (20), a number of 2-substituted ethenylboro-
nates 2 and 4 and trialkylethenylstannanes 19 were prepared
by hydroboration and hydrostannylation, respectively, of the
corresponding terminal alkynes 3.
The hydroborations were performed with catecholborane,
[15]
described by Brown et al., and pinacolborane introduced
[16]
by Knochel et al. One advantage of the pinacol boronates
over the catechol boronates 2 is their stability towards
4
water. In addition, the hydroborations of terminal alkynes 3
with pinacolborane occur under milder conditions than
those with catecholborane (Scheme 1). The low yields of the
pinacol (2-tert-butylethenyl)boronate 4a and the (2-tert-pen-
tylethenyl)boronate 4e are due to losses upon purification
by chromatography on silica gel. Flash chromatography, as
applied to the hydroboration products 4g and 4h, provided
Scheme 2. Syntheses of sterically encumbered alkynes 3 from corre-
sponding carboxylic acids 5 via methyl ketone enol phosphates, from
silyl-protected cyclopropylacetylene 7 and from 3,3-dimethylpentanone
(
9).
[17]
higher yields (Table 1).
For the synthesis of adamantylethyne (3b), a much more
(1’-Methylcyclopropyl)ethyne (3d) was prepared by treat-
ment of the lithiated species of (2’-trimethylsilylethynyl)cy-
[18]
efficient route than the published one
was developed.
[20]
Commercially available adamantanecarboxylic acid (5b)
was converted to the methyl ketone 6b, and this was trans-
clopropane (7) with dimethyl sulfate followed by hydro-
[21]
desilylation in 64% overall yield.
Chem. Eur. J. 2005, 11, 308 – 320
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ꢀ 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
309

A. de Meijere et al.
Due to the low boiling point of tert-pentylethyne (3e), it
is difficult to obtain a pure product by the method presented
above for 3b and c. A significantly improved method com-
pared to that reported by Meshcheryakov et al., was used.
The direct dehydrochlorination with KOH in 2-ethoxyetha-
nol of the crude product obtained by the chlorination of 3,3-
dimethylpentanone with PCl5 gave 3e in 65% yield
Compounds 19 were obtained as mixtures of (E)- and (Z)-
diastereomers in moderate to very high yields (42–97%).
The particularly low yield of 19k was due to partial decom-
position of the product upon distillation at a rather high
temperature. The E/Z-isomer ratios (Table 2) were deter-
[22]
1
mined after distillation from the H NMR spectra. E/Z-dia-
stereomeric mixtures of 19 were used without separation,
(
Scheme 2).
because the Stille cross-coupling always yields the thermo-
dynamically more stable (E)-isomers.
[28,29]
The functionally substituted alkynes 3 f–h were prepared
from dimethylpropargylic alcohol 10 (Scheme 3), following
[23,24]
in part literature procedures.
Thus, the tertiary alcohol
1
0 was transformed in high yield (94%) into the chloride
[
25]
11. Treatment of 11 with diethyl sodiomalonate gave the
[26]
substituted malonate 12 (62%) which,
upon heating with
Scheme 4. Hydrostannylation of terminal alkynes 3. For details see
sodium bromide in moist dimethyl sulfoxide, underwent
Table 2.
clean desethoxycarbonylation to give the monoester 13
(
88%). The latter was reduced with LiAlH to the primary
4
Table 2. Hydrostannylation of terminal alkynes 3 with tri-n-butyltin hy-
alcohol 16 (90%), part of which was methylated to yield the
methoxypropyl-substituted alkyne 3h (81%). Another ali-
quot of the alcohol 16 was converted in almost quantitative
yield to the corresponding mesylate 15 (99%), which upon
treatment with methylmercaptane in the presence of sodium
methoxide provided the methylthiopropyl-substituted
alkyne 3g (67%). A fraction of the mesylate 15 was also
transformed with sodium cyanide to the nitrile 14 (91%)
which was saponified to the hexynoic acid 17 (94%). Reduc-
tion to the corresponding alcohol 18 (98%) followed by
methylation, provided the methoxybutyl-substituted alkyne
dride (see Scheme 4).
3
R
Yield of 19 [%]
E:Z
a
b
i
tert-butyl
729:1
91
97
86
425:1
1-adamantyl
trimethylsilyl
phenyl
9:1
9:1
9:1
j
k
3,5-di-tert-butylphenyl
Sixfold cross-couplings with hexabromobenzene: An initial
attempt to perform a sixfold coupling of hexabromobenzene
3
f (55%).
(20)
with
tert-butylethenylboronate
2a,
applying
[
PdCl (PPh ) ] as a catalyst and sodium ethoxide in ethanol
2
3 2
as a base, only led to partial dehalogenation of 20. This kind
of reductive dehalogenation has frequently been observed in
[13a]
Suzuki couplings,
of sodium hydroxide as a base. Under optimized conditions
[PdCl (PPh ) ], NaOH, toluene/THF (1:1), 1008C, 24 h} the
and found to be suppressed upon use
{
2
3 2
cross-coupling of 20 with 2a gave hexakis-(tert-butylethe-
[30]
nyl)benzene (1a) in 73% yield.
This corresponds to an
average yield of 95% for each cross-coupling step.
In an attempt to further optimize this coupling, cesium
[31]
[32]
fluoride
and barium hydroxide,
which have been re-
ported to be particularly efficient bases for the Suzuki reac-
tion, were also tested. However, the yield of 1a was signifi-
cantly lower in both cases (5 and 22%, respectively), and
with barium hydroxide a small amount (9%) of the partially
reduced fivefold coupling product pentakis(3,3-dimethyl-1-
butenyl)benzene (21a) was obtained. With the pinacol ethe-
nylboronate 4a and sodium hydroxide under the conditions
optimized for catechol (3,3-dimethyl-1-butenyl)boronate
Scheme 3. Syntheses of functionally substituted alkynes 3 f–h. a) CaCl
CuCl , Cu, conc. HCl, 08C, 1 h; b) NaCH(COOEt) , EtOH; c) NaBr,
DMSO (wet), 1808C, 20 h; d) LiAlH , Et O; e) NaCN, DMSO, r.t., 19 h;
f) MeSO Cl, Et N, CH Cl , 08C, 30 min; g) NaOH, EtOH, H O, 1008C,
7 h; h) HSMe, NaOMe, MeOH, r.t., 18 h; i) NaH, Et O, MeI; j) LiAlH
Et O, 36 8C, 1 h; k) NaH, Et O, MeI.
2
,
2
2
4
2
(
2a), 1a was obtained in 45% yield along with 38% of 21a.
2
3
2
2
2
The formation of such reduction products must be a conse-
quence of the steric shielding of the palladium residue on
the benzene ring after oxidative addition of the vicinally di-
alkenyl-substituted bromoarene by which the rate of trans-
metallation will be reduced, so that the transfer of hydride
from a different source to palladium can compete with the
transfer of the alkenyl residue. It has been reported that
such dehalogenation products can also be derived from re-
1
2
4
,
2
2
Tri-n-butylstannylethene derivatives 19 as reagents to be
applied in Stille cross-couplings of 20 were prepared by hy-
[27]
drostannylation of the corresponding alkynes 3 with tri-n-
butyltin hydride at 808C without any solvent (Scheme 4).
310
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Chem. Eur. J. 2005, 11, 308 – 320

Cross-Coupling Reactions
FULL PAPER
duction of arylpalladium hydroxide intermediates with tri-
[33]
phenylphosphine.
Even under the optimized conditions, attempted analo-
gous cross-coupling reactions of hexabromobenzene (20)
with styryl- and n-nonenylboronates did not yield any of the
[29]
sixfold coupling products,
but only octadecadiene 22 as
the homocoupling product of the corresponding boronate,
when dichloro[1,1-bis(diphenylphosphano)ferrocene]palladi-
um in THF/DMF was applied. With [PdCl (PPh ) ], only a
Scheme 5. Sixfold Suzuki coupling of hexabromobenzene (20) with vari-
ous alkenylboronates and side reactions. For details see Table 3.
2
3 2
mixture of reduction products derived from hexabromoben-
zene (20) was obtained. Apparently, the tert-butyl groups in
[34]
2
a are essential for the success of the sixfold coupling, and
mann. For each bromine substituent on the arene approxi-
mately 1 mol% of the catalyst was used, and the reaction
time was increased to up to 5 d (Scheme 6, Table 4). The
coupling of the tert-butylethenylstannane 19a gave 1a in a
moderate yield of 35%. The sixfold Stille coupling was also
successful with the trimethylsilyl(ethenyl)stannane 19i and
indeed catechol (alkenyl)boronates with other tert-alkyl
groups gave the corresponding sixfold coupling products 1c–
h reasonably well in yields ranging from 10 to 44%
(
Table 3).
[30]
gave 1i in an acceptable yield of 41%. However, the at-
tempted coupling of 20 with the sterically encumbered (ada-
mantylethenyl)stannane 19b gave only an inseparable mix-
ture of 1b and pentakis[2-(1’-adamantyl)ethenyl]benzene.
The attempted sixfold Stille coupling of 20 with the (aryl-
ethenyl)tributylstannane 19k produced only an oil which ex-
hibited a strong fluorescence under UV light. NMR and
mass spectra indicated the presence of the sixfold coupling
product 1k in this oil, but it could not be purified any fur-
ther.
Table 3. Sixfold Suzuki coupling of hexabromobenzene (20) with a varie-
ty of alkenylboronates in THF/toluene (1:1) at 1008C (Scheme 5).
[
a]
Boronate
Conditions
t [h]
Product (Yield/%)
2
2
2
2
4
2
2
2
2
4
4
4
2
4
a
a
a
a
a
b
c
d
e
e
f
A, NaOH
A, CsF
24
24
24
48
24
48
18
24
43
24
24
24
24
24
1a (73)
1a (5)
1a (22), 21a (9)
1a (24)
A, Ba(OH)
2
[
b]
B, NaOH
A, NaOH
1a (45), 21a (38)
1b (6), 21b (6)
1c (44), 21c (54), 22c (3)
[
c]
B, NaOH
A, NaOH
A, NaOH
A, NaOH
A, NaOH
A, NaOH
A, NaOH
A, NaOH
A, NaOH
[
d]
1d (16), 21d (40) , 22d (3)
1e (10), 21e (55)
1e (16), 21e (74)
1 f (18), 21 f (34), 22 f (6)
1g (22), 21g (38), 22g (4)
1h (16), 21h (75), 22h (8)
1h (24), 21h (25), 22h (24)
g
h
h
[
2 3 2
a] A: [PdCl (PPh ) ]; B: trans-di(m-acetato)bis[2-(di-o-tolylphosphino)-
benzyl]dipalladium(ii). [b] Toluene, 908C. [c] Toluene, 1108C. [d] Yield
determined from the NMR spectrum.
Scheme 6. Sixfold Stille coupling of hexabromobenzene (20) with alke-
nylstannanes 19. For details see Table 4.
The coupling of the sterically most encumbered (2-ada-
mantylethenyl)boronate 2b yielded only a small amount
(
6%) of the corresponding hexakisadamantylethenyl deriva-
Table 4. Yields for the coupling of hexabromobenzene (20) with alkenyl-
stannanes 19 under various conditions (Scheme 6).
tive 1b. To achieve this, the palladacycle from palladium
acetate and tris(o-tolyl)phosphine first reported by Herr-
[a]
1
9
R
Conditions
Yield of 1 [%]
[34]
mann and Beller, had to be used, while for all other alke-
nylboronates with mimics of the tert-butyl group bis(triphe-
nylphosphine)palladium dichloride could be applied. In
most cases the pentakis(tert-alkylethenyl)benzene deriva-
tives 21 (Scheme 5) resulting from reductive removal of one
of the six bromine substituents was isolated as the major
product (up to 75%). In addition, small amounts of the 1,4-
disubstituted butadienes 22c,d,f–h, arising from homocou-
pling of the corresponding alkenylboronates 2/4, were
a
b
i
j
k
tert-butyl
A, 12 08C, 4 d
A, 1108C, 3 d
A, 1008C, 1 d
B, 1108C, 4 d
A, 1108C, 5 d
35
–
[b]
1-adamantyl
trimethylsilyl
phenyl
41
16
[
c]
3,5-di-tert-butylphenyl
–
[a] A:
trans-Di(m-acetato)bis[2-(di-o-tolylphosphino)benzyl]dipalladi-
1
3 4
um(ii); B: [Pd(PPh ) ], CuI. [b] According to the H NMR spectrum, the
crude product contained 1b and pentakis[2-(1’-adamantylethenyl]ben-
zene (21b); an attempted purification failed. [c] The product 1k was
formed according to the H NMR and mass spectrum, but could not be
separated from by-products.
1
[13f,32b,35]
obtained.
To test the accessibility of hexaalkenylbenzenes 1 by the
Stille cross-coupling reaction, sixfold alkenylations of hexa-
bromobenzene (20) with various 2-substituted (tri-n-butyl-
stannyl)ethenes 19 were carried out in refluxing toluene
with the palladacycle catalyst developed by Beller and Herr-
Szeimies et al. recently reported the sixfold cross-coupling
of 20 with 1-(tri-n-butylstannyl)cyclobutene applying
[Pd(PPh ) ] as a precatalyst leading to an air-sensitive hexa-
3
4
Chem. Eur. J. 2005, 11, 308 – 320
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ꢀ 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
311

A. de Meijere et al.
[
36]
alkenylbenzene derivative. When hexabromobenzene (20)
was treated with tri-n-butyl(phenylethenyl)stannane (19j)
in the presence of [Pd(PPh ) ] and copper iodide as a co-cat-
Such molecules with six heteroatom-containing arms,
stretching out from a rigid central structure, do bind simple
[5,39]
cations.
In view of this, attempts were made to prepare
3
4
alyst, which is well known to accelerate Stille-type cou-
plings, the sparely soluble hexakis(phenylethenyl)benzene
hexakisalkenylbenzene derivatives with six functionally sub-
stituted arms by sixfold cross-coupling of hexabromoben-
zene (20). In fact, the sixfold Suzuki coupling of 20 with cat-
echol 2h and pinacol (1,1-dimethyl-3-methoxypropyl)ethe-
nylboronate (4h), respectively, worked out to give the corre-
spondingly substituted hexakis[(1,1-dimethyl-3-methoxypro-
pyl)ethenyl]benzene (1h), albeit only in poor to moderate
yield of 16 and 24%, respectively. The corresponding meth-
ylthio-substituted analogue 1g was obtained from 20 with
4g in 22% yield (Table 3).
[37]
(
1j) was obtained in 16% yield which is lower than those of
[2b]
the previously reported alternative approaches to 1j.
Any of the attempted Suzuki- and Stille-type couplings of
hexabromobenzene (20) with alkenylboronates and -stan-
nanes without a tert-butyl group or a mimic thereof did not
furnish the corresponding sixfold coupling product at all or
at best in very low yield. Apparently, the steric demand of
the tert-butyl groups or its mimics is indispensible for these
sixfold couplings to occur with moderate to high yields, and
this may have to do with attractive van der Waals interac-
tions during the self-assembly in the consecutive coupling
steps. This leads to interestingly cup-shaped molecules with
all six arms on the same side of the central ring in the case
of 1a and 1i (Figures 1 and 2).
Surprisingly, the six functionally substituted arms of 1h in
the crystal do not point to the same side of the central ring,
but alternatingly up and down (Figure 3). This must be due
to weak intermolecular—possibly dipole–dipole—interac-
tions between the methoxypropyl groups in the crystal of
1h. Anyhow, intramolecular attractive van der Waals inter-
actions between tert-butyl groups as in 1a are not essential
for the six arms of a hexaalkenylbenzene to point to the
same side, since the parent hexaethenylbenzene has been
[40]
shown to have the same orientation in the crystal.
The closest intermolecular contacts in 1h are those be-
tween b-vinylic hydrogen and oxygen atoms which, with
2
.67 Š are shorter than the sum of their van der Waals
[41]
radii. In addition, the distance between a hydrogen atom
of the methoxy groups and a carbon atom of a neighboring
benzene ring with 2.88 Š is also shorter than the sum of
their van der Waals radii.
It is noteworthy that hexakis-(tert-butylethyl)benzene
(
23), which was obtained by catalytic hydrogenation of 1a
over palladium on charcoal in hexane at room temperature
in 89% yield (Scheme 7), in the crystal also assumes a con-
formation in which its six arms are rotated alternatingly up
and down out of the central plane with a torsional angle of
89.28. This same conformation has also been found for hexa-
Figure 1. Stacking of the cup-shaped molecules of hexakis(tert-butylethe-
nyl)benzene (1a) in the crystal.
[
30,38]
[42]
ethylbenzene,
and must be attributed to intramolecular
repulsion between neighboring benzylic hydrogen atoms. In
addition, at least for 23, there is a contribution from inter-
molecular attractive van der Waals interactions between
methyl groups, as the molecules of 23 are stacked in col-
umns along the axis of the central rings with interlocking
tert-butyl groups of nearest neighbors within the stacks
(
Figure 4).
Multifold couplings with other perbromoarenes: The suc-
cessful sixfold coupling of hexabromobenzene (20) with a
variety of sterically encumbered alkenylboronates inspired
attempts to perform multiple coupling reactions of other
perbromoarenes. Indeed, six- and even eightfold Suzuki cou-
pling reactions could be brought about between catechol
(
(
tert-butylethenyl)boronate 2a and hexabromotriphenylene
24) as well as octabromonaphthalene (26), respectively. The
sixfold coupling of 2a with the less sterically congested 24
was particularly efficient and furnished hexakis-(tert-butyl-
ethenyl)triphenylene (25) in a yield of 93% (Scheme 8).
Figure 2. Stacking of the cup-shaped molecules of hexakis(trimethylsilyl-
ethenyl)benzene (1i) in the crystal.
[
30,38]
312
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Chem. Eur. J. 2005, 11, 308 – 320

Cross-Coupling Reactions
FULL PAPER
2
1% yield, when the reaction
was carried out in an ultrasonic
bath with a large excess of the
alkenylboronate 2a (Scheme 9).
An eightfold Suzuki coupling of
a
porphyrine derivative in
which the bromine subtituents
are not as close to each other
as in 26, has previously been re-
[44]
ported.
After a long series of unsuc-
cessful attempts, good-quality
light-yellow crystals of 27 were
eventually grown from ethanol/
pentane and subjected to an X-
[38]
ray crystal structure analysis.
It disclosed (Figure 6) that the
four arms on C-1,4,6,7 are ro-
tated upward with respect to
the central plane while the four
others are downward, or vice
versa.
Some physical properties of the
new peralkenylarenes: Arnett
et al., who first synthesized the
parent hexavinylbenzene in
Figure 3. Structure and packing of hexakis[(1,1-dimethyl-3-methoxypropyl)ethenyl]benzene (1h) in the crys- 1966, already discovered that
[
38]
tal.
the colorless crystals of this
Scheme 7. Catalytic hydrogenation of hexakis-(tert-butylethenyl)benzene
1a).
(
This corresponds to a nearly quantitative yield (~99%) for
each newly generated CÀC bond. According to an X-ray
structure analysis the six arms of 25 in the crystal are irregu-
larly rotated out of the plane of the central core, with two
neighboring arms up, the two next down, and the last two
[43]
almost in the plane (Figure 5).
Under the same conditions, 2a and octabromonaphtha-
lene (26) gave only complex mixtures, which according to
mass spectra contained the eightfold coupling product as the
minor component along with heptakis(3,3-dimethyl-1-bute-
nyl)naphthalene and other partially reduced oligofold cou-
pling products. This must be attributed to the severe steric
congestion of twofold substitution in the peri-positions. Nev-
ertheless, the octaalkenylnaphthalene 27 was obtained in
Figure 4. Packing of hexakis-(tert-butylethyl)benzene (23) in the crys-
tal.
[30,38]
[45a]
compound changed to yellow upon exposure to daylight.
This same effect was observed for hexakis-(tert-butylethe-
Chem. Eur. J. 2005, 11, 308 – 320
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ꢀ 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
313

A. de Meijere et al.
Figure 6. Structure of octakis-(tert-butylethenyl)naphthalene (27) in the
crystal.
Scheme 8. Sixfold Suzuki coupling of hexabromotriphenylene (24) with
catechol (2-tert-butylethenyl)boronate (2a).
[
38]
The major absorption band in the UV spectrum of 1a at
lmax =262 nm (emax =53600) is very close to that of the
parent hexavinylbenzene (lmax =258 nm). Thus, the six addi-
tional tert-butyl substituents on the vinyl groups in 1a have
almost no apparent effect on the absorption maximum.
[45b]
However, Arnett et al.
report a hypsochromic shift of the
absorption maximum of hexaisopropenylbenzene compared
with that of a-methylstyrene which they attribute to an out
of plane rotation of the alkenyl substituents leading to de-
creased conjugation. Although such a conformation is also
indicated for 1a and 1i, respectively—at least in the crystals
according to X-ray structure analyses—the major absorp-
tions of the hydrocarbons 1a and 1c around 262 nm are at
Figure 5. Structure of hexakis-(tert-butylethenyl)triphenylene (25) in the
crystal.
slightly longer wavelengths than that of b-methylstyrene
[
43]
[46]
(
lmax =248 nm) and b-tert-butylstyrene (lmax =250 nm).
Presumably, the topomerization of 1a is less hindered in so-
lution than it is in the case of hexaisopropenylbenzene.
The band of octakis-(tert-butylethenyl)naphthalene (27) at
l=290 nm with a shoulder at l=341 nm, is significantly
red-shifted in comparison to that of the absorption of the
analogous benzene derivative 1a (see Table 5). However, the
bathochromic shift for this pair of arene derivatives is not as
large as for the related hexaphenylbenzene (l=247 nm) and
octaphenylnaphthalene (l=329 nm), respectively.
Monitoring the change of color of a solution of 1a in cy-
clohexane upon irradiation with a 250 Watt xenon high-pres-
sure lamp at a wavelength of l=262 nm showed that the
original maximum disappeared, and new maxima at l=444,
Scheme 9. Eightfold Suzuki coupling of octabromonaphthalene (26).
2
78 nm slowly emerged. When the irradiation was continued
nyl)benzene (1a) and its analogues during this work. The
freshly recrystallized, colorless crystals turned intensively
yellow upon storage in open daylight on the bench, while no
such change took place in the dark. Furthermore, when
stored for at least 24 h in the dark, the yellow crystals re-
turned to a completely colorless appearance. The same re-
versible discoloration also occurs in solution. However, the
reverse process, the loss of the yellow color, in solution re-
quires much longer than in the solid state of 1a.
for more than 30 min, all maxima started to decrease, appa-
rently because the compound was decomposing. When a
sample of 1a in solution was irradiated for 7 min and then
stored in the dark for 24 h, the extinction at 262 nm was re-
stored to approximately the same value as before the irradi-
ation (Figure 7), and the new absorption at 444 nm had
almost completely disappeared again. It is an open question,
what is really happening during the initial phase of the irra-
diation. As indicated by the observation of isosbestic points,
314
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Chem. Eur. J. 2005, 11, 308 – 320

Cross-Coupling Reactions
FULL PAPER
Table 5. Absorption maxima of selected benzene and naphthalene deriv-
atives.
served a progressive disappearance of the diffraction pattern
without significant change of the crystal structure.
[40]
Compound
Absorption
maximum
Extinction
coefficient
(emax/10 )
4
(
l
max/nm)
Conclusion
[
a]
a-methylstyrene
(
(
243
248
250
225
258
262
263
290, 341
247, 266
329
1.02
–
18.29
2.55
4
5.36
4.91
6.61, 0.78
5.68, 3.47
1.42
[
b]
[c]
E)-b-methylstyrene
E)-b-tert-butylstyrene
hexaisopropenylbenzene
[
d]
Six- and eightfold Suzuki and Stille couplings of hexa- and
octabromoarenes lead to interestingly shaped molecules
with extraordinary efficiency. Some of the functionally sub-
stituted hexaalkenylbenzene derivatives thus accessible may
have applications as hosts or ligands for supramolecular ag-
gregates and metal complexes, respectively.
[
e]
[
f]
hexavinylbenzene
1
1
2
a
c
7
[
g]
hexaphenylbenzene
octaphenylnaphthalene
[
h]
[
[
a] Ref. [45b]. [b] Ref. [47]. [c] Not reported. [d] Ref. [46]. [e] Ref. [45b].
f] Ref. [40,45]. [g] Ref. [48]. [h] Ref. [49].
Experimental Section
1
General: H NMR spectra were recorded with a Bruker AM 250 spec-
trometer (250 MHz) at ambient temperature in CDCl
.26) or tetramethylsilane (d=0.00) as internal standard. Chemical shifts
d) are quoted in ppm and coupling constants (J) are given in absolute
3 3
, using CHCl (d=
7
(
values in Hz to the nearest 0.1 Hz. The following abbreviations are used
for the signal multiplicities and shapes: s (singlet), d (doublet), t (triplet),
1
3
m (multiplet) and br (broad). C NMR spectra were recorded with a
Bruker AM250 spectrometer (62.9 MHz) or Varian VXR 500S
125.7 MHz) at ambient temperature in CDCl , using CDCl (d=77.0) as
internal standard. Multiplicities were determined by the DEPT pulse se-
quence and are described as follows: + = CH or CH and
, À = CH
quat =C. Signals which could not be assigned unambiguously are marked
a
(
3
3
3
2
C
1
3
with an asterisk (*). Under the routine conditions employed, C signals
of carbon atoms directly attached to boron could not be detected. Infra-
red spectra were recorded with a Bruker IFS 66 FT-IR spectrometer.
Low and high-resolution mass spectra were recorded with a Finnigan
MAT 95 instrument using electron impact ionization at 70 eV or direct
Figure 7. Absorption spectra of 1a in cyclohexane: without irradiation
c), after irradiation for 7 min at l=262 nm (a), after 24 h in dark-
ness (··–).
(
chemical ionization with NH
tra (HRMS) were obtained using preselected ion peak matching at R ꢀ
0000 to be within Æ2ppm. Elemental analyses were performed by the
3
as reactant gas. High-resolution mass spec-
1
a distinct, long-lived intermediate must be formed upon irra-
diation. However, there is absolutely no clue to what the
structure of this intermediate might be. Both IR and
H NMR spectra of the yellow modification disclosed no sig-
nificant differences as compared to the ones of the initial
colorless compound.
Mikroanalytisches Labor des Instituts für Organische Chemie der Uni-
versität Gçttingen, Germany. For routine chromatography Merck silica
gel 60 (230–400 mesh, 0.063–0.200 mm) and for flash chromatography
Macherey–Nagel silica gel 60 (70–230 mesh, 0.040–0.063 mm) was used.
TLC plates: Macherey–Nagel foils: Alugram Sil G/UV, detection under
UV light at 254 or 366 nm. If the substances were not UV active, the
plates were developed with anisaldehyde solution. All solvents were dis-
tilled before use. Anhydrous solvents were prepared according to stan-
dard laboratory techniques. All reactions with organometallic reagents
were performed under nitrogen and anhydrous conditions. In these cases
the glassware used was heated in vacuo to remove all of the residual
1
It is noteworthy that the development of the yellow color
in solution can be almost completely suppressed by flushing
the solution of 1a with argon for 5 min before irradiation.
This observation would make one suspect that the yellow
moisture. Unless specified otherwise, solutions of NH
NaCl were saturated aqueous solutions.
4 3
Cl, NaHCO and
[50]
compound is a photooxygenation product formed by addi-
tion of photochemically generated singlet oxygen molecules
to one or more of the double bonds of 1a. However, such
Starting materials: All chemicals were used as commercially available,
[15]
[53]
[54]
[55]
[20]
unless otherwise noted. The compounds 2a,
3a,
3i,
3k,
7,
[51]
[56]
[57]
[28]
[58]
[59]
an assumed dioxetane
would have to have the unlikely
9, 19i, 19j, 24 and 26 were prepared according to literature
procedures. For further starting materials and intermediates see Support-
ing Information.
feature of not undergoing retro-[2+2] cycloaddition to two
carbonyl fragments, but cleavage back to the hexaalkenyl-
benzene 1a and oxygen in the dark.
General procedure for the multifold Suzuki couplings (GP 6): To a so-
lution of the hexabromoarene (2mmol) in a mixture of anhydrous tolu-
ene and THF (50 mL each), which had been flushed with argon for
5 min, was added the palladium catalyst (30 mol%), the respective alke-
nylboronate 2 or 4 (13 mmol) as well as powdered NaOH (36 mmol), and
the mixture was heated under an argon atmosphere at 1008C for the
stated time. After the mixture had been cooled down to ambient temper-
ature, it was treated with 3m NaOH (18 mL) and 30% hydrogen perox-
ide (2mL) and the mixture stirred at ambient temperature for 1 h. The
organic layer was then separated, washed with 3m NaOH (5”12mL),
Upon prolonged irradiation, the compound 1a probably
undergoes polymerization such as Meier et al. interpret the
complete disappearance of the main absorption band of hexa-
styrylbenzenes during irradiation as a “statistical CÀC bond
formation of the olefinic centers (cross-linking) which yields
[52]
oligomers”. In an attempt to monitor the discoloration of
a single crystal of hexavinylbenzene, Krüger et al. only ob-
Chem. Eur. J. 2005, 11, 308 – 320
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ꢀ 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
315

A. de Meijere et al.
and dried (MgSO
4
). The solvent was removed under reduced pressure,
matography on silica gel (60 g, hexane, column 3”50 cm) yielded fraction
and the residue purified by chromatography on silica gel.
I: 21 mg (3%) of 1,4-bis(1’-methylcyclohexyl)buta-1,3-diene (22c) as a
colorless solid, R
f
=0.64. M.p. 988C; IR (KBr): n˜ =2983 (CÀH), 2854,
General procedure for sixfold Stille couplings (GP 7): A solution of hexa-
bromobenzene (1 mmol) in toluene (20 mL) was flushed with argon for
À1 1
1
611, 1475, 1384, 1321, 1259, 821 cm ; H NMR (250 MHz, CDCl
3
): d=
0
.99 (s, 6H, CH ), 1.26–1.51 (m, 20H, CH ), 5.55–5.61 [AA’ part of an
3
2
5
min. Then palladium catalyst (30 mol%) and the respective alkenyl-
AA’BB’ system, 2H, 3(6)-H], 5.94–6.01 ppm [BB’ part of an AA’BB’
stannane 19 (6.6 mmol) were added, and the mixture heated at 1108C for
the stated time. The reaction mixture was diluted with diethyl ether
1
3
system, 2H, 4(5)-H]; C NMR (62.9 MHz, CDCl
d=22.4 (À, CH ), 26.3 (À, CH ), 27.3 (+, CH ), 35.8 (Cquat, C-2), 38.0 (À,
CH ), 127.1 [+, C-3(6)], 142.5 ppm [+, C-4(5)]; MS (70 eV): m/z (%):
46 (35) [M] , 149 (30) [MÀcHexMe] , 97 (100) [cHexMe] , 55 (20); el-
emental analysis calcd (%) for C H (246.4): C 87.73, H 12.27; found C
3
, additional DEPT):
(
20 mL), mixed with a saturated aqueous solution of KF (20 mL), and
2
2
3
after 15 min filtered through a bed of Celite. The organic layer was sepa-
rated, and the treatment with the KF solution was repeated until no col-
2
+
+
+
2
[
60]
orless solid was observed. Then the organic layer was dried (MgSO
4
),
18 30
8
f
7.48, H 12.11. Fraction II: 285 mg (44%) of 1c (R =0.55). Recrystalliza-
the solvent was removed under reduced pressure, and the residue puri-
fied by chromatography on silica gel.
tion from ethanol/pentane yielded colorless crystals. M.p. 2618C; IR
À1
(
KBr): n˜ =2951 (CÀH), 2900, 1475, 1452, 1311, 1256, 1215, 963, 820 cm
;
Hexakis-[(E)-(3,3-dimethyl-1-butenyl)]benzene (1a)—Variant 1: Accord-
ing to GP 6, hexabromobenzene (1.001 g, 1.815 mmol) was treated with
1
UV (isooctane):
CDCl
l
max (log e)=263 nm (4.69); H NMR (250 MHz,
3
3
): d=1.06 (s, 18H, CH
3
), 1.34–1.56 (m, 60H, CH
2
), 5.55 (d, J=
2
a (2.453 g, 12.08 mmol) in the presence of dichlorobis(triphenylphos-
phine)palladium (363 mg, 0.517 mmol) and powdered sodium hydroxide
1.302g, 3 2. 55 mmol) in THF/toluene (1:1, 100 mL) at 100 8C for 24 h.
Column chromatography on silica gel (100 g, pentane, column 5”50 cm),
=0.64, and subsequent recrystallization from hexane yielded 1a
3
13
1
6.6 Hz, 6H, 2’-H), 6.27 ppm (d, J=16.6 Hz, 6H, 1’-H); C NMR
(
62.9 MHz, CDCl
3
, additional DEPT): d=22.4 (À, CH
2 3
), 26.1 (+, CH ),
), 125.7 (+, C-2’), 135.3
(
2
6.3 (À, CH
2
), 36.4 (Cquat, C-3’), 37.7 (À, CH
2
(
C
quat, Ph-C), 144.8 ppm (+, C-1’); MS (70 eV): m/z (%): 811/810 (58/90)
R
f
+
+
+
[
M] , 713 (10) [MÀcHexMe] , 618/617 (90/45), 97 (100) [cHexMe] , 55
(
2
761 mg, 73%) as colorless crystals. M.p. 2028C; IR (KBr): n˜ =2947,
(
20); elemental analysis calcd (%) for C60H90 (811.4): C 88.82, H 11.18;
À1
863, 1473, 1385, 1361, 1282, 1259, 1200, 965, 911, 826 cm ; UV (cyclo-
found C 88.94, H 10.91. Fraction III: 298 mg (54%) of a colorless solid
1
hexane): lmax (log e)=262 nm (4.72); H NMR (250 MHz, CDCl
3
): d=
1
which, according to its H NMR spectrum was pentakis[2-(1’-methylcy-
1
1
2
.09 [s, 54H, C(CH
6.5 Hz, 6H, 1’-H); C NMR (62.9 MHz, CDCl
3
1
)
3
3
], 5.57 (d, J=16.5 Hz, 6H, 2’-H), 6.24 ppm (d, J=
1
clohexyl)ethenyl]benzene (21c). M.p. 1078C; H NMR (250 MHz,
3
, additional DEPT): d=
3
CDCl
3
): d=1.08 (brs, 15H, CH
3
), 1.31–1.69 (m, 50H, CH
2
), 5.61 (d, J=
9.7 [+, C(CH ], 33.8 [Cquat, C(CH ], 124.7 (+, C-2’), 134.8 (Cquat, Ph-
3
)
3
3
)
3
3
3
1
2
6.4 Hz, 2H, 2’-H), 5.63 (d, J=16.4 Hz, 1H, 2’-H), 6.04 (d, J=16.5 Hz,
H, 2’-H), 6.22 (d, J=16.4 Hz, 1H, 1’-H), 6.70 (d, J=16.4 Hz, 2H, 1’-
+
C), 145.5 ppm (+, C-1’); MS (70 eV): m/z (%): 570 (55) [M] , 513 (5)
3
3
+
+
[
(
MÀC
4
H
9
] , 457 (60) [MÀC
4
H
9
ÀC
4
H
8
+
] , 401 (10), 345 (10), 230 (10), 111
3
H), 6.62(d, J=16.4 Hz, 2H, 1’-H), 7.46 ppm (s, 1H, Ph-H); C51
H
76
4 9
15), 97 (25), 69 (30), 57 (100) [C H ] ; elemental analysis calcd (%) for
(
689.2).
42
C H66 (571.0): C 88.35, H 11.65; found C 88.57, H 11.71.
Hexakis-[2-(1’-methylcyclopropyl)ethenyl]benzene (1d): According to
GP 6, hexabromobenzene (276 mg, 500 mmol) was treated with 2d
1.00 g, 5.00 mmol) in the presence of dichlorobis(triphenylphosphine)-
palladium (105 mg, 150 mmol) and powdered sodium hydroxide (520 mg,
3.0 mmol) in THF/toluene (1:1, 40 mL) at 1008C for 24 h. Column chro-
Hexakis-[2-(1-adamantyl)ethenyl]benzene (1b)—Variant 1: According to
GP 6, hexabromobenzene (149 mg, 0.270 mmol) was treated with 2b
(
(
770 mg, 2.75 mmol) in the presence of trans-di(m-acetato)bis[2-(di-o-tol-
ylphosphino)benzyl]dipalladium(ii) (75 mg, 0.080 mmol) and powdered
sodium hydroxide (160 mg, 4.00 mmol) in toluene (10 mL) at 1108C for
1
matography on silica gel (40 g, pentane, column 3”50 cm) yielded frac-
tion I: 10 mg (2.5%) of 1,4-bis(1’-methylcyclopropyl)buta-1,3-diene (22d)
2
5
d. Column chromatography on silica gel (80 g, pentane, column 5”
0 cm) yielded fraction I: 1b (18 mg, 6%) (R =0.44). Recrystallization
/ethanol yielded a colorless solid. M.p. >3208C; IR (KBr):
f
=0.48), colorless solid. M.p. 588C; IR (KBr): n˜ =3053, 2951, 2844 (CÀ
(
R
f
from CHCl
3
À1 1
H), 1635, 1478, 1320, 912, 852 cm ; H NMR (250 MHz, CDCl
s, 8H, cPr-H), 1.17 (s, 6H, CH ), 5.17–5.28 [AA’ part of an AA’BB’
system, 2H, 3(6)-H], 5.92–6.04 ppm [BB ’ part of an AA’BB’ system, 2H,
3
): d=0.57
n˜ =2963, 2905, 2848 (CÀH), 1751, 1450, 1413, 1260, 1013, 865, 793,
(
3
À1
1
7
2
1
01 cm
3
; H NMR (250 MHz, CDCl ): d=1.70 (brs, 72H, 2’’-H, 4’’-H),
.01 (brs, 18H, 3’’-H), 5.45 (d, J=16.6 Hz, 6H, 2’-H), 6.13 ppm (d, J=
6.6 Hz, 6H, 1’-H); C NMR (62.9 MHz, CDCl ): d=28.6 (C-3’’), 35.9
3
13
4
(5)-H]; C NMR (62.9 MHz, CDCl
cPr-C), 17.31 (Cquat cPr-C), 21.47 (+, CH
39.14 ppm [+, C-4(5)]; MS (70 eV): m/z (%): 162(55) [ M] , 147 (30)
3
, additional DEPT): d=15.47 (À,
1
3
,
3
), 126.01 [+, C-3(6)],
(
(
C-1’’), 37.1 (C-4’’*), 42.3 (C-2’’*), 124.8 (C-2’), 134.6 (Ph-C), 145.8 ppm
+
1
+
C-1’); MS (70 eV): m/z (%): 1039/1038 (25/30) [M] , 903 (100)
+
+
[
MÀCH
3
] , 105 (40), 91 (75), 81 (40) [CHꢁCHC(ethano)CH
3
] , 79 (60),
18 (162.3): 162.1408, found
=0.25). Recrystallization
+
+
+
[
C
MÀC10
H
15] , 768 (80) [MÀ2C10
H
15] , 619 (50), 135 (100) [C10
H
15] .
7
1
7 (40), 41 (100); HRMS: m/z: calcd for C12H
78
H102 (1039.7): calcd 1038.7981 (Without an authentic standard with ap-
62.1408. Fraction II: 45 mg (16%) of 1d (R
f
proximately this value an accurate relative molecular mass could not be
obtained by HRMS). Fraction II: 15 mg (6%) of pentakis[2-(1-adamantyl)-
from pentane/ethanol (2:1) yielded a colorless solid. M.p. 185 8C; IR
À1
(
KBr): n˜ =3059, 2951, 2842 (CÀH), 1633, 1475, 1382, 1242, 961 cm
;
ethenyl]benzene (21b) (R
f
=0.35), colorless solid. M.p. >3208C;
): d=1.72(brs, 60H, 2- H adam. , 4-Hadam.), 2.05
brs, 15H, 3-Hadam.), 5.50 (d, J=16.5 Hz, 2H, 2’-H), 5.53 (d, J=16.5 Hz,
H, 2’’-H), 5.89 (d, J=16.5 Hz, 2H, 2’’-H), 6.10 (d, J=16.5 Hz, 1H, 1’’’-
H), 6.15 (d, J=16.5 Hz, 2H, 1’-H), 6.50 (d, J=16.5 Hz, 2H, 1’’-H),
1
H NMR (250 MHz, CDCl
3
): d=0.57 (s, 24H, cPr-H), 1.24 (s, 18H, CH
3
),
1
H NMR (250 MHz, CDCl
3
3
3
5
.21 (d, J=16.3 Hz, 6H, 2’-H), 6.18 ppm (d, J=16.3 Hz, 6H, 1’-H);
(
1
13
C NMR (125.7 MHz, CDCl
7.9 (Cquat, cPr-C), 21.6 (+, CH
43.1 ppm (+, C-1’); MS (70 eV): m/z (%): 559/558 (44/100) [M] , 503
3
, additional DEPT): d=14.6 (À, cPr-C),
1
1
(
3
), 125.1 (+, C-2’), 134.1 (Cquat, Ph-C),
+
7
.39 ppm (s, 1H, Ph-H); MS (70 eV): m/z (%): 832 (20), 718 (20)
+
30), 484 (40), 91 (35), 81 (100) [CHꢁCHC(ethano)CH
3
] , 44 (80);
54 (558.9): 558.4225, found 558.4225. Fraction
=0.21) which, according to its
+
+
[
[
MÀC12
H
16] , 342 (60), 264 (40), 203 (35) [MÀ5C10
H
15] , 135 (100)
HRMS: m/z: calcd for C42
H
+
10
C H15] ; C66H86 (879.4).
III: 121 mg of a pale yellow solid (R
f
1
Variant 2: According to GP 7, hexabromobenzene (136 mg, 0.247 mmol)
was treated with 19b (1.013 g, 2.245) in the presence of trans-di(m-aceta-
to)bis[2-(di-o-tolylphosphino)benzyl]dipalladium(ii) (30 mg, 32 mmol) in
toluene (15 mL) at 1108C for 68 h. Column chromatography (50 g, petro-
leum ether, column 3”30 cm), and subsequent recrystallization from pen-
H NMR spectrum was a 2:9 mixture of 1d and pentakis[2-(1’-methylcy-
1
3
3
3
clopropyl)ethenyl]benzene (21d). H NMR (250 MHz, CDCl ): d=0.63
(brs, 20H, cPr-H), 1.31 (brs, 15H, CH ), 5.32(d, J=16.3 Hz, 2H, 2’-H),
3
3
5.36 (d, J=16.2Hz, 1H, 2 ’-H), 5.61 (d, J=16.4 Hz, 2H, 2’-H), 6.21 (d,
3
3
3
J=16.2Hz, 1H, 1 ’-H), 6.27 (d, J=16.4 Hz, 2H, 1’-H), 6.58 (d, J=
16.3 Hz, 2H, 1’-H), 7.35 ppm (s, 1H, Ph-H); C H (478.8).
2 2
tane/CH Cl yielded 36 mg of a pale yellow solid which, according to its
3
6
46
1
H NMR spectrum, contained mainly 1b and a small amount of 21b.
Hexakis-(2-tert-pentylethenyl)benzene (1e)—Variant 1: According to
GP 6, hexabromobenzene (149 mg, 270 mmol) was treated with 2e
(585 mg, 2.71 mmol) in the presence of dichlorobis(triphenylphosphine)-
palladium (10 mg, 14 mmol) and powdered sodium hydroxide (271 mg,
6.77 mmol) in THF/toluene (1:1, 20 mL) at 1008C for 43 h. Column chro-
Hexakis-[2-(1’-methylcyclohexyl)ethenyl]benzene (1c): According to
GP 6, hexabromobenzene (441 mg, 800 mmol) was treated with 2c
(
1.28 g, 5.29 mmol) in the presence of dichlorobis(triphenylphosphine)-
palladium (168 mg, 240 mmol) and powdered sodium hydroxide (576 mg,
4.4 mmol) in THF/toluene (1:1, 40 mL) at 1008C for 18 h. Column chro-
1
f
matography on silica gel (40 g, hexane, column 3”50 cm, R =0.46) yield-
316
ꢀ 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
Chem. Eur. J. 2005, 11, 308 – 320

Cross-Coupling Reactions
FULL PAPER
ed a colorless solid. Recrystallization from hexane gave fraction I: 83 mg
(540 mg, 13.5 mmol) in THF/toluene (1:1, 36 mL) at 1008C for 24 h.
Column chromatography on silica gel [100 g, pentane/diethyl ether
(20:1), column 2.5”35 cm] gave fraction I: 1,10-dimethylthio-3,3,8,8-te-
(
55%) of pentakis(2-tert-pentylethenyl)benzene (21e) as colorless crys-
tals. M.p. 1878C; IR (KBr): n˜ =3029 (CÀH), 2953, 2861 (CÀH), 1472,
À1
1
1
0
425, 1282, 1254, 973, 851 cm
;
H NMR (250 MHz, CDCl
], 1.37–1.43 (m, 10H, CH
.58 (d, J=16.6 Hz, 2H, 2’-H*), 5.60 (d, J=16.4 Hz, 1H, 2’-H), 5.96 (d,
3
): d=0.81–
tramethyldeca-4,6-diene (22g) as a colorless solid (61 mg, 4.3%). R
f
=
.88 (m, 15H, 5’-H), 1.05 [brs, 30H, C(CH
3
)
2
2
),
0.65; IR (KBr): n˜ =3025 (CÀH), 2960, 2913, 2851 (CÀH), 1457, 1380,
3
3
À1
1
5
1363, 1314, 1261, 1240, 1001, 802 cm ; H NMR (250 MHz, CDCl
3
): d=
3
3
3
J=16.1 Hz, 2H, 2’-H*), 6.18 (d, J=16.4 Hz, 1H, 1’-H), 6.24 (d, J=
1.02[s, 12H, C(CH ], 1.59 [m, 4H, 2(9)-H], 2.09 (s, 6H, SCH ), 2.39 [m,
3
)
2
3
3
1
6.6 Hz, 2H, 1’-H*), 6.54 (d, J=16.1 Hz, 2H, 1’-H*), 7.42ppm (s, 1H,
4H, 1(10)-H], 5.53 [AA’ part of an AA’BB’ system, 2H, 4(7)-H],
1
3
13
Ph-H); C NMR (62.9 MHz, CDCl
C-5’*), 9.3 (+, 1C, C-5’*), 9.3 (+, 2C, C-5’*), 26.7 [+, 4 C, C(CH
6.8 [+, 2 C, C (C H ], 26.8 [+, 4C, C(CH
], 35.3 (À, 1C, C-4’*), 35.3
À, 2C, C-4’*), 35.8 (À, 2C, C-4’*), 36.7 (Cquat, 2C, C-3’*), 36.9 (Cquat, 1C,
C-3’*), 37.1 (Cquat, 2C, C-3’*), 123.1 (+, 1C, C-2’*), 124.0 (+, 2C, C-2’*),
24.7 (+, 1C, Ph-C), 126.8 (+, 2C, C-2’*), 134.1 (Cquat, 2C, Ph-C), 134.9
3
, additional DEPT): d=9.2( +, 2 C,
5.92ppm [BB ’ part of an AA’BB’ system, 2H, 5(6)-H]; C NMR
)
2
],
(62.9 MHz, CDCl
3 3
, additional DEPT): d=15.6 (+, SCH ), 27.1 [+,
3
2
(
3
)
2
3
)
2
C(CH
3 2
)
], 29.8 [À, C-1(10)], 36.2[C quat, C-3(8)], 42.7 [À, C-2(9)], 127.2
[+, C-4(7)], 141.4 ppm [+, C-5(6)]; MS (70 eV): m/z (%): 288/287/286
+
+
(10/16/100) [M] , 271 (14) [MÀCH
3
] , 211 (30), 107 (18), 75 (70), 61 (28)
(286.6): C 67.07, H
+
1
[C
2
H
5
S] ; elemental analysis calcd (%) for C16
H
30
S
2
(
1
6
C
quat, 2C, Ph-C), 136.4 (Cquat, 1C, Ph-C), 139.7 (+, 2C, C-1’*), 145.6 (+,
10.55; found C 67.01, H 10.39. Fraction II: 50 mg of a pale yellow oil
1
C, C-1’*), 145.8 ppm (+, 2C, C-1’*); MS (70 eV): m/z (%): 559/558 (26/
0) [M] , 462(100), 417 (100), 363 (80), 3 21 (85), 71 (90); HRMS: m/z:
(R
duction products. Fraction III: pentakis[(E)-3’,3’-dimethyl-5’-methylthio-
1’-pentenyl]benzene (21g) as a colorless solid (148 mg, 38%). R =0.30;
IR (KBr): n˜ =3024, 2958, 2914, 2865, 1652, 1472, 1437, 1383, 1361, 1253,
f
=0.41) which, according to its H NMR spectrum was a mixture of re-
+
calcd for C41
H
66 (559.0): 558.5164, found 558.5164. Fraction II: 18 mg
f
(
2
10%) of 1e as colorless crystals. M.p. 2638C; IR (KBr): n˜ =2945 (CÀH),
À1
1
À1 1
867 (CÀH), 1762, 1461, 1412, 1364, 1209, 965, 911 cm
; H NMR
9
72cm
;
H NMR (250 MHz, CDCl
3
): d=1.13 [brs, 30H, C(CH
3 2
) ],
3
1
.63–1.73 (m, 10H, 4’-H), 2.09 (brs, 15H, SCH
3
), 2.41–2.56 (m, 10H, 5’-
(
250 MHz, CDCl
3
): d=0.84 (t, J=7.5 Hz, 18H, 5’-H), 1.04 [s, 36H,
3
3
3
3
H), 5.57 (d, J=16.5 Hz, 2H, 2’*-H), 5.59 (d, J=16.5 Hz, 1H, 2’-H), 5.98
(d, J=16.2Hz, 2H, 2 ’*-H), 6.17 (d, J=16.5 Hz, 1H, 1’-H), 6.24 (d, J=
3 2
C(CH ) ], 1.36 (q, J=7.5 Hz, 12H, 4’-H), 5.50 (d, J=16.5 Hz, 6H, 2’-
H), 6.22 ppm (d, J=16.5 Hz, 6H, 1’-H); C NMR (125.7 MHz, CDCl
additional DEPT): d=9.2( +, C-5’), 26.6 [+, C(CH
3
1
3
3
3
3
13
3
,
3
1
6.5 Hz, 2H, 2’**-H), 6.51 (d, J=16.2Hz, 2H, 2 ’**-H), 7.42ppm (s, 1H,
3
)
2
], 35.4 (À, C-4’),
1
3
Ph-H); C NMR (62.9 MHz, CDCl
3
, additional DEPT): d=15.6 (+,
6.7 (Cquat, C-3’), 125.9 (+, C-2’), 135.2(C quat, Ph-C), 144.1 ppm (+, C-
’); MS (70 eV): m/z (%): 655/654 (10/20) [M] , 618 (30), 560 (10), 321
+
SCH ), 15.7 (+, SCH ), 27.2 [+, C(CH ) ], 27.2 [+, C(CH ) ], 30.0 (À,
3
3
3
2
3 2
C-5’), 30.1 (À, C-5’), 36.9 (Cquat, C-3’), 37.1 (Cquat, C-3’), 37.2(C quat, C-3’),
2.6 (À, C-4’), 42.9 (À, C-4’), 123.4 (+, C-2’*), 124.3 (+, C2’*), 125.1 (+,
Ph-C*), 126.9 (+, C2’*), 133.9 (Cquat, Ph-C), 134.8 (Cquat, Ph-C), 136.2
(
100), 71 (90); elemental analysis calcd (%) for C48H78 (655.1): C 88.00,
4
H 12.00; found C 90.02, H 11.92.
Variant 2: According to GP 6, hexabromobenzene (275 mg, 500 mmol)
was treated with 4e (1.05 g, 4.68 mmol) in the presence of dichlorobis(tri-
phenylphosphine)palladium (105 mg, 150 mmol) and powdered sodium
hydroxide (530 mg, 13.3 mmol) in THF/toluene (1:1, 40 mL) at 1008C for
2
5
(
(
Cquat, Ph-C), 139.2( +, C-1’), 145.0 (+, C-1’), 145.3 ppm (+, C-1’); MS
+
70 eV): m/z (%): 790/789/788 (5/11/22) [M] , 673/672/671 (10/18/36)
+
+
+
[
MÀC
6
H
13S] , 117 (78) [C
6
H
13S] , 61 (100) [C
2
H
5
S] ; elemental analysis
calcd (%) for C46
76 5
H S (789.4): C 69.99, H 9.70; found C 70.08, H 9.80.
4 h. Column chromatography on silica gel (40 g, hexane, column 3”
0 cm, R =0.48) yielded 225 mg of a colorless solid. Recrystallization
Fraction IV: 102mg ( 22 %) of 1g as a waxy solid. IR (KBr): n˜ =2959,
f
À1
2
916, 2677, 1652, 1472, 1437, 1383, 1363, 1261, 1036, 971, 804 cm
;
from hexane gave fraction I: 207 mg (74%) of 21e. Fraction II: 52mg
16%) of 1e as colorless crystals.
1
H NMR (250 MHz, CDCl
1
1
3
): d=1.10 [s, 36H, C(CH
2H, 4’-H), 2.08 (s, 18H, SCH ), 2.41–2.48 (m, 12H, 5’-H), 5.49 (d, J=
6.5 Hz, 6H, 2’-H), 6.22 ppm (d, J=16.5 Hz, 6H, 1’-H); C NMR
, additional DEPT): d=15.6 (+, SCH ), 26.9 [+,
], 29.9 (À, C-5’), 36.9 (Cquat, C-3’), 42.7 (À, C-4’), 126.1 (+, C-2’),
3 2
) ], 1.61–1.67 (m,
(
3
3
Hexakis-[(E)-6’-methoxy-3’,3’-dimethyl-1’-hexenyl]benzene (1 f): Accord-
ing to GP 6, hexabromobenzene (165 mg, 300 mmol) was treated with 4 f
3
13
(
62.9 MHz, CDCl
3
3
(
805 mg, 3.00 mmol) in the presence of dichlorobis(triphenylphosphine)-
palladium (63 mg, 90 mmol) and powdered sodium hydroxide (324 mg,
.10 mmol) in THF/toluene (1:1, 40 mL) at 1008C for 24 h. Column chro-
matography on silica gel [100 g, pentane/diethyl ether (2:1), column 2.5”
5 cm] gave fraction I: 26 mg (3%) of 1,12-dimethoxy-4,4,9,9-tetrame-
3 2
C(CH )
1
9
35.1 (Cquat, Ph-C), 143.6 ppm (+, C-1’); MS (70 eV): m/z (%): 934/933/
8
+
32/931 (5/11/12/20) [M] , 816/815/814/813 (6/12/15/25), 118/117 (28/100)
+
+
[
C
6
H
13S] , 61 (57) [C
2
H
5
S] ; elemental analysis calcd (%) for C54
H
90
S
6
4
(
931.7): C 69.61, H 9.74; found C 69.69, H 9.53.
1
thyldodeca-5,7-diene (22 f) as
250 MHz, CDCl ): d=1.01 [s, 12H, C(CH
.51 [m, 4H, 2(11)-H], 3.34 (s, 6H, OCH ), 3.36 [t, J=7.2Hz, 4H, 1(1 2) -
a
colorless solid.
f
R =0.62; H NMR
Hexakis-[(E)-5’-methoxy-3’,3’-dimethyl-1’-pentenyl]benzene (1h)—Var-
iant 1: According to GP 6, hexabromobenzene (276 mg, 500 mmol) was
treated with 2h (1.23 g, 5.00 mmol) in the presence of dichlorobis(triphe-
nylphosphine)palladium (53 mg, 75 mmol) and powdered sodium hydrox-
ide (540 mg, 13.5 mmol) in THF/toluene (1:1, 36 mL) at 1008C for 24 h.
Column chromatography on silica gel [60 g, pentane/diethyl ether (1:1),
column 2.5”30 cm]: Fraction I: 53 mg (8.3%) of 1,10-dimethoxy-3,3,8,8-
(
1
3
3 2
)
], 1.26 [m, 4H, 3(10)-H],
3
3
H], 5.54 [AA’ part of an AA’BB’ system, 2H, 5(8)-H], 5.91 ppm [BB’
part of an AA’BB’ system, 2H, 6(7)-H]. Fraction II: 23 mg of a pale
yellow oil (R
mixture of reduction products. Fraction III: 80 mg (34%) of penta-
kis[(E)-5’-methoxy-3’,3’-dimethyl-1’-hexenyl]benzene (21 f) as a colorless
solid.
C(CH
1
f
=0.38) which, according to its H NMR spectrum was a
tetramethyldeca-4,6-diene (22h). R
f
=0.65; M.p. 498C; IR (KBr): n˜ =
1
R
f
=0.26; H NMR (250 MHz, CDCl
3
): d=1.11 [brs, 30H,
), 3.30–3.41
3
1
[
027 (CÀH), 2977, 2922, 2867 (CÀH), 1434, 1376, 1353, 1311, 1257, 1235,
3
)
2
], 1.33–1.61 [m, 20H, 4’(5’)-H], 3.31 (brs, 15H, OCH
3
À1 1
014 cm
;
H NMR (250 MHz, CDCl
3
): d=1.02[s, 1 2H , C(CH
3
)
2
], 1.61
), 3.31 [t, J=7.2Hz, 4H,
(10)-H], 5.54 [AA’ part of an AA’BB’ system, 2H, 4(7)-H], 5.94 ppm
3
3
(
m, 10H, 6’-H), 5.59 (d, J=18.3 Hz, 2H, 2’-H), 5.62(d, J=18.4 Hz, 1H,
3
3
t, J=7.2 Hz, 4H, 2(9)-H], 3.28 (s, 6H, OCH
3
3
3
2
6
’-H), 5.98 (d, J=18.3 Hz, 2H, 2’-H), 6.18 (d, J=18.4 Hz, 1H, 1’-H),
.25 (d, J=18.3 Hz, 2H, 1’-H), 6.56 (d, J=18.3 Hz, 2H, 1’-H), 7.39 ppm
1
3
3
13
[
BB’ part of an AA’BB’ system, 2H, 5(6)-H]; C NMR (62.9 MHz,
CDCl , additional DEPT): d=27.6 [+, C(CH ], 35.0 [Cquat, C-3(8)],
2.0 [À, C-2(9)], 58.5 (+, OCH ), 70.0 [À, C-1(10)], 126.7 [+, C-4(7)],
41.8 ppm [+, C-5(6)]. Fraction II: 51 mg of a pale yellow oil (R =0.45),
(
s, 1H, Ph-H). Fraction IV: 49 mg (18%) of 1 f as a colorless solid. R
f
=
3
3 2
)
0
1
1
1
6
.16; IR (KBr): n˜ =2989, 2936, 2599, 1654, 1447, 1435, 1379, 1345, 1222,
045, 977 cm
.31–1.59 [m, 24H, 4’(5’)-H], 3.30 (s, 18H, OCH
2H, 6’-H), 5.51 (d, J=18.4 Hz, 6H, 2’-H), 6.22 ppm (d, J=18.4 Hz,
H, 1’-H); C NMR (62.9 MHz, CDCl
], 36.3 (À, C-5’), 39.6 (Cquat, C-3’), 58.5 (À, C-6’),
25.9 (+, C-2’), 135.0 (Cquat, Ph-C), 144.1 ppm (+, C1’).
4
1
3
À1
1
;
H NMR (250 MHz, CDCl
3
): d=1.05 [s, 36H, C(CH
3
)
2
],
f
3
), 3.35 (t, J=6.9 Hz,
1
3
according to H NMR spectrum a mixture of reduction products. Fraction
3
3
III: 270 mg (75%) of pentakis[(E)-5’-methoxy-3’,3’-dimethyl-1’-pentenyl]-
1
3
3
, additional DEPT): d=25.1 (À,
benzene (21h). R
472, 1424, 1368, 1224, 972 cm
brs, 30H, C(CH ], 1.68–1.76 (m, 10H, 4’-H), 3.31 (brs, 15H, OCH
3.38–3.47 (m, 10H, 5’-H), 5.60 (d, J=18.3 Hz, 2H, 2’-H), 5.62(d, J=
f
=0,22; IR (KBr): n˜ =3029, 2981, 2921, 2877, 1661,
C-4’), 27.0 [+, C(CH
1
3
)
2
À1
1
1
[
;
H NMR (250 MHz, CDCl
3
): d=1.15
),
3
)
2
3
3
3
Hexakis-[(E)-3’,3’-dimethyl-5’-methylthio-1’-pentenyl]benzene (1g): Ac-
cording to GP 6, hexabromobenzene (276 mg, 500 mmol) was treated
with 4g (1.35 g, 5.00 mmol) in the presence of dichlorobis(triphenylphos-
phine)palladium (105 mg, 150 mmol) and powdered sodium hydroxide
3
3
18.4 Hz, 1H, 2’-H), 6.03 (d, J=18.3 Hz, 2H, 2’-H), 6.18 (d, J=18.4 Hz,
3
3
1H, 1’-H), 6.27 (d, J=18.3 Hz, 2H, 1’-H), 6.55 (d, J=18.3 Hz, 2h, 1 ’-
H), 7.46 ppm (s, 1H, Ph-H); C NMR (62.9 MHz, CDCl
1
3
3
, additional
Chem. Eur. J. 2005, 11, 308 – 320
www.chemeurj.org
ꢀ 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
317

A. de Meijere et al.
DEPT): d=27.6 [+, C(CH
3
3
)
2
], 27.6 [+, C(CH
5.6 (Cquat, C-3’), 35.8 (Cquat, C-3’), 35.9 (Cquat, C-3’), 41.9 (À, C-4’), 42.4
), 70.1 (À, C-5’), 70.1 (À, C-5’), 70.2( À, C-5’),
23.4 (+, C-2’*), 123.9 (+, C-2’), 124.6 (+, Ph-C*), 126.4 (+, C2’), 133.9
3
)
2
], 27.7 [+, C(CH
3
)
2
],
not reliable. Nevertheless the isotope ratio for the molecular peak is
identical to the one calculated for C102H .
138
(
1
À, C-4’), 58.5 (+, OCH
3
Hexakis-(3,3-dimethylbutyl)benzene (23): A solution of hexakis(3,3-di-
methyl-1-butenyl)benzene (1a) (52mg, 91 mmol) in hexane (5 mL) with
added palladium on charcoal (10%, 21 mg) was stirred under an atmo-
sphere of hydrogen for 18 h. After removal of the catalyst by filtration,
the solvent was distilled off under reduced pressure. Recrystallization
(
C
quat, Ph-C), 134.9 (Cquat, Ph-C), 136.1 (Cquat, Ph-C), 139.6 (+, C-1’),
1
45.4 (+, C-1’), 145.7 ppm (+, C-1’). Fraction IV: 67 mg (16%) of 1h,
f
R =0.20. IR (KBr): n˜ =2962, 2921, 2687, 1654, 1456, 1441, 1383, 1345,
À1
1
1
225, 1031, 980 cm
;
H NMR (250 MHz, CDCl
3
): d=1.12[s, 36H,
from hexane yielded 23 (47 mg, 89%) as colorless crystals. M.p. 1878C;
3
À1
C(CH
3
)
2
], 1.67 (t, J=6.9 Hz, 12H, 4’-H), 3.30 (s, 18H, OCH
3
), 3.41 (t,
IR (KBr): n˜ =2961, 2896, 2865, 1477, 1459, 1391, 1363, 1247 cm
;
3
3
3
1
J=6.9 Hz, 12H, 5’-H), 5.52(d, J=18.4 Hz, 6H, 2’-H), 6.22 ppm (d, J=
H NMR (250 MHz, CDCl
12H, 2’-H), 2.43–2.50 ppm (m, 12H, 1’-H); C NMR (62.9 MHz, CDCl
additional DEPT): d=24.1 (À, C-2’), 29.5 [+, C(CH ], 30.9 [Cquat
C(CH
3 3 3
): d=0.99 [s, 54H, C(CH ) ], 1.36–1.43 (m,
1
3
13
1
2
(
(
8.4 Hz, 6H, 1’-H); C NMR (62.9 MHz, CDCl
7.4 [+, C(CH
3
, additional DEPT): d=
), 70.1
3
,
,
3
)
2
], 35.6 (Cquat, C-3’), 41.9 (À, C-4’), 58.5 (+, OCH
3
3 3
)
À, C-5’), 125.7 (+, C-2’), 135.0 (Cquat, Ph-C), 143.9 ppm (+, C-1’); MS
3
)
3
], 46.2( À, C-1’), 135.6 ppm (Cquat, Ph-C); MS (70 eV): m/z (%):
+
+
+
70 eV): m/z (%): 836/835 (54/100) [M] , 69 (28); elemental analysis
582(100) [ M] , 511 (5) [MÀC
5
H
11] , 333 (10), 231 (10), 161 (10), 57 (15)
78 (583.1): C 86.52, H
+
calcd (%) for C54
H
90
O
6
(835.3): C 77.65, H 10.85; found C 77.48, H 10.45.
[C
4
H
9
] ; elemental analysis calcd (%) for C42
H
1
3.48; found C 86.48, H 13.38.
,3,6,7,10,11-Hexakis-[(E)-3’,3’-dimethyl-1’-butenyl]triphenylene
to GP 6, solution of
Variant 2: According to GP 6, hexabromobenzene (276 mg, 500 mmol)
was treated with 4h (1.27 g, 5.00 mmol) in the presence of dichlorobis(tri-
phenylphosphine)palladium (105 mg, 150 mmol) and powdered sodium
hydroxide (540 mg, 13.5 mmol) in THF/toluene (1:1, 36 mL) at 1008C for
2
(25):
hexa-
According
a
bromotriphenylene (24) (351 mg, 500 mmol) and 2-[(E)-3’,3’-dimethylbu-
tenyl]-1,3,2-benzodioxaborol (2a) (1.01 g, 5.00 mmol) in THF/toluene
2
4 h. Column chromatography on silica gel [100 g, pentane/diethyl ether
(
1:1, 40 mL) was treated with powdered NaOH (600 mg, 15.0 mmol) and
PdCl (PPh ] (105 mg, 150 mmol) at 1008C for 12h. Recrystallization of
the crude product from pentane and CH Cl yielded 25 (335 mg, 93%) as
(
1:1), column 2.5”40 cm] gave: Fraction I: 155 mg (24%) of 22h, R =
f
[
2
3 2
)
0
.65. Fraction II: 98 mg of a pale yellow oil, R
f
=0.40, see above. Fraction
2
2
III: 88 mg (25%) of 21h, R
.12.
f
=0.22. Fraction IV: 101 mg (24%) 1h, R =
f
colorless needles. M.p. 2758C (decomp); IR (KBr): n˜ =3040 (CÀH), 2957,
0
À1
1
2
900 (CÀH), 2864, 1474, 1463, 1362, 1265, 966, 888 cm
; H NMR
Hexakis-(2-trimethylsilylethenyl)benzene (1i): According to GP 7, hexa-
bromobenzene (108 mg, 0.196 mmol) was treated with 19i (770 mg,
3
(
250 MHz, CDCl
3
): d=1.24 (s, 54H, CH
3
), 6.31 (d, J=16.0 Hz, 6H, 2’-
3
13
H), 6.75 (d, J=16.0 Hz, 6H, 1’-H), 8.51 ppm (s, 6H, Ar-H); C NMR
62.9 MHz, CDCl , additional DEPT): d=29.7 [+, C(CH ], 33.9 [Cquat
C(CH ], 121.3 (+, Ar-C*), 123.7 (+, C-1’*), 128.5 (Cquat, Ar-C), 135.5
quat, Ar-C), 144.7 ppm (+, C-2’); MS (70 eV): m/z (%): 722/721/720
1
.98 mmol) in the presence of trans-di(m-acetato)bis[2-(di-o-tolylphosphi-
no)benzyl]dipalladium(ii) (10 mg, 0.011 mmol) at 1008C for 20 h. Column
chromatography on silica gel (50 g, pentane, column 3”30 cm, R =0.69),
and subsequent recrystallization from ethanol/hexane yielded 1i (53 mg,
(
3
3
)
3
,
3 3
)
f
(
(
C
+
15/59/100) [M] , 315 (9), 300 (15); elemental analysis calcd (%) for
72 (721.2): C 89.94, H 10.06; found C 89.78, H 9.88.
4
1
5
6
1%) as colorless crystals. M.p. 227–2308C; IR (KBr): n˜ =2955, 2897,
54
C H
À1
1
595, 1247, 1205, 986, 864 cm ; H NMR (250 MHz, CDCl
3
): d=0.12[s,
Octakis-(3,3-dimethyl-1-butenyl)naphthalene (27): According to GP 6,
octabromonaphthalene (550 mg, 0.725 mmol) was treated with 2a (6.30 g,
4H, Si(CH ], 5.93 (d, J=19.6 Hz, 6H, 2’-H), 6.86 ppm (d, J=19.6 Hz,
3 3
)
1
3
H, 1’-H); C NMR (62.9 MHz, CDCl
+, Si(CH ], 135.8 (Cquat, Ph-C), 137.1 (+, C-2’), 143.9 ppm (+, C-1’);
MS (70 eV): m/z (%): 666 (40) [M] , 593 (90) [MÀSi(CH
MÀC=CHSi(CH ] , 495 (90), 73 (100) [Si(CH ] ; HRMS: m/z: calcd
for C36 (667.4): 666.3780; found: 666.3780.
Hexastyrylbenzene (1j): According to GP 7, hexabromobenzene
200 mg, 0.363 mmol) was treated with 19j (1.396 g, 3.550 mmol) in the
3
, additional DEPT): d=À1.10
3
(
5
1.2mmol) in the presence of dichlorobis(triphenylphosphine)palladium
204 mg, 0.290 mmol) and powdered sodium hydroxide (2.02 g,
0.6 mmol) in THF/toluene (1:1, 35 mL) in an ultrasonic bath for 24 h.
Column chromatography on silica gel (80 g, hexane, column 3”30 cm),
=0.45 and subsequent recrystallization from CH Cl /ethanol yielded 27
[
3 3
)
+
+
3 3
) ] , 568 (100)
+
+
[
3
)
3
3 3
)
H
66Si
6
R
f
2
2
(120 mg, 21%) as light-yellow crystals. M.p. 1728C (decomp); IR (KBr):
n˜ =2958, 2901, 2864, 1475, 1461, 1390, 1361, 1262, 1201, 964, 945 cm
UV (hexane): lmax (log e)=290 nm (4.82); H NMR (250 MHz, CDCl
d=1.07 [s, 36H, C(CH
À1
(
;
1
presence of tetrakis(triphenylphosphine)palladium (126 mg, 0.109 mmol)
and additional copper iodide (15 mg, 0.079 mmol) in 20 mL of toluene at
3
):
3 3 3 3
) ], 1.11 [s, 36H, C(CH ) ], 4.91 (d, J=16.3 Hz,
1
108C for 4 d. Column chromatography on silica gel [50 g, petroleum
ether/CH Cl (3:1), column 3”30 cm], yielded 1j (40 mg, 16%) as a pale
yellow oil. R =0.25; IR (film): n˜ =3026, 2923, 2853, 1699, 1599, 1494,
449, 1261, 1075, 1030, 966, 754, 697 cm
d=6.61–7.40 (m, 30H), 7.08 ppm (s, 12H); C NMR (62.9 MHz, CDCl
4H, 2’-H), 5.75 (d, J=16.3 Hz, 4H, 2’-H), 6.24 (d, J=16.3 Hz, 4H, 1’-H),
1
3
6.65 ppm (d, J=16.3 Hz, 4H, 1’-H); C NMR (62.9 MHz, CDCl
tional DEPT): d=29.2 [+, C(CH ], 29.8 [+, C(CH ], 33.6 [Cquat
C(CH ], 33.9 [Cquat, C(CH ], 124.3 (+, C-2’), 129.9 (+, C-2’), 133.0
quat, Ph-C), 133.8 (Cquat, Ph-C), 133.9 (Cquat, Ph-C), 141.2( +, C-1’),
45.9 ppm (+, C-1’); MS (70 eV): m/z (%): 788/787/786/785 (5/22/66/100)
3
, addi-
2
2
3
)
3
3
)
3
,
f
À1
1
1
;
H NMR (250 MHz, CDCl
3
3
):
):
3
)
3
3 3
)
1
3
(
C
1
d=126.2 [C-2’’(6’’)], 127.5 (C-4’’), 128.0 (C-1’*), 128.4 [C-3’’(5’’)], 128.7
C-2’*), 134.9 (C-1*), 137.7 ppm (C-1’’*); MS (70 eV): m/z (%): 690 (10)
+
+
[
4 9
M] , 715/714 (10/22), 658 (8), 57 (14) [C H ] ; elemental analysis calcd
(
+
+
(%) for C H (785.3): C 88.71, H 11.29; found C 88.73, H 11.10.
[
9
M] , 599 (5) [MÀC
7
H
7
] , 542 (5), 378 (10), 250 (30), 154 (20), 105 (40),
42 (690.9): 690.3286, found
58 88
+
1 (100) [C
90.3286.
7
H
7
] ; HRMS: m/z: calcd for C54
H
Crystallography: Information concerning the crystallographic data and
structure determinations of the five compounds is summarized in Table 6.
6
À1
Intensities were collected with a Nicolet R3mV four-circle diffractom-
Hexakis-[2-(3,5-di-tert-butylphenyl)ethenyl]benzene (1k): According to
GP 7, hexabromobenzene (233 mg, 0.422 mmol) was treated with 19k
eter for 1a, with a STOE-AED2diffractometer for 1i and 23, with a
STOE-IPDS II diffractometer for 1h using in all cases graphite-mono-
chromated MoKa radiation. Compound 27 was measured with a Bruker
SMART 6000 area detector using monochromated CuKa radiation. All
calculations were performed with the SHELXTL-Plus program pack-
(
1.500 g, 2.968 mmol) in the presence of trans-di(m-acetato)bis[2-(di-o-tol-
ylphosphino)benzyl]dipalladium(ii) (58 mg, 0.062mmol) in toluene
30 mL) at 1108C for 5 d. Column chromatography on silica gel (100 g,
petroleum ether, column 3”30 cm) yielded 19k (30 mg, 5%) as a pale
(
[
61]
1
age. All non-hydrogen atoms were refined anisotropically.
yellow oil.
R
f
=0.23; H NMR (250 MHz, CDCl
], 6.39–7.06 [m, 12H, 1’-H, 2’-H], 7.29–7.43 ppm (m, 18H,
Ph-H); C NMR (62.9 MHz, CDCl , additional DEPT): d=31.4 [+,
C(CH ], 34.8 [Cquat, C(CH ], 120.6 [+, C-2’’(6’’)], 122.0 (+, C-4’’),
28.9 (+, C-2’), 133.4 (+, C-1’), 135.7 (Cquat, C-1), 136.6 (Cquat, C-1’’),
3
): d=1.38–1.42[m,
1
08H, C(CH )
3 3
1
3
3
3
)
3
3 3
)
1
1
1
Acknowledgement
50.9 ppm [Cquat, C-3’’(5’’)]; MS (70 eV): m/z (%): 1365/1364/1363 (14/20/
+
8) [M] , 1248 (1), 1229 (5), 1162 (10), 1149 (5), 960 (5), 430 (15), 203
This work was supported by the State of Niedersachsen and the Fonds
der Chemischen Industrie. Generous gifts of chemicals by BASF AG,
Bayer AG, Chemetall GmbH, Degussa AG and Merck KGaA have been
+
(
20), 57 (100) [C(CH
3
)
3
] ; C102
H
138 (1364.2): Without an authentic cali-
bration standard for this relative molecular mass region, the HRMS is
318
ꢀ 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
Chem. Eur. J. 2005, 11, 308 – 320

Cross-Coupling Reactions
FULL PAPER
[
38]
Table 6. Summary of structure determination data for new arene derivatives.
Angew. Chem. 1996, 108, 1842–
1
845; Angew. Chem. Int. Ed.
1
a
1h
1i
23
27
Engl. 1996, 35, 1701–1704.
F
w
C
42
H
571.0
colorless
66
C
54
H
90
O
6
C
36
H
66Si
6
C
42
H
78
58 88
C H
785.28
light
[
7] a) R. Dierks, J. C. Armstrong, R.
Boese, K. P. C. Vollhardt, Angew.
Chem. 1986, 98, 270–271; Angew.
Chem. Int. Ed. Engl. 1986, 25,
M
w
835.3
667.4
583.1
colorless
color
colorless
4.0”0.3”0.5
rhombohedral
colorless
4.0”2.0”2.0
triclinic
yellow
crystal size
5.2”3.1”4.5
6.0”6.0”5.0
5.0”4.0”4.0
2
68–269; b) R. Boese, J. R.
Green, J. Mittendorf, D. L.
Mohler, K. P. C. Vollhardt,
Angew. Chem. 1992, 104, 1643–
645; Angew. Chem. Int. Ed.
[
10 mm]
crystal system
space group
unit cell
a [Š]
b [Š]
c [Š]
triclinic
rhombohedral
monoclinic
¯
¯
¯
¯
P1
R3
P1
R3
1
P2 /c
1
10.691(3)
14.697(3)
14.714(4)
60.29(2)
77.78(2)
73.35(2)
1917.2(8)
2
636
0.989
0.71069
125
14.5509(14)
14.5509(14)
21.846(3)
90
90
120
4005.7(7)
3
13.288(6)
14.039(6)
14.760(6)
66.44(3)
67.88(3)
68.95(3)
2266 (17)
2
23.819(3)
23.819(3)
61.908(12)
90
90
120
3041.8(9)
3
13.904(2)
18.781(2)
10.547(2)
90
103.28(2)
90
Engl. 1992, 31, 1643–1645.
8] a) K. Sonogashira in Metal-cata-
lyzed Cross-coupling Reactions
[
[
a [8]
b [8]
(
Eds.: F. Diederich, P. J. Stang),
Wiley-VCH, Weinheim, 1998,
pp. 203–229; b) K. Sonogashira,
Y. Tohda, N. Hagihara, Tetrahe-
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Metal-Catalyzed Cross-Coupling
Reactions (Eds.: A. de Meijere, F.
Diederich), 2nd ed., Wiley-VCH,
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b) A. de Meijere, F. Meyer,
Angew. Chem. 1994, 106, 2473–
g [8]
V [Š ]
3
2680.5(7)
2
Z
F(000)
1386
1.039
0.71073
133
0.061
732990
872
À3
1
calcd [gcm
]
1.467
0.71073
153
0.306
25.00
0.955
0.71073
153
0.0520.393
22.54
2142
0.973
1.54178
100
l [Š]
T [K]
m [mm
À1
]
0.05
25.00
5015
q
max [8]
24.69
5579
59.01
12970
reflections
measured
10334
2
506; Angew. Chem. Int. Ed.
Fabs >4s(Fabs
)
38721330
5015
7955
1519
890
3502
894
Engl. 1994, 33, 2379–2411; c) A.
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d) I. P. Beletskaya, A. V. Chepra-
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unique
reflections
7959
3758
R
int
0.0573
-
0.0491
380
0.0774
0.1117
0.0404
91
0.0365
0.1436
0.0616
397
0.0367
0.1040
0.0450
67
0.0211
0.0864
0.0358
276
2
2
wR (F )
R(F)
3
066.
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parameters
refined
GOF
[
1
–
1.036
1.031
1.110
1.027
1
1
provided. We thank Olga Eremenko for the synthesis of 3d. B.S. is in-
debted to the Niedersächsisches Ministerium für Wissenschaft und For-
schung for a Graduate Student Fellowship. The authors are grateful to
Dr. Burkhard Knieriem for his careful proofreading of the final manu-
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Received: July 14, 2004
Published online: November 18, 2004
320
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