Practical Synthesis of Vinyl-Substituted p-Phenylenevinylene Oligomers and Their Triethoxysilyl Derivatives

Article abstract of DOI:10.1002/1615-4169(20010430)343:4<351::AID-ADSC351>3.0.CO;2-2

Luminescent semiconducting organic compounds are widely used as active layers in electro-optical devices. Apart from conjugated polymers, monodisperse oligomers also represent attractive materials. The synthesis of stilbenoid oligomers with polymerizable

Full text of DOI:10.1002/1615-4169(20010430)343:4<351::AID-ADSC351>3.0.CO;2-2

FULL PAPERS
Practical Synthesis of Vinyl-Substituted
p-Phenylenevinylene Oligomers
and Their Triethoxysilyl Derivatives
Erli Sugiono, Thorsten Metzroth, Heiner Detert*
Institut fuÈ r Organische Chemie, UniversitaÈt Mainz, Duesbergweg 10-14, 55099 Mainz, Germany
Fax: (+49) 6131-392-5396, e-mail: detert@mail.uni-mainz.de
Received December 15, 2000; Accepted March 7, 2001
Keywords: cross me-
tathesis; materials
science; olefinations;
oligomers; p-phenyle-
nevinylene oligomers;
silane
Abstract: Luminescent semiconducting organic the iodo-substituted oligo-
compounds are widely used as active layers in elec- mers 15, 16 with com-
tro-optical devices. Apart from conjugated poly- pressed ethene. Triethoxy-
mers, monodisperse oligomers also represent at- silyl groups can be linked
tractive materials. The synthesis of stilbenoid via rigid 1,2-vinylene units
oligomers with polymerizable end groups is pre- to the chromophores 26±
sented. Oligo(phenylenevinylene)s with terminal vi- 30, either in the direct reaction of 14, 24 with silanes
nyl groups 17±19 are prepared in good yields by Hor- 21, 22 or by cross-metathesis of 17±19 with the vinyl-
ner±Emmons olefinations or by the Heck reaction of silanes 21, 22 using Grubbs catalyst.
paration of multi-layer devices, which are coated
from solution, one must ensure that the lower layers
Introduction
are not redissolved during the coating of subsequent
The use of conjugated polymers in electro-optical de-
vices has steadily increased since the first reports[1]
layers. A successful route to achieve this goal is the
casting of a soluble precursor and its thermal conver-
about light-emitting diodes with poly(p-phenylenevi-
nylene) (PPV) as active layer. The properties, perfor-
sion to an insoluble polymer, as it is used for the pre-
paration of non-substituted PPV. Electroluminescent
mance and processability of PPV and related materi-
materials with vinyl end groups or side chains[10] are
susceptible to thermal or photochemical cross-link-
ing thus allowing the soluble and processable materi-
als to be cured into insoluble layers.
als have been tremendously improved since.[2]
Besides conjugated polymers, well-defined oligomers
are attractive materials: they serve as model com-
pounds for the polymers and are electronic materials
in their own right.[3] Oligomers can be prepared in
high purity, with monodisperse chain lengths and
free of structural defects. A broad variety of substitu-
ents can easily be introduced[4] to alter the electrical
and optical properties of the chromophore. Whereas
the film forming capabilities of polymers are often ex-
cellent, amorphous films of most oligomers are meta-
stable and tend to recrystallise. Flexible polymers
with conjugated segments in the main chain[5] or
these units as side chains[6] combine the advantages
of both groups, monodisperse chromophores and
high-quality films. To prepare flexible polymers with
oligo(phenylenevinylene) (OPV) side chains, Grei-
ner[7] and Leising[8] grafted vinylstilbene and bro-
mostyrene on partially brominated polystyrene.
Schrock[9] used the ring-opening metathesis poly-
merisation of norbornenes with conjugated side
chains. These polymers are suitable materials for sin-
gle-layer light-emitting diodes. However, for the pre-
In this paper, we describe a convenient route to
monodisperse oligo(phenylenevinylene)s with term-
inal vinyl groups and the cross-metathesis of these
compounds to chromophores with vinyltriethoxysi-
lane end groups. The alkoxysilane group can be hy-
drolyzed and cross-linked to form polymeric net-
works[11] or organic-inorganic hybrid materials,
which can be used for coatings of glass surfaces or
electro-optical devices.[12]
Synthesis and Vinylation
of Iodo-Substituted
Oligo(phenylenevinylene)s
The PO-activated (Horner±Emmons) olefination of
aromatic aldehydes with benzyl phosphonates is a
versatile, convenient and high-yield route to stilbenes
Adv. Synth. Catal. 2001, 343, No. 4
Ó WILEY-VCH Verlag GmbH, 69451 Weinheim, Germany, 2001
1615-4150/01/34301-351±359 $ 17.50-.50/0
351

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and stilbenoid oligomers with (E)-configured double monoprotected terephthal dialdehyde 5 led to stil-
bonds. Small amounts of accompanying (Z)-stilbenes bene aldehyde 6, the key compound for the synthesis
can be removed easily by chromatography, crystalli- of 14±19. For the extension of the conjugated system
zation, or isomerization to the (E)-form. For the of the aldehyde 6, two strategies were employed: the
synthesis of the monodisperse oligo(phenyleneviny- PO-activated olefination of 6 with phosphonate 9[13]
lene)s (17±19, 27±30) with a terminal reactive group carrying an ester group that was reduced to the alco-
(vinyl or trialkoxysilyl) and good solubility, a benzyl hol 10 and reoxidized to an aldehyde 7. The second
phosphonate with two branched alkoxy side chains 4 approach is the olefination of this aldehyde 7 with
was prepared via alkylation of methylhydroqui- synthon 11 followed by cleavage of the protecting
none 1, chloromethylation and subsequent Michae- group to yield aldehyde 8. It is true that this route suf-
lis±Arbusov reaction. A Horner reaction with the fers from the lengthy preparation and purification of
synthon 11,[14] but it is very convenient for small scale
homologizations.
Scheme 2. Heck and Horner reactions to vinyl-substituted
OPVs 17±19.
a) Pd(OAc)2, P(o-tol)3, Et3N, DMF, ethene (30 bar), 100±
110 °C; b) KOtBu, THF, 18-crown-6.
The following conversions to the oligomers with bro-
mine 14 or iodine 15, 16 in the p-position of the term-
inal rings were performed with the 4-halophospho-
nates 12,[15] 13, prepared from the corresponding
benzyl bromides.[16] The Heck coupling of ethene
with bromoarenes to extended conjugated systems
Scheme 1. Synthesis of OPV-aldehydes 6±8.
like the laser dye stilbene I has been investigated by
352
Adv. Synth. Catal. 2001, 343, 351±359

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de Meijere;[17] and a series of styrenes from substi- temperature, sonication, or additional catalyst. The
tuted bromobenzenes and ethene was obtained by yield increased significantly when the conjugated
Heitz et al.[18] Whereas electron-withdrawing groups system was extended. From the homologous com-
activate the bromine atom in the Heck reaction,[19] pound 18 the triethoxysilyl-OPV 30 was obtained in
the reactivity of donor-substituted bromobenzenes is 33% yield and the yield increased to 48% in the trans-
only poor. The rather low yield of 41% of 17 in the pal- formation of 19 to 30. No products derived from
ladium-catalyzed vinylation of bromo-distyrylben- homocoupling in the metathesis reaction were ob-
zene (DSB) 14 required vigorous conditions (140 °C, served.
5 d). When the Heck reaction of iodo-OPVs 15 and 16
was performed under a pressure of 30 bar ethene, the
vinyl-substituted oligo(phenylenevinylene)s 18 and
19 were produced in good to excellent yields (73%
and 91%, respectively) and no traces of the two-fold
coupling products could be detected. A bypass to
avoid the use of iodoarenes is opened when the viny-
lation step is performed on the phosphonate. More
forcing conditions than used for the previous reac-
tions had to be applied in the synthesis of 4-vinylben-
zylphosphonate 20 (140 °C, 70 bar ethene) from 12,
which has already been prepared by Michaelis±Beck-
er reaction of 4-chloromethyl styrene.[20] The yields
of vinyl-OPVs obtained via Horner olefination with
20 (17: 89%, 19: 75%) are comparable to the two-step
procedure with 13 and vinylation with ethene.
The Connection of
Oligo(phenylenevinylene)s with
Alkoxysilanes
Hallberg[21] investigated the Heck reaction of iodoar-
enes with vinylsilanes, the arylethenylsilanes are pro-
duced in moderate yields provided that equimolar
amounts of silver nitrate are present to immobilize
the iodide. These conditions are also suitable for the
conversion of iodo-substituted stilbenes like 24.
Triethoxyvinylsilane 21 could be coupled with 24[22]
to yield 26 (32%) in the presence of AgNO3, with 26
not being detected in an analogous reaction with the
bromostilbene 25.[23] The Hallberg conditions are un-
satisfactory in three aspects: moderate yield, the lim-
itation to iodine-substituted OPVs, and, in particular,
the need for equimolar amounts of silver salts.
Recently, the cross-metathesis of different alkenes
with allylsilanes[24] and alkoxyvinylsilanes[25] with
Schrock's[26] molybdenum or Grubbs'[27] ruthenium
catalyst 23 were reported. These results and the now
Scheme 3. Synthesis of alkoxysilyl-substituted OPVs; a)
readily available vinyl-substituted OPVs (17±19)
cross-metathesis: [Cl2(PCy3)2Ru=CHPh], benzene, ambient
prompted us to study the synthesis of alkoxysilyl-sub-
temperature; b) Pd(OAc)2, P(o-tol)3, Et3N, DMF, 100 °C.
stituted oligomers via cross-metathesis using Grubbs
catalyst 23 [Cl2(PCy3)2Ru=CHPh]. The reaction of the
vinyl-distyrylbenzene 17 with triethoxyvinylsilane 22 The homologization from 17 to 18 and 19 reduces the
was rather disappointing: only small amounts of 17 influence of the 2,5-dialkoxy-substituted terminal
were consumed to yield 28 (5%) and the reaction benzene ring on the electronic properties of the vinyl
could not be completed by removal of ethene in a gen- group on the opposite side of the conjugated system.
tle flow of dry and oxygen-free nitrogen, elevated In the same sequence, the yield improved consider-
Adv. Synth. Catal. 2001, 343, 351±359
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asc.wiley-vch.de
dures and distilled. DMF was stirred with CaH2 for 5 h at
120 °C, distilled in vacuum and stored over activated mole-
cular sieves.
ably. On the other hand, altering the electronic prop-
erties of the silicon-bound vinyl group by replacing an
ethoxy group for methyl on the silane reduced the
conversion dramatically, as it was observed with styr-
ene;[25] with diethoxymethylvinylsilane not even
traces of the desired product were detected. Electro-
nic decoupling of the vinyl group from the silane, as
in the more flexible allylsilane 22, increases the reac-
tivity of the vinyl group in both metal-catalyzed reac-
tions: a yield of 51% of the DSB-silane 27 was ob-
tained via Heck reaction of the bromide 14 compared
to 41% of 17 obtained by the reaction of 14 with
ethene. The cross-metathesis of 17 too, benefited
from the additional methylene group: the yield in-
creased from 5% with silane 21 to 25% in the conver-
sion of silane 22.
In the isolated (by chromatography) compounds, the
stereochemistry of the connecting 1,2-vinylene unit,
generated via Heck reactions (26, 27) or cross-metath-
esis (27±30) was found to be exclusively E, indicated by
large vicinal coupling constants of 19±21 Hz. The vi-
nyl-substituted OPVs (17, 18, limited for 19), as well as
26±30 with siloxane moieties are well soluble in com-
mon solvents, the intensively yellow compounds and
their solutions being strongly fluorescent.
Diether 2
Methylhydroquinone 1 (124 g, 1.0 mol), K2CO3 (346 g, 2,5
mol), KI (5 g, 0.03 mol) and Aliquat 336 (5 g) were added to
a solution of 2-ethylbromohexane (482 g, 2.5 mol) in diox-
ane (800 mL). The mixture was purged with nitrogen and
heated and stirred under N2 for 8 days. The mixture was
cooled, the liquid phase transferred into a separatory funnel
and the solids dissolved with water and added to the organic
solution. Petroleum ether (500 mL) was added, the aqueous
layer was separated and extracted with petroleum ether
(2 ´ 200 mL). The combined organic layers were washed
with water (3 ´ 250 mL), dried with CaCl2, the solvents were
evaporated and the product distilled in vacuum; bp 156±
158 °C (0.04 mbar); yield: 254 g (73%), yellowish oil; IR
(neat): m = 3010, 2950, 2920, 2840, 1580, 1485, 1455, 1370,
1270, 1210, 1160, 1120, 1045, 860, 785 cm±1
;
1H NMR
(CDCl3): d = 0.87 (m, 12 H, CH3), 1.20±1.55 (m, 16 H, CH2),
1.70 (m, 2 H, b-CH), 2.18 (s, 3 H, CH3), 3.77 (m, 4 H, OCH2),
7.70 (m, 3 H, 3-H, 5-H, 6-H); 13C NMR (CDCl3): d = 11.1, 11.3,
14.1 (2 C), 16.4 (CH3), 23.1 (2 C), 23.9, 24.1, 29.1, 29.2, 30.6,
30.8 (CH2), 39.5, 39.7 (CH,), 71.0, 71.1 (OCH2), 111.5, 111.8
(C-5, C-6), 117.7 (C-3), 128.0 (C-2), 151.6, 153.1 (C±O); MS
(EI): m/z = 348 (79) [M+], 236 (46) [M+ ± C8H16], 124 (100)
[M+ ± 2 C8H16]; anal.: calcd. for C23H40O2 (348.563):
C 79.25%, H 11.57%; found: C 79.01%, H 11.23%.
Conclusion
Chloromethylbenzene 3
A stepwise synthesis of a series of vinyl-substituted
oligo(phenylenevinylene)s 17±19 with solubilizing
alkoxy side chains on the opposite side of the conju-
gated system is described. The vinyl group was intro-
duced via palladium-catalyzed reaction of iodo-sub-
stituted OPVs with ethene or in a one-step procedure
with vinylbenzyl phosphonate 20. Access to OPVs with
alkoxysilane-substituted vinyl groups is possible by
Heck reactions (26, 27) and via cross metathesis of vi-
nyl-substituted OPVs with triethoxyvinyl- and allylsi-
lane (27±30). These highly fluorescent molecules,
OPV chromophores rigidly connected to hydrolyzable
alkoxysilane moieties, are curable compounds that
are interesting for electrical and optical applications.
Paraformaldehyde (7.5 g, 0.25 mol) was added to a solution
of diether 2 (70.0 g, 0.2 mol) and concentrated hydrochloric
acid (50 mL) in dioxane (300 mL). The mixture was cooled
with iced water and saturated with gaseous HCl. The satu-
rated solution was slowly heated to a gentle reflux and kept
at this temperature for 2 h. The cooled solution was diluted
with water (1.5 L) and extracted with petroleum ether
(4 ´ 200 mL). The combined organic layers were washed
with water until the washings were neutral and dried with
CaCl2. The solvents were stripped off and the residue puri-
fied by chromatography on silica gel using petroleum ether
(40±70) as an eluent; yield: 56.1 g (71%), colorless oil; IR
(neat): m = 3030, 2960, 2920, 2870, 1508, 1460, 1408, 1370,
1210, 1040, 860 cm±1 1H NMR (CDCl3): d = 0.93 (m, 12 H,
;
CH3), 1.15±1.60 (m, 16 H, CH2), 1.70 (m, 2 H, b-CH), 2.26 (s,
6 H, CH3), 3.82 (2 ´ d, 4 H, OCH2), 4.62 (s, 2 H, CH2Cl), 6.70,
6.81 (2 ´ s , 2 ´ 1 H, 3-H, 6-H); 13C NMR (CDCl3): d = 11.2,
14.1, 16.3 (CH3), 23.1, 24.0. 24.1, 29.1, 30.6, 30.7, 39.1, (CH,
CH2), 41.9 (CH2Cl), 71.0, 71.2 (OCH2), 113.4, 115.9 (C-3, C-
6), 123.5, 128.7 (C-1, C-4), 150.6, 151.1 (C-2, C-5); MS (EI):
m/z = 396 (61) Cl-pattern [M+], 284 (28) Cl-pattern [M+ ±
C8H16], 172 (100) Cl-pattern [M+ ± 2 C8H16]; anal.: calcd. for
C24 H41 ClO2 (397.041): C 72.60%, H 10.41%; found:
C 72.94%, H 10.68%.
Experimental Section
General Methods
IR spectra: in KBr, Beckman Acculab 4. NMR spectra: in
CDCl3, Bruker AC 200 and AM 400. Mass spectra: 70 eV, Var-
ian MAT 711 (EI), MAT 95 (FD). Chemical shifts are reported
in ppm and referenced to the solvent as internal standard.
The elemental analyses were performed in the microanaly-
tical laboratory of the Chemical Institute of the Johannes
Gutenberg±UniversitaÈt, Mainz, Germany, melting points:
not corrected. Eluent mixtures are v/v. Chemicals were used
as received, solvents dried according to standard proce-
Phosphonate 4
A mixture of triethyl phosphite (33 g, 0.2 mol) and benzyl
chloride 3 (40 g, 0.1 mol) was stirred and heated in a round-
354
Adv. Synth. Catal. 2001, 343, 351±359

FULL PAPERS
bottom flask equipped with a reflux condenser and bubble
counter until the evolution of chloroethane started (ca.
160 °C). This temperature was held until the evolution of
gas ceased and then raised to 180 °C for 30 min. Residual
triethyl phosphite was removed by vacuum distillation and
the product purified by chromatography on silica gel. Elu-
tion was performed with petroleum ether/ethyl acetate (10/
1) first to separate some impurities and the product was
eluted with ethyl acetate; yield: 47 g (94%), nearly colorless
oil; IR (neat): m = 2960, 2820, 2860, 1504, 1455, 1405, 1245,
b-CH), 2.23 (s, 3 H, CH3), 3.87 (m, 4 H, OCH2), 6.73 (s, 1 H,
3-H, Ph''), 7.03 (s, 1 H, 6-H, Ph''), 7.06 (d, J = 16.6 Hz, 1 H,
vin), 7.12 (d, J = 16.1 Hz, 1 H, vin'), 7.26 (d, J = 16.3 Hz, 1 H,
vin'), 7.51 (d, J = 16.6 Hz, 1 H, vin), 7.51 (s, 4 H, Ph'), 7.64
(d, J = 8.3 Hz, 2 H, 3-H, 5-H, Ph), 7.86 (d, J = 8.3 Hz, 2 H, 2-H,
6-H, Ph), 9.98 (s, 1 H, CHO); 13C NMR (CDCl3): d = 11.3, 14.1,
16.5 (CH3, superimposed), 23.1 (2 C), 24.1, 24.2, 29.2, 29.2,
30.8, 30.9, 39.8, 39.8 (CH, CH2), 71.0, 72.0 (OCH2), 108.8,
115.8 (C-3, C-6, Ph), 126.7, 126.8, 127.3, 130.3 (CH, Ph, Ph'),
124.2, 124.5, 126.9, 128.2, 132.0, 135.2, 135.3, 138.7, 143.6
(CH vin, Cqar, superimposed), 150.8, 151.6 (C±O), 191.6
(C±O); MS (FD): m/z = 581 (100) [M+]; anal.: calcd. for
1210, 1030, 960, 880 cm±1 1H NMR (CDCl3): d = 0.79±0.99
;
(m, 12 H, CH3), 1.15±1.63 (m, 22 H, CH2, CH3), 1.68 (m, 2 H,
b-CH), 2.16 (s, 3 H, CH3), 3.20 (d, J = 22.5 Hz, 2 H, CH2P),
3.75 (d, J = 6.2 Hz, 4 H, OCH2), 4.00 (qui, J = 7.5 Hz, 4 H,
POCH2), 6.66 (s, 1 H), 6.85 (s, 1 H); 13C NMR (CDCl3):
d = 11.2, 11.2, 14.0, 16.3 (CH3), 16.4 (d, J = 6.4 Hz, CH3), 23.1,
24.0, 24.1, 29.1, 30.6, 30.7 (CH2), 25.0 (d, J = 139.0 Hz, CH2-
P), 39.7, 39.7 (b-CH), 61.8 (d, J = 7.4 Hz, OCH2), 71.0, 71.3
(OCH2), 114.3 (d, J = 4.8 Hz), 114.7 (d, J = 3.2 Hz) (C-3, C-6),
117.5 (d, J = 9.6 Hz), 126.2 (d, J = 4.1 Hz) (C-1, C-4), 150.4 (d,
J = 7.9 Hz, C-2), 151.2 (C-5); MS (FD): m/z = 998 (7) [M2+], 499
(100) [M+]; anal.: calcd. for C28H51O5P (498.675): C 67.44%,
H 10.31%; found: C 67.62%, H 10.20%.
C40H52O3 (580.839): C 82.71%, H 9.02%; found: C 82.46%,
H 8.83%.
Aldehyde 8
KOtBu (1.5 g, 13.0 mmol) was added to a nitrogen-purged
solution of phosphonate 11 (2.2 g, 6.5 mmol), aldehyde 7
(3.8 g, 6.5 mmol) and 18-crown-6 (50 mg) in anhydrous
THF (30 mL). The mixture was stirred at room temperature
for 4 h, 2 N hydrochloric acid was added until pH = 1 and the
mixture was stirred for further 2 h. Water (50 mL) was
added and the product was extracted with dichloromethane
(3 ´ 30 mL). The combined organic solutions were washed
with water and brine and dried with MgSO4. Purification by
chromatography on silica gel with toluene/petroleum ether
(4/1); yield: 3.9 g (92%), yellow solid, mp 97 °C; IR (KBr):
m = 3012, 2950, 2910, 2850, 1689, 1580, 1503, 1457, 1405,
Aldehyde 6
KOtBu (11.2 g, 0.1 mol) was added to a nitrogen-purged so-
lution of phosphonate 4 (25.0 g, 0.05 mol), 4-(diethoxy-
methyl)benzaldehyde 5 (10.5 g, 0.05 mol) and 18-crown-6
(250 mg) in anhydrous THF (150 mL). The mixture was stir-
red at room temperature for 4 h, 2 N hydrochloric acid was
added until pH = 1 and the mixture was stirred for further
3 h. Water (250 mL) was added and the product was ex-
tracted with dichloromethane (3 ´ 70 mL). The combined
organic solutions were washed with water and brine and
dried with MgSO4. Purification by chromatography on silica
gel with toluene as an eluent; yield: 19.5 g (82%), yellow oil;
IR (neat): m = 3030, 2950, 2910, 2860, 2725, 1690, 1590, 1501,
1204, 1164, 1037, 965, 852, 830, 788 cm±1 1H NMR (CDCl3):
;
d = 0.85±1.00 (m, 12 H, CH3), 1.17±1.64 (m, 16 H, CH2), 1.78
(m, 2 H, b-CH), 2.23 (s, 3 H, CH3), 3.87 (2 ´ d, 4 H, OCH2),
6.71 (s, 1 H), 7.02 (s, 1 H), 7.06±7.22 (m, 4 H), 7.42±7.58 (m,
10 H), 7.64 (d, J = 8.0 Hz, 2 H), 7.88 (d, J = 8.0 Hz, 2 H), 9.98
(s, 1 H, CHO); 13C NMR (CDCl3): d = 11.3, 14.1 (CH3), 16.5
(CH3), 23.1, 24.1, 29.2, 30.8, 30.9 (CH2), 39.8 (CH), 71.0, 72.0
(OCH2), 108.8, 115.8 (CH), 124.0, 124.3, 126.7, 126.9, 127.1,
127.3, 127.6, 128.0, 128.9, 130.3, 131.8, 135.3, 135.8, 136.0,
137.8, 137.9, 143.5 (CH, Cq, superimposed), 150.7, 151.6
(C±O), 191.6 (CHO); MS (FD): m/z = 683 (100) [M+], 342 (2)
[M2+]; anal.: calcd. for C48H58O3 (683.972): C 84.41%,
H 8.56%; C 84.22%, H 8.52%.
1458, 1405, 1375, 1301, 1202, 1162, 1035, 968, 856, 815 cm±1
;
1H NMR (CDCl3): d = 0.9 (m, 12 H, CH3), 1.2±1.6 (m, 16 H,
CH2), 1.83 (m, 2 H, b-CH), 2.23 (s, 3 H, CH3), 3.88 (d,
J = 6.2 Hz, 4 H, OCH2), 6.72 (s, 1 H), 7.01 (s, 1 H), 7.11 (d,
J = 16.0 Hz, 1 H), 7.62 (d, J = 16.0 Hz, 1 H), 7.62 (d, J = 8.1 Hz,
2 H), 7.84 (d, J = 7.9 Hz, 2 H), 9.97 (s, 1 H, CHO); 13C NMR
(CDCl3): d = 11.3, 14.1, 16.6 (CH3), 23.1, 24.1, 24.2, 29.2,
29.2, 30.8, 30.9 (CH2), 39.7 (b-CH), 71.0, 71.9 (OCH2), 109.0,
115.8 (C-3, C-6, Ph'), 126.2, 127.6 (CH, vin), 126.6, 130.2 (C-2,
C-3, C-5, C-6, ph), 123.4, 129.1, 134.9, 144.5 (Cq), 151.1, 151.6
(C±O), 191.6 (CHO); MS (FD): m/z = 958 (49) [M2+], 479 (100)
[M+]; anal.: calcd. for C32H46O3 (478.706): C 80.29%,
H 9.69%; found: C 79.92%, H 9.88%.
Benzylic Alcohol 10
KOtBu (2.0 g, 18 mmol) was added to a nitrogen-purged so-
lution of 4-methoxycarbonylbenzyl phosphonate 9[13] (2.6 g,
9 mmol), aldehyde
6 (3.4 g, 9 mmol) and 18-crown-6
(80 mg) in anhydrous THF (50 mL). The mixture was stirred
at room temperature for 4 h, and diluted with water
(150 mL). The product was extracted with toluene
(3 ´ 60 mL) and the combined organic layers were dried with
MgSO4. The solvent was evaporated, the residue dissolved in
anhydrous ether (60 mL) and added dropwise to a stirred
and refluxing mixture of LiAlH4 (0.6 g, 15.8 mmol) in anhy-
drous ether (20 mL). Heating and stirring were continued
for 6 h, the mixture was cooled in ice and residual hydride
was destroyed and dissolved with 2 N sulfuric acid. The or-
ganic layer was separated, the aqueous layer extracted with
dichloromethane (2 ´ 30 mL) and the combined organic so-
lutions were washed with brine until neutral, dried with
Na2SO4 and concentrated. Purification by chromatography
Aldehyde 7
DDQ (2.2 g, 0.01 mol) was added to a solution of alcohol 10
(5.8 g, 0.01 mol) in dioxane (15 mL). The mixture was stir-
red for 18 h, filtered and concentrated. The residue was pur-
ified by chromatography on silica gel with toluene as an elu-
ent; yield: 3.6 g (63%), greenish, yellow oil; IR (neat):
m = 2950, 2905, 2850, 1688, 1590, 1505, 1455, 1408, 1204,
1165, 1038, 968, 852, 822 cm±1 1H NMR (CDCl3): d = 0.90
;
(m, 12 H, CH3), 1.20±1.60 (m, 16 H, CH2), 1.73 (qui, 2 H,
Adv. Synth. Catal. 2001, 343, 351±359
355

asc.wiley-vch.de
on silica gel with petroleum ether/ether (6/1); yield: 3.9 g
(74%), yellow, soft wax; IR (KBr): m = 3490, 3020, 2960, 2920,
2860, 1510, 1492, 1460, 1408, 1380, 1200, 1040, 1012, 972,
Iodophosphonate 12
A solution of 4-iodobenzyl bromide (23.8 g, 0.08 mol) in
triethyl phosphite (33.2 g, 0.2 mol) was heated while stirring
in a round-bottom flask equipped with a reflux condenser.
The condenser was thermostated at 60 °C and connected to
a distillation bridge. The reaction started at 140 °C and heat-
ing was continued until the evolution of bromoethane
ceased. The temperature was raised to 160 °C for 30 min
and residual triethyl phosphite was removed by vacuum dis-
tillation;[16] yield: 27.7 g (98%), yellowish oil; IR (neat):
840 cm±1 1H NMR (CDCl3): d = 0.93 (m, 12 H, CH3), 1.20±
;
1.65 (m, 16 H, CH2), 1.68 (s, 1 H, OH), 1.77 (m, 2 H, b-CH),
2.24 (s, 3 H, CH3), 3.88 (2 ´ d, 4 H, OCH2), 4.69 (s, 2 H, CH2Cl),
6.73 (s, 1 H, 3-H Ph'''), 7.08 (m, 4 H), 7.34 (d, 2 H), 7.49 (m, 8
H); 13C NMR (CDCl3): d = 11.3, 14.1 (CH3), 16.5, 23.1, 24.2,
24.2, 29.3, 30.8, 30.9, 39.8 (CH, CH2, CH3), 65.2 (CH2OH),
71.0, 72.0 (OCH2), 108.8, 115.9 (C-3, C-6 Ph'''), 123.9, 124.4,
126.7 (4 C), 126.8 (2 C), 127.2, 127.4 (2 C), 127.8, 127.9,
128.5, 136.1, 137.0, 140.2 (CH, Cq), 150.7, 151.6 (C-2, C-5
Ph'''); MS (FD): m/z = 583 (100) [M+]; anal.: calcd. for
m = 2970, 2890, 1578, 1390, 1240, 1050, 1025, 960 cm±1
;
1H NMR (CDCl3): d = 1.25 (t, 6 H, CH3), 3.05 (d, J = 21.5 Hz,
2 H, CH2P), 4.00 (m, 4 H, OCH2), 7.05 (dd, J = 8.2 Hz,
J' = 2.4 Hz, 2 H, 2-H, 6-H), 7.60 (d, J = 7.9 Hz, 2 H, 3-H, 5-H);
13C NMR (CDCl3): d = 16.4 (d, J = 5.5 Hz, CH3), 33.5 (d,
J = 138.0 Hz, CH2P), 62.2 (d, J = 6.0 Hz, OCH2), 92.3 (C-4),
131.3 (d, J = 8.5 Hz, C-1), 131.8, 137.5 (C-2, C-3, C-5, C-6);
MS (EI): m/z = 354 (54) [M+], 326 (18) [M+ ± C2H4], 227 (29)
[M+ ± I]; anal.: calcd.: for C11H16IO3P (354.121): C 37.31%,
H 4.55%; found: C 37.69%, H 4.73%.
C40H54O3 (582.855): C 82.43%, H 9.34%; found: C 82.35%,
H 9.29%.
Phosphonate 11
A solution of 4-(diethoxymethyl)benzaldehyde 5 (36.5 g,
0.176 mol) in anhydrous ether (100 mL) was added drop-
wise during 30 min to a stirred, boiling mixture of LiAlH4
(2.3 g, 0.060 mol) and ether (400 mL). Refluxing and stir-
ring were continued for further 3.5 h, then a solution of
NaOH (6.0 g, 0.15 mol) in water (12 mL) and methanol
(13 mL) was added very cautiously dropwise to the stirred
and boiling solution. After 30 min a saturated solution of
NaCl in water was dropped into the still stirred and reflux-
ing mixture until the organic layer separated from the inor-
ganic compounds, stirring and heating were stopped in this
moment. The mixture was cooled to room temperature, the
organic layer was separated and the residual slurry was
washed with ether (150 mL). The combined organic layers
were thoroughly dried with MgSO4 and the solvent was
evaporated to yield 4-(diethoxymethyl)benzylic alcohol
quantitatively. The alcohol (30 g, 0.140 mol) was added to
a solution of triphenylphosphine (37.5 g, 0.14 mol) and N-
ethyldicyclohexylamine in anhydrous CCl4 (750 mL) and
heated to reflux for 46 h. The cooled mixture was washed
with water (400 mL) and a saturated solution of NaHCO3
(2 ´ 200 mL) and dried with MgSO4. CCl4 (700 mL) was dis-
tilled off and the residue was filtered, the precipitated tri-
phenylphosphine oxide was washed thoroughly with petro-
leum ether. The combined organic solutions were
concentrated and dried under vacuum to yield a dark
brown oil. A sample of this oil (2.5 g) was mixed with
triethyl phosphite (1.84 g, 11.1 mmol) and heated to 160 °C
until the evolution of chloroethane had stopped. Purifica-
tion by chromatography on basic alumina with ethyl acetate
first, followed by silica gel using toluene/ethyl acetate (1/1)
as an eluent; yield: 20% (over 3 steps), yellow oil; IR (neat):
m = 2960, 2880, 1600, 1510, 1445, 1380, 1365, 1240, 1150,
BromoOPV 14
KOtBu (448 mg, 4 mmol) was added to a solution of aldehyde
6 (960 mg, 2 mmol) and phosphonate 12 (622 mg, 2 mmol)
and 18-crown-6 (40 mg) in anhydrous THF (30 mL). The
mixture was stirred at ambient temperature under nitrogen
for 3.5 h, water (50 mL) was added and the product was iso-
lated by extraction with chloroform (3 ´ 30 mL), washing of
the pooled organic solutions with water, drying with MgSO4,
evaporation of the solvent and chromatography on silica gel
with petroleum ether/ethyl acetate as an eluent; yield: 1.1 g
(87%), yellow solid, mp 65±67 °C; IR (KBr): m = 2950, 2910,
2850, 1508, 1458, 1410, 1375, 1205, 1073, 1040, 1008, 958,
854, 822 cm±1 1H NMR (CDCl3): d = 0.83±1.00 (m, 12 H,
;
CH3), 1.24±1.67 (m, 16 H, CH2), 1.77 (m, 2 H, b-CH), 2.23 (s,
3 H, CH3), 3.88 (2 ´ d, 4 H, OCH2), 7.73 (s, 1 H, 5-H, Ph''),
7.01±7.12 (m, 4 H), 7.30±7.52 (m, 9 H); 13C NMR (CDCl3):
d = 11.3, 14.1, 16.5 (CH3), 23.1 (2C), 24.1, 24.2, 29.2 (2 C),
30.7, 30.9, 39.7, 39.8 (CH, CH2), 70.9, 71.9 (OCH2), 108.7,
115.8, 121.2, 124.0, 124.2, 127.9, 135.7, 136.4, 138.0 (CH, Cq),
126.7, 126.9, 129.1, 131.8 (CH, Ph, Ph'), 150.7, 151.6 (C±O);
MS (FD): m/z = 631 (100) Br-pattern [M+]; anal.: calcd. for
C39H51BrO2 (631.725): C 74.15%, H 8.14%; found: C 74.17%,
H 8.01%.
IodoOPV 15
Preparation from 7 (700 mg, 1.12 mmol) and 13 (396 mg,
1.12 mmol) according to the procedure described for 14.
Purification by recrystallization from chloroform/ethanol;
yield: 54%, yellow solid, mp 145 °C; IR (KBr): m = 2990, 2950,
2890, 1640, 1500, 1475, 1435, 1350, 1228, 1090, 1065, 1036,
1040, 1020, 720, 690 cm±1 1H NMR (CDCl3): d = 1.16 (m,
;
12 H, CH3), 3.08 (d, J = 21.8 Hz, 2 H, CH2-P), 3.50 (m, 4 H,
OCH2), 3.95 (m, 4 H, OCH2), 5.43 (s, 1 H, O±CH±O), 7.22 (d,
2 H), 7.34 (d, 2 H); 13C NMR (CDCl3): d = 15.2 (CH3), 16.3 (d,
J = 6.1 Hz, CH3), 33.5 (d, J = 136.8 Hz, CH2-P), 60.9 (CH2O),
62.1 (d, 6.4 Hz, OCH2), 101.2 (O±C±O), 126.8 (d, J = 3.3 Hz,
CH), 129.6 (d, J = 7.2 Hz, CH), 131.6 (d, J = 9.6 Hz, C-1),
137.8 (Cq); MS (FD): m/z = 331 (100) [M+]; anal.: calcd. for
990, 960, 875, 829 cm±1 1H NMR (CDCl3): d = 0.80±1.00 (m,
;
12 H, CH3), 1.20±1.60 (m, 16 H, CH2),1.80 (m, 2 H, b-CH),
6.71 (s, 1 H, Ph'''), 2.23 (s, 3 H, CH3), 3.88 (2 ´ d, 4 H, OCH2),
6.95±7.15 (m, 6 H), 7.20±7.26 (m, 2 H), 7.42±7.53 (m, 9 H),
7.68 (d, J = 7.8 Hz, 2 H); 13C NMR (CDCl3): d = 11.3, 14.1,
16.5 (CH3), 23.1 (2 C), 24.1, 24.2, 29.2, 29.2, 30.8, 30.9 (CH2),
39.7, 39.8 (b-CH), 71.0, 72.0 (OCH2), 92.7 (C±I), 108.8, 115.9
(CH), 126.7 (2 C), 126.9 (2 ´ 2 C), 127.0 (2 C), 128.2 (2 C),
C16H27O5P (330.356): C 58.17%, H 8.24%; found: C 57.91%,
H 8.29%.
356
Adv. Synth. Catal. 2001, 343, 351±359

FULL PAPERS
137.8 (2 C) (CH), 123.9, 124.3, 127.1, 127.3, 127.7, 127.9,
128.6, 129.1, 136.1, 136.2, 136.9, 137.2, 137.8 (CH vin, Cqar),
151.0, 152.9 (C±O); MS (FD): m/z = 781 (100) [M+]; anal.:
calcd. for C47H57IO2 (780.859): C 72.29%, H 7.36%; found:
C 72.25%, H 7.51%.
m = 3008, 2960, 2920, 1580, 1505, 1418, 1215 cm±1
;
1H NMR
(CDCl3):d = 0.85±1.03 (m, 12 H, CH3), 1.18±1.63 (m, 16 H,
CH2), 1.76 (quin, J = 5.5 Hz, 2 H, b-CH), 2.25 (s, 3 H, CH3),
3.88 (2 ´ d, 4 H, OCH2), 5.25 (d, J = 11.2 Hz, 1 H, vin), 5.77 (d,
J = 16.4 Hz, 1 H, vin), 6.71 (dd, J = 16.4 Hz, J = 11.2 Hz, 1 H,
vin), 6.74 (s, 1 H, Ph'''), 7.04 (s, 1 H, Ph'''), 7.06±7.15 (m, 5 H,
vin, Ar), 7.32±7.55 (m, 13 H); 13C NMR (CDCl3): d =11.4,
14.2, 16.5 (CH3), 21.0, 21.4, 24.2, 24.3, 29.2, 29.3, 30.8, 31.0
(CH2), 39.8, 39.8 (b-CH), 71.0, 72.0 (OCH2), 108.8, 113.8,
115.9 (C-3, C-6, Ph''', CH2 vin), 126.2 (2 C), 126.9 (2 C), 128.7
(2 C) 130.6 (2 C), 130.2 (2 C), 133.1 (2 C) (CH, Ph, Ph', Ph''),
123.9, 124.4, 126.6, 126.7, 127.2, 127.8, 127.9, 128.3, 128.4,
134.4, 134.6, 136.3, 136.5, 137.0, 137.8 (CH, Cq), 150.7, 151.6
(C±O); MS (FD): m/z =681 (100) [M+]; anal. calcd. for
IodoOPV 16
Preparation from aldehyde 8 (480 mg, 0.7 mmol) and phos-
phonate 13 (290 mg, 0.8 mmol) according to the procedure
described for 14. Purification by recrystallization from to-
luene; yield: 620 mg (89%), yellow solid, mp 270 °C; IR
(KBr): m = 3000, 2940, 2900, 2840, 1570, 1500, 1445, 1399,
1365, 1190, 1100, 1030, 958, 825 cm±1 1H NMR (CDCl3):
;
C49H60O2 (680.999): C 86.42%, H 8.88%; found: C 86.78%,
d = 0.82±1.00 (m, 12 H, CH3), 1.20±1.62 (m, 16 H, CH2), 1.80
(m, 2 H, b-CH2), 2.23 (s, 3 H, CH3), 3.88 (m, 4 H, OCH2), 6.73
(s, 1 H), 7.00±7.15 (m, 8 H), 7.20±7.25 (m, 2 H), 7.42±7.58 (m,
13 H), 7.68 (d, J = 7.0 Hz, 2 H); MS (FD): m/z = 883 (100) [M+],
442 (14) [M2+]: anal.: calcd. for C55H63IO2 (882.992):
C 74.81%, H 7.19%; found: C 74.46%, H 7.28%.
H 8.55%.
VinylOPV 19
Synthesis via Heck reaction with ethene according to the
procedure described for 18 in 91% yield, and also via Horner
olefination of 8 with 20 according to the procedure described
for 17 in 73% yield. Purification by chromatography on silica
gel using petroleum ether/ethyl acetate (10/1) as an eluent;
yellow solid, mp >190 °C; IR (KBr): m = 3010, 2950, 2910, 2850,
VinylOPV 17
Preparation from 6 and 20 according to the procedure de-
scribed for 14 in 89% yield. Via Heck reaction from 14 and
ethene according to the procedure described for 18 using
the two-fold amount of catalyst, and stirring for 5 d at 140 °C
gave 17 in 41% yield. Purification by chromatography on si-
lica gel using petroleum ether/ethyl acetate (10/1) as an elu-
ent. Viscous yellow oil; IR (neat): m = 2900, 2820, 1485, 1440,
1505, 1455, 1402, 1370, 1200, 1035, 965, 910, 840 cm±1
;
1H NMR (CDCl3): d = 0.85±0.99 (m, 12 H, CH3), 1.45±1.68 (m,
16 H, CH2), 1.73 (m, 2 H, b-CH), 2.23 (s, 3 H, CH3), 3.86 (t,
J = 6.2 Hz, 4 H, OCH2), 5.24 (d, J = 10.8 Hz, 1 H, vin), 5.76 (d,
J = 18.2 Hz, 1 H, vin), 6.70 (dd, J = 10.8 Hz, J = 18.4 Hz, 1 H,
vin), 6.72 (s, 1 H, Ph), 7.02 (s, 1 H, Ph), 7.06 (d, J = 16.4 Hz,
1 H, vin), 7.10 (m, 6 H), 7.39 (m, 2 H), 7.46±7.52 (m, 15 H);
13C NMR (CDCl3): d = 11.2, 14.0 (CH3), 16.4 (CH3), 23.0,
24.2, 24.2, 29.2, 29.2, 30.8, 30.9, (CH2), 39.8 (CH), 71.1, 72.1
(OCH2), 124.0, 126.6, 126.7, 126.8 128.2, 128.4, 136.5, 136.7,
136.8, 151.8 (superimposed signals 125±127 ppm, some sig-
nals missing due to poor solubility); MS (FD): m/z = 783
(100) [M+]; anal.: calcd. for C57H66O2(783.133): C 87.42%,
H 8.49%; found: C 87.09%, H 8.30%.
1390, 1185, 1020, 950, 887, 840, 815 cm±1 1H NMR (CDCl3):
;
d = 0.80±0.98 (m, 12 H, CH3), 1.23±1.64 (m, 16 H, CH2), 1.73
(qui, 2 H, b-CH), 2.24 (s, 3 H, CH3), 3.84 (2 ´ d, 4 H, OCH2),
5.23 (d, J = 11.2 Hz, 1 H, vin), 5.76 (d, J = 16.8 Hz, 1 H, vin),
6.70 (dd, J = 11.2 Hz, J = 17.0 Hz, 1 H, vin), 6.72 (s, 1 H, 3-H,
Ph''), 7.03 (s, 1 H, 6-H, Ph''), 7.06 (d, J = 16.0 Hz, 1 H, vin),
7.10 (s, 2 H, vin), 7.36±7.53 (m, 9 H, Ph, Ph', vin); 13C NMR
(CDCl3): d = 11.2, 14.0, 16.3 (CH3), 23.0 (2 C), 24.1, 24.2,
29.1, 29.2, 30.7, 30.9 (CH2), 39.7, 39.8 (CH), 71.0, 72.0
(OCH2), 108.9, 113.5, 115.8 (C-3, C-6, Ph'', CH2 vin), 126.5
(2 C), 126.5 (2 ´ 2 C), 126.7 (2 C) (CH, Ph, Ph'), 123.9, 124.4,
127.1, 127.8, 127.8, 128.3, 136.1, 136.4, 137.0, 137.7 (CH, Cq),
150.7, 151.6 (C±O); MS (FD): m/z = 579 (100) [M+]; anal.:
calcd. for C41H54O2 (578.866): C 85.07%, H 9.40%; found:
C 85.03%, H 9.37%.
4-Vinylphosphonate 20
Pd(OAc)2 (44 mg, 0.2 mmol) and tri-o-tolylphosphine
(120 mg, 0.4 mmol) were added to a solution of phosphonate
12 (6.15 g, 0.02 mol) in a mixture of anhydrous DMF (30 mL)
and triethylamine (10.0 g, 0.1 mol). The mixture was placed
in an autoclave (100 mL), purged with nitrogen, ethene was
added (pressure 50 bar) and while stirring the temperature
was brought to 140 °C for 8 h (the pressure increased to 70
bar). The cooled mixture was diluted with water (100 mL),
the product was extracted with chloroform (5 ´ 60 mL) and
the combined organic solutions were washed with water
(2 ´ 100 mL) and brine (50 mL). After drying with MgSO4,
the solvent was evaporated and the residue was purified by
chromatography on silica gel using dichloromethane/ethyl
acetate as an eluent;[28] yield: 2.75 g (54%), yellowish oil; IR
(neat): m = 2960, 2870, 2850, 1611, 1497, 1435, 1395, 1235,
VinylOPV 18
Pd(OAc)2 (4.4 mg, 20 mmol) and tri-o-tolylphosphine
(12.0 mg, 40 mmol) were added to a solution of OPV 15
(390 mg, 0.5 mmol) in
a mixture of anhydrous DMF
(30 mL) and triethylamine (0.5 g, 5 mmol). The mixture
was placed in an autoclave (100 mL), purged with nitrogen,
ethene was added (pressure 30 bar) and while stirring the
temperature was brought to 100 °C for 8 h. The cooled mix-
ture was diluted with water (100 mL), the product was ex-
tracted with chloroform (5 ´ 30 mL). The combined organic
solutions were washed with water (2 ´ 100 mL) and brine
(50 mL). After drying with MgSO4, the solvent was evapo-
rated and the residue was purified by chromatography on si-
lica gel using petroleum ether/ethyl acetate (20/1) as an elu-
ent; yield: 250 mg (73%), yellow solid, mp 126 °C; IR (CDCl3):
1
1175, 1045, 1015, 950, 845, 797, 772, 745, 680 cm±1; H NMR
(CDCl3): d = 1.24 (t, J = 7.2 Hz, 6 H, CH3), 3.11 (d, J = 22.0 Hz,
2 H, CH2-P), 4.01 (quin, J = 7.0 Hz, 4 H, OCH2), 5.22 (d,
J = 10.8 Hz, 1 H, vin), 5.71 (d, J = 17.0 Hz, 1 H, vin), 6.68 (d,
J = 10.8 Hz, J = 17 Hz, 1 H, vin), 7.23 (d, J = 8.2 Hz, 2 H, Ph),
Adv. Synth. Catal. 2001, 343, 351±359
357

asc.wiley-vch.de
7.33 (d, J = 8.2 Hz, 2 H, Ph); 13C NMR (CDCl3): d = 16.4 (d,
J = 6.4 Hz, CH3), 33.6 (d, J = 136.8 Hz, CH2-P), 62.1 (d,
J = 7.2 Hz, OCH2), 113.7 (CH2, vin), 128.5 (CH), 129.9 (d,
J = 7.2 Hz, CH), 132.9 (d, J = 7.5 Hz, Cq), 136.2 (Cq), 136.4
(CH, vin); MS (FD): m/z = 255 (100) [M+].
16.5 (CH3), 17.8 (Si-CH2), 18.2 (CH3), 23.1, 24.1, 24.2, 29.2,
29.2, 30.8, 30.9 (CH2), 58.7 (OCH2), 71.0, 72.0 (OCH2), 108.8,
115.9 (C-3, C-6, ph), 123.8, 124.3, 125.2, 126.0 (2 C), 126.6
(2 ´ 2 C), 126.7 (2 C), 127.2, 127.8, 128.0, 129.7, 135.7, 136.3,
137.6 (CH, Cq, 2 signals superimposed), 150.7, 151.6 (C±O);
MS (FD): m/z = 755 (100) [M+], 378 (4) [M2+]; anal.: calcd.
Â
Â
for
C48H70O5Si (755.152): C 76.34%, H 9.34%; found.:
Silane 26
C 76.28%, H 9.46%.
Iodostilbene 24 (1.0 g, 3 mmol), Pd(OAc)2 (20 mg,
0.09 mmol), triphenylphosphine (47 mg, 0.18 mmol), and
AgNO3 (0.50 g, 3 mmol) were added to a solution of silane
21 (0.68 g, 3.6 mmol) and triethylamine (0.36 g, 3.6 mmol)
in anhyd acetonitrile (20 mL). The mixture was transferred
to an autoclave (100 mL), purged with nitrogen and stirred
at 120 °C for 19 h. The mixture was diluted with water
(50 mL) and the product extracted with ethyl acetate
(3 ´ 30 mL). The pooled organic solutions were washed with
iced water, dried with MgSO4, and, after evaporation of the
solvent, the residue was purified by chromatography on sili-
ca gel using petroleum ether/ethyl acetate (10/1) as an elu-
ent; yield: 0.38 g (32%), slightly yellow solid, mp 152 °C; IR
(KBr): m = 2970, 2890, 1600, 1510, 1388, 1260, 1180, 1100,
Silane 28
Grubbs catalyst 23 (ca. 3 mg) was added to a solution of vi-
nyl-DSB 17 (1.0 g, 1.72 mmol) and silane 21 (1.6 g 8.4 mmol)
in anhydrous benzene (100 mL) in a round-bottom flask
equipped with nitrogen inlet tube and a reflux condenser
with bubble counter. A gentle flow of dry and oxygen-free ni-
trogen was bubbled through the solution for 20 h. The solu-
tion was concentrated and the product isolated by chromato-
graphy on silica gel with toluene/cyclohexane 10/1 as an
eluent; yield: 60 mg (5%) of 28, yellow oil, and 820 mg
(82%) of unchanged 17. 28: IR (CDCl3): m = 2955, 2918,
2850, 1588, 1500, 1445, 1400, 1195, 1065 cm±1 1H NMR
;
970, 830 cm±1 1H NMR (CDCl3): d = 1.26 (t J = 6.9 Hz, 9 H,
;
(CDCl3): d = 0.80±0.95 (m, 12 H, CH3), 1.30 (t, J = 6.5 Hz, 9 H,
CH3), 1.20±1.60 (m, 16 H, CH2), 1.74 (qui, 2 H, b-CH), 2.22 (s,
3 H, CH3), 3.81±3.93 (m, 10 H, OCH2), 6.16 (d, J = 19.0 Hz,
1 H, Si-vin), 6.73 (s, 1 H, 3-H, Ph''), 7.02 (s, 1 H, 6-H, Ph''),
7.06 (d, J = 16.2 Hz, 1 H, vin), 7.11 (s, 2 H, vin), 7.20 (d,
J = 19.0 Hz, 1 H, Si-vin), 7.49 (m, 9 H, Ph, Ph', vin); 13C NMR
(CDCl3): d = 11.3, 14.0, 16.4 (CH3), 18.3 (CH3), 23.1, 24.2,
24.3, 29.2, 29.3, 30.8, 31.0 (CH2), 39.8, 39.9 (CH), 58.6 (Si-
OCH2), 71.2, 72.1 (OCH2), 108.8, 115.9, 117.5, 124.0, 126.7
(2 C), 126.9 (2 C), 127.1 (2 ), 127.2 (2 C), 127.7, 128.5, 128.9,
148.6 (CH), 124.5, 127.9, 136.1, 137.9, 138.0 (Cq), 150.8,
151.7 (C±O); MS (FD): m/z = 741 (100) [M+], 371 (2) [M+];
anal.: calcd. for C47H68O5Si (741.125): C 76.17%, H 9.25%;
found: C 76.07%, H 9.37%.
CH3), 3.83 (s, 3 H, OCH3), 3.87 (q, J = 7.0 Hz, 6 H, OCH2),
6.15 (d, 1 H, J = 21.1 Hz, 1 H, ethene-Si), 6.85 (d, J = 8.0 Hz,
2 H, 3-H, 5-H, Ph', 9.92 (d, J = 16.2 Hz, 1 H, CH ethene, 7.10
(d, J = 21.1 Hz, 1 H, ethene-Si), 7.20 (d, 1 h ethene, 7.44 (m,
6 H); 13C NMR (CDCl3): d = 18.3 (CH3), 55.3 (OCH3), 58.6
(OCH2), 114.2 (C-3, C-5 Ph'), 126.4, 127.2, 127.8 (3 ´ 2 C, CH,
Ph, Ph'), 117.2, 126.0, 128.7 (CH), 130.1, 136.6, 138.2 (Cq),
148.7 (CH±CHSi), 159.5 (C±O); MS (FD): m/z = 399 (100)
[M+]; anal.: calcd. for C23H30O4Si (398.567): C 69.31%,
H 7.59%; found: C 69.27%, H 7.55%.
Silane 27
Method a): Pd(OAc)2 (20 mg, 0.09 mmol) and tris-o-tolyl-
phosphine (54 mg, 0,8 mmol) were added to a solution of
bromo-DSB 14 (0.30 g, 0.47 mmol), silane 22 (0.10 g,
0.47 mmol) and triethylamine (0.24 g, 2.35 mmol) in anhy-
drous DMF (30 mL). The mixture was purged with N2 and
stirred under N2 for 3 h at 120 C. Toluene (100 mL) was
added, the mixture washed with iced water (3 ´ 70 mL) and
dried with Na2SO4. Evaporation of the solvent was followed
by chromatography of the residue on silica gel with toluene/
cyclohexane (10/1) to afford the product; yield: 0.18 g (51%),
yellow oil.
Method b): Grubbs catalyst 23 (ca. 3 mg) was added to a
solution of the vinyl-DSB 17 (0.23 g, 0.4 mmol) and silane 22
(0.40 g, 2 mmol) in anhydrous benzene (50 mL) and a gentle
flow of dry and oxygen-free N2 was passed through the solu-
tion for 6 h. The solvent was evaporated and the product iso-
lated by chromatography; yield: 25%; IR (neat): m = 3015,
2960, 2910, 2850, 1631, 1590, 1505, 1455, 1405, 1385, 1200,
1163, 1100, 1075, 1035, 960, 852, 785, 755, 730 cm±1; 1H NMR
(CDCl3): d = 0.88±0.94 (m, 12 H, CH3), 1.25 (t, J = 6.9 Hz, 9 H,
CH3), 1.28±1.58 (m, 16 H, CH2), 1.74 (m, 2 H, b-CH), 1.81 (d,
J = 8.0 Hz, 2 H, Si-CH2), 3.22 (s, 3 H, CH3), 3.85 (m, 10 H,
OCH2), 6.26 (dt, J = 16.1 Hz, J = 8.0 Hz, 1 H, vinyl), 6.34 (d,
J = 16.1 Hz, 1 H, vin), 6.71 (s, 1 H, 3-H, Ph''), 7.00±7.09 (m, 4
H), 7.29 (m, 2 H, J = 8.4 Hz, 2 H), 7.42 (d, J = 8.4 Hz, 2 H),
7.45±7.50 (m, 7 H); 13C NMR (CDCl3): d = 11.3, 14.1 (CH3),
Silane 29
Preparation from 18 according to the procedure described
for 28. Yield: 33%, yellow, greenish oil; IR (CDCl3): m = 2955,
2918, 2850, 1588, 1500, 1445, 1400, 1195, 1065 cm±1; 1H NMR
(CDCl3): d = 0.80±1.00 (m, 12 H, CH3), 1.27 (t, J = 6.5 Hz, 9 H,
CH3), 1.20±1.60 (m, 16 H, CH2), 1.74 (qui, 2 H, b-CH), 2.22 (s,
3 H, CH3), 3.80±3.95 (m, 10 H, OCH2), 6.16 (d, J = 19.0 Hz,
1 H, Si-vin), 6.72 (s, 1 H, 3-H, Ph''), 7.02 (s, 1 H, 6-H, Ph''),
7.11 (m, 6 H), 7.43±7.56 (m, 13 H, Ph, Ph', vin); 13C NMR
(CDCl3): d = 11.2, 13.9 (CH3), 16.3 (CH3), 18.2 (CH3), 22.9,
23.0, 24.1, 24.2, 29.2, 29.5, 30.8, 30.9 (CH2), 39.7, 39.8 (CH),
58.5 (Si-OCH2), 71.1, 72.1 (OCH2), 109.0, 115.9, 117.7, 123.9,
126.6 (2 C), 126.7 (4 C), 126.8 (2 C), 127.1 (2 C), 127.2, 127.7,
127.9, 128.4, 128.6, 148.5 (CH), 124.4, 127.8, 128.8, 136.1,
136.5, 137.0, 137.8, 137.9 (Cq), 150.8, 151.8 (C±O) (1 ´ CH
superimposed); MS (FD): m/z = 844 (100) [M+], 422 (2)
[M2+]; anal. calcd. for C55H74O5Si (843.259): C 78.34%,
H 8.85%; found: C 78.01%, H 8.64%.
Silane 30
Preparation from 19 according to the procedure described
for 28, due to the limited solubility of 19, the flask was im-
mersed into a ultrasonic cleaning bath. Yield: 48%, yellow
358
Adv. Synth. Catal. 2001, 343, 351±359

FULL PAPERS
solid, mp 126 °C; IR (CDCl3): m = 2910, 2900, 2840, 1580, 1500,
107, 129±135; (b) C. Yang, G. He, R. Wang, Y. Li, J.
Appl. Polym. Sci. 1999, 73, 2535±2539.
1
1440, 1400, 1195, 1070 cm±1; H NMR (CDCl3): d = 0.80±1.00
(m, 12 H, CH3), 1.29 (m, 9 H, CH3), 1.20±1.65 (m, 16 H, CH2),
1.75 (m, 2 H, b-CH2), 2.22 (s, 3 H, CH3), 3.85±3.92 (m, 10 H,
OCH2), 6.20 (d, J = 19.6 Hz, 1 H, vin), 6.73 (s, 1 H), 7.0±7.24
(m, 9 H), 7.38±7.57 (m, 15 H); 13C NMR (CDCl3): d = 11.3,
14.1 (CH3), 16.5 (CH3), 18.3 (CH3), 23.1 (2 C), 24.1, 24.2, 29.7
(2 C), 30.8, 30.9 (CH2), 39.7, 39.8 (CH), 58.7 (OCH2), 71.0,
72.0 (OCH2), 108.8, 115.8, 117.6, 123.9, 126.9±127.2 superim-
posed signals, 148.6 (CH) 124.3, 136.2, 136.6, 136.9, 137.8,
137.8, (Cq), 127.2, 127.8, 127.9, 128.1, 128.3, 128.4, 128.7,
130.3 (CH, Cq), 150.7, 151.6 (C±O); MS (FD): m/z = 946 (100)
[M+], 473 (36) [M2+]; anal.: calcd. for C63H80O5Si (945.392):
C 80.04%, H 8.53%; found: C 80.02%, H 8.50%.
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