Synthesis of Perylene-Tagged Internal and External Electron Donors for Magnesium Dichloride Supported Ziegler-Natta Catalysts

Article abstract of DOI:10.1055/s-0037-1611085

We report on the synthesis of three perylene-tagged electron donors representing three major types- phthalates, diethers, and alkoxysilanes - which are of importance for the subsequent studies of MgCl ₂ -supported Ziegler-Natta catalysts by means of laser scanning confocal fluorescence microscopy. The obtained products were unambiguously characterized, including by X-ray crystal structure analysis; their photophysical properties (absorption and emission spectra) were investigated as well. Additionally, a reliable and convenient protocol for the multigram synthesis of the required starting material - 3-bromoperylene (PerBr) - was developed. The key step of this method was synthesis of trialkylsilyl-substituted perylenes, which were further separated by means of flash chromatography followed by conversion of the isolated 3-trialkylsilyl-substituted product to PerBr.

Full text of DOI:10.1055/s-0037-1611085

SYNTHESIS
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© Georg Thieme Verlag Stuttgart · New York
2018, 50, A–I
paper
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de
B. A. Guzeev et al.
Paper
Synthesis
Synthesis of Perylene-Tagged Internal and External Electron Donors
for Magnesium Dichloride Supported Ziegler–Natta Catalysts
Bogdan A. Guzeev
CO2nBu
Dmitry Y. Mladentsev
Mikhail I. Sharikov
Per
CO2nBu
Br
Georgy P. Goryunov
Dmitry V. Uborsky
O
O
3 steps
Si
Per
perylene
Alexander Z. Voskoboynikov*
yield > 70%
scale > 20 g
Department of Chemistry, Lomonosov Moscow State University,
1/3 Leninskie Gory, GSP-1, 119991 Moscow, Russian Federation
voskoboy@med.chem.msu.ru
O
Per
purity > 99%
O
Per = 3-perylenyl
Received: 27.08.2018
Accepted after revision: 08.10.2018
Published online: 06.11.2018
ed to the final catalytic system. The Ziegler–Natta catalysts
most broadly used for polypropylene production are those
of the fourth generation; they include dialkylphthalates as
internal donors and dialkoxysilanes as external donors. In
the fifth generation catalysts, the phthalates are replaced
with diethers (derivatives of 1,3-dialkoxypropane) or succi-
nates.5
DOI: 10.1055/s-0037-1611085; Art ID: ss-2018-t0471-op
Abstract We report on the synthesis of three perylene-tagged elec-
tron donors representing three major types – phthalates, diethers, and
alkoxysilanes – which are of importance for the subsequent studies of
MgCl2-supported Ziegler–Natta catalysts by means of laser scanning
confocal fluorescence microscopy. The obtained products were unam-
biguously characterized, including by X-ray crystal structure analysis;
their photophysical properties (absorption and emission spectra) were
investigated as well. Additionally, a reliable and convenient protocol for
the multigram synthesis of the required starting material – 3-bromo-
perylene (PerBr) – was developed. The key step of this method was syn-
thesis of trialkylsilyl-substituted perylenes, which were further separat-
ed by means of flash chromatography followed by conversion of the
isolated 3-trialkylsilyl-substituted product to PerBr.
Although Ziegler–Natta catalysts have been known for
over half a century, due to their complex nature, they are
still in the focus of numerous studies aiming to further elu-
cidate the details of their structure and behavior. The mech-
anisms of the polymerization reactions and the catalyst
structure and fragmentation have been investigated by
NMR spectroscopy,6 scanning electron microscopy (SEM),7
transmission electron microscopy (TEM),8 X-ray microsco-
py,9 and other methods. In recent years, laser scanning con-
focal fluorescence microscopy (LSCFM) has been introduced
as a powerful method to study fragmentation of Ziegler–
Natta catalysts.10 This method is very simple and appeared
to be a faster alternative to electron microscopy.11 For ex-
ample, catalyst fragmentation was investigated by this tech-
nique by using tagged supports, but there are no examples
of using perylene-tagged or other tagged electron donors in
the literature (although applications of perylene-based
compounds were reported in the fields of development of
semiconducting materials,12 OLEDs,13 and cell imaging14). In
this regard, the aim of the present work was to synthesize
and characterize compounds 1–3 (Figure 1), representing
three main types of organic electron donors, with the
perylenyl fragment as the fluorescent dye. The perylene
core was chosen for tagging electron donors because of its
stability under polymerization conditions and high fluores-
cence quantum yields.15 An additional aspect of this work
was to develop a preparative method for the synthesis of
the not readily available key starting material – 3-bromo-
Key words 3-substituted perylenes, electron donors, Ziegler–Natta
catalysts, emission spectra, fluorescence spectra
One of the most important milestones in chemistry and
in chemical industry in the last century was the discovery
of Ziegler–Natta olefin polymerization catalysts in the
1950s.1,2 Since then, countless improvements of the
Ziegler–Natta catalysts were introduced by industry, giving
rise to novel systems that are chronologically combined
into several generations.3 Polymerization using supported
Ziegler–Natta catalysts of the latest generations is the most
important method for the industrial production of isotactic
polypropylene.4 These systems, which can be described as
TiCl4/MgCl2/ID/R3Al/ED, consist of titanium(IV) chloride,
the solid support (MgCl2), an aluminum alkyl cocatalyst
(R3Al), and internal (ID) and external (ED) donors. The do-
nors are of crucial importance for achieving high polymer
tacticity and regulation of the molecular weight distribu-
tion. Internal donors are used for the preparation of the
supported catalyst itself, whereas external donors are add-
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2018, 50, A–I

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B. A. Guzeev et al.
Paper
Synthesis
perylene. Finally, we aimed to study the photophysical
properties of 1–3 to confirm their possible use as fluores-
cent tags.
values for all the compounds shown in Scheme 1 made this
kind of purification ineffective. Therefore, we needed to de-
velop a new protocol for large-scale preparation of 3-bro-
moperylene, since it is the starting material for all three
target donors. The idea was to modify the perylene core
with a substituent that would increase solubility, so that
flash chromatography could be easily applied to separate
mixtures of the substituted perylenes. An additional re-
quirement was that this new functional group could be
changed back to a halogen atom in good yield. An example
of such a group is a trialkylsilyl moiety, which should im-
prove the solubility of the products, but can be easily re-
placed with bromine by treatment with NBS under suitable
conditions.21
CO2nBu
iPr
nBuO2C
MeO
OMe
OMe
Me
Si OMe
1
2
3
Figure 1 Electron donors to be synthesized
Before modification of a mixture of the bromide and di-
bromides, we decided to conduct the bromination of
perylene with a maximum yield of monobromo derivative
and reduce the content of the starting perylene to an as low
as possible level. Having varied the bromination conditions,
we found that the addition of 1.3 equivalents of NBS gave an
8:1 mixture of PerBr and PerBr2 with a small trace (<1%) of
perylene (as judged by GC). To obtain a mixture of the cor-
responding TMS derivatives, i.e., TMSPer and TMS2Per, the
obtained mixture of PerBr and PerBr2 was treated with a
slight excess of nBuLi in THF followed by the addition of an
excess of TMSCl (Scheme 2).
The synthesis of 1–3 started with the bromination of
perylene16–19 to provide the key intermediate, 3-bromo-
perylene (PerBr), which formed along with significant
amounts of both isomeric dibromoperylenes (PerBr2)
(Scheme 1). Additionally, depending on the ratio of the re-
agents, the products are usually contaminated (up to 30%)
with unreacted perylene.
Br
Br
conditions
TMS
TMS
+
1. BuLi (1.2 equiv)
PerBr + PerBr2
X
PerBr2
X = H, Y = Br or X = Br, Y = H
Y
+
2. TMSCl
54%
perylene
PerBr
X
Y
Scheme 1 Bromination of perylene
TMS2Per
TMSPer
X = H, Y = TMS or X = TMS, Y = H
Although isolation of PerBr by recrystallization of crude
mixtures of products from various solvents had been re-
ported,16–19 the isolated samples of PerBr were contaminat-
ed with PerBr2 and unreacted perylene; that is undesirable
for many applications. Furthermore, for a larger scale syn-
thesis, all the published procedures have two major draw-
backs: high dilution (up to 30 mL per mmol) and formation
of the target material contaminated with PerBr2 and/or un-
reacted perylene, which are difficult to remove using re-
crystallization. It should be noted that all our attempts to
follow the literature purification procedures were unsuc-
cessful; we obtained only mixtures of the desired monobro-
mide PerBr with varied content of starting perylene and di-
brominated derivatives. The plausible reason is π-stacking,
a type of intermolecular interaction known for polyaromat-
ics.20
Scheme 2 Synthesis of trimethylsilyl-substituted perylene
Actually, this mixture of the TMS-substituted perylenes
showed much higher solubility in the common solvents
than the corresponding bromo derivatives, but the differ-
ences between the Rf values of the components were not
high enough for easy and effective purification of multi-
gram samples by flash chromatography. Nevertheless, a
smaller sample of TMSPer successfully isolated in this man-
ner was found to react with NBS to give PerBr in almost
quantitative yield.
To develop a more practical procedure, the solubility of
the substituted perylene derivatives to be separated should
be increased dramatically. Synthesis of similar silylated
perylenes bearing a longer alkyl chain at silicon could be a
solution to this problem (Scheme 3). OctMe2SiPer and
(OctMe2Si)2Per were found to be significantly more soluble
in all common solvents than the TMS-substituted ana-
For the purpose of our work we needed multigram
quantities of pure PerBr. After failures with purification by
recrystallization, we tried to use column chromatography,
but the poor solubility of perylene derivatives and close Rf
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C
B. A. Guzeev et al.
Paper
Synthesis
logues, and so their separation could be performed on a
multigram scale. As before, OctMe2SiPer reacted with NBS
in CH2Cl2 to form PerBr in almost quantitative yield.
tallized from methylcyclohexane to give almost pure mate-
rial in 58% yield. The final product 2 was also purified by re-
crystallization from methylcyclohexane.
To synthesize the target electron donor 3, we decided to
use a cross-coupling reaction26 between PerBr and a suit-
able organometallic reagent (Scheme 6). First, according to
Scheme 6, aldehyde 10 was synthesized and then used as a
precursor in a number of attempts to prepare the corre-
sponding alkyl halide, from which an organometallic re-
agent could be obtained. Unfortunately, our attempts to
convert 10 (after reduction to alcohol 10a with NaBH4) to
the corresponding alkyl bromide or iodide failed, since the
only obtained compound was the product of the rearrange-
ment shown in Scheme 7. As a result, 11 was isolated in al-
most quantitative yield in all three cases.
R = SiMe2nOct
R
R
1. BuLi (1.2 equiv)
PerBr + PerBr2
+
2. nOctMe2SiCl
78%
X
Y
OctMe2SiPer
(OctMe2Si)2Per
X = H, Y = R or X = R, Y = H
Scheme 3 Synthesis of (octyldimethylsilyl)-substituted perylene
EtO2C
Thus, we have developed a new three-step protocol that
can be used for large-scale preparation of 3-bromoperylene.
This procedure gave analytically pure PerBr in >70% overall
yield starting from a 25 gram sample of perylene.
EtO2C
EtO2C
HO
HO
i
ii
iii
iPr
iPr
iPr
97%
99%
93%
EtO2C
7
8
O
M
Synthesis of the perylene-tagged dibutylphathalate 1 is
illustrated in Scheme 4. Bromination of phthalic anhydride
with bromine in aqueous NaOH22 followed by esterification
with nBuOH gave 4, which was then borylated with (BPin)2
via the Miyaura protocol23 in the presence of 5 mol% of
Pd(OAc)2/2Ph3P and anhydrous KOAc. The boronic acid es-
ter 5 was introduced into the Pd(PPh3)4-catalyzed Suzuki–
Miyaura reaction24 with PerBr to give the desired coupling
product 1.
MeO
MeO
MeO
MeO
MeO
MeO
iv
iPr
iPr 46%
iPr
M = MgX, ZnX,
B(OR)2, etc.
10
9
Scheme 6 Synthesis of aldehyde 10. Reagents and conditions: (i) NaH,
AllBr; (ii) LAH; (iii) NaH, MeI; (iv) OsO4/NaIO4.
OH
MeO
MeO
MeO
i or ii or iii
R
R
R
O
iPr
10a
R
R
iPr
R
i
ii
11
85%
62%
Br
BPin
Per
4
5
1
Scheme 7 Cyclization of 10a to 11. Reagents and conditions: (i) MsCl,
Et3N, then KBr; (ii) MsCl, Et3N, then KI; (iii) Ph3P, CBr4.
Scheme 4 Synthesis of diester 1 (R = CO2nBu). Reagents and conditions:
(i) (BPin)2, Pd(OAc)2, Ph3P, KOAc, THF; (ii) Pd(PPh3)4, K2CO3, toluene–
EtOH–H2O.
After this failure, we decided to carry out addition of
perylenyllithium (derived from PerBr) to aldehyde 10, fol-
lowed by catalytic reduction of alcohol 12 thus formed
(Scheme 8). This addition was performed as expected, but
the subsequent reduction of 12 with hydrogen over Pd/C re-
sulted in partial hydrogenation of the perylene aromatic
core. Alternatively, the so-called ionic hydrogenation was
Synthesis of the perylene-tagged silane-based donor 2
was carried out via reaction of 3-perylenyllithium with
MeSiCl325 followed by substitution of the chlorine atoms at
silicon with OMe moieties by treatment with methanol–
pyridine (Scheme 5). The crude chlorosilane 6 was recrys-
O
O
Cl
OMe
Me
Me
i
ii
Si Cl
Si OMe
i
ii
PerBr
O
O
PerBr
Per
Per
58%
92%
OH
Per
77%
71%
6
2
Per
Scheme 5 Synthesis of silylated perylene 2. Reagents and conditions: (i)
12
3
nBuLi, MeSiCl3; (ii) MeOH, pyridine.
Scheme 8 Synthesis of 3. Reagents and conditions: (i) nBuLi, then 9; (ii)
Et3SiH, AcFOH (AcF = CF3C(O)).
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2018, 50, A–I

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B. A. Guzeev et al.
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Synthesis
used,27 and the desired electron donor 3 was obtained in
good yield. It should be noted that the main side product of
the ionic hydrogenation was a cyclic ether similar to 11,
presumably formed via trapping of the intermediate benzyl
cation by oxygen from one of the two methoxy groups.
The molecular structure of 3 was determined by X-ray
crystallography (Figure 2). Single crystals of this compound
were grown from methylcyclohexane. As confirmed by
crystallography analysis, the perylenyl moiety is not planar.
The central six-membered ring is twisted with dihedral an-
gles of 0.5° and 3.2° related to the C(7A)–C(6A)–C(19A)–
C(18A) and C(3A)–C(4A)–C(11A)–C(12A) carbon atoms.
The molecular structure of TMS2Per as established by X-
ray crystallography is shown in Figure 4. Suitable crystals of
the compound were obtained from a methylcyclohexane
solution. The central six-membered ring is twisted with di-
hedral angles 8.1° and 9.9° related to the C(9)–C(8)–C(18)–
C(19) and C(5)–C(6)–C(16)–C(15) carbon atoms. In the
crystal state, each independent molecule forms a stacking
polymer (Figure 5). Fragment of crystal packing: ladder
shape stack with interplane distance of 3.33 Å, shortest C···C
contacts of C(9)···C(15A)x–1,y,z 3.389(6) Å and C(9)···C(14A)x–1,y,z
3.412(6), and distance between centroids of the polycyclic
fragments of 7.02 Å.
Figure 2 Molecular structure of 3 (thermal ellipsoids drawn at the 50%
probability level). Selected bond lengths (Å) are C(1A)–C(21A),
1.511(3); C(1A)–C(2A), 1.366(3); C(2A)–C(3A), 1.402(3); C(3A)–C(4A),
1.379(3); C(4A)–C(11A), 1.474(3); C(4A)–C(5A), 1.428(3); C(5A)–
C(10A), 1.433(3).
Figure 4 Molecular structure of TMS2Per (thermal ellipsoids are drawn
at the 50% probability level). Selected bond lengths (Å) are C(1)–Si(1),
1.883(4); C(11)–Si(2), 1.885(4); C(1)–C(2), 1.432(6); C(1)–C(10),
1.384(5); C(2)–C(7), 1.441(5); C(7)–C(8), 1.422(5); C(8)–C(9),
1.382(5); C(8)–C(18), 1.472(5); C(9)–C(10), 1.404(5).
In the crystal state, each independent molecule forms a
centrosymmetric stacking dimer (Figure 3). The distances
between the average planes of the polyaromatic fragments
in the dimers of molecules A and B are 3.44 and 3.47 Å, re-
spectively. The shortest interatomic distances (Å) in the di-
mers are: C(1A)···C(5A)2–x,–y,–z, 3.432(3); C(3A)···C(9A)2–x,–y,–z
,
3.466(4); C(1B)···C(5B)1–x,1–y,–z, 3.466(3); and C(3B)···C(9B)1–
x,1–y,–z, 3.496(4).
Figure 5 Molecular structure of stacking polymer of TMS2Per
The UV-vis absorption and fluorescence behavior of
perylene and its derivatives was studied in acetonitrile
solution. The absorption spectra of the compounds are
shown in Figure 6; the quantitative data are summarized in
Table 1. UV-vis absorptions of perylene and its derivatives
display very similar profiles: the spectra contain a strong
Figure 3 Molecular structure of the stacking dimer of 3
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2018, 50, A–I

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B. A. Guzeev et al.
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Synthesis
absorption maximum at about 250 nm, with a more or less
pronounced shoulder, as well as a strong absorption at 330-
450 nm with a vibronic structure. As one could expect, in-
troduction of substituents at the third position of perylene
led to a bathochromic shift in the absorption maxima com-
pared to unsubstituted perylene; the largest shift (10 nm)
was observed for 1.
ing electronic communication between the perylene and
phenyl units. The emission quantum yields (Φf) are in the
range of 0.67–0.91.
We developed a reliable and reproducible method for
the preparation of multigram quantities of 3-bromo-
perylene via a three-step protocol starting from unsubsti-
tuted perylene with an overall yield as high as 70%. The key
step of this protocol was the synthesis of trialkylsilyl-sub-
stituted perylenes, which were further separated by means
of flash chromatography. The desired mono(trialkylsi-
lyl)perylene was converted into the corresponding bro-
mide. In addition, three perylene-based electron donors
(which are examples of three main types of donors: phthal-
ates, diethers, and alkoxysilanes) were successfully synthe-
sized from the thus obtained 3-bromoperylene; the solid-
state structure of one target compound was examined by
means of X-ray crystallography. Furthermore, we recorded
absorption and emission spectra as well as calculated emis-
sion quantum yields for all electron donors obtained. The
structure and photophysical properties make the electron
donors ideal candidates for labeling MgCl2-supported
Ziegler–Natta catalysts for subsequent investigation of their
properties by means of fluorescence spectroscopy methods.
Figure 6 Absorption spectra of donors 1–3 and perylene in MeCN (10–5
M) at 20 °C
Table 1 Optical Properties of Donors 1–3 and Perylene in MeCN (10–5
M) at 20 °C
Compound λmaxa (nm)
λmaxb (nm) Stokes shiftc (×105 cm–1
)
Φfd
0.67
perylene
432
442
439
440
442
474
451
452
10
1
2
3
3.1
8.3
8.3
0.81
0.75
0.91
All reagents were obtained from commercial sources and used as re-
ceived. Hydrocarbon solvents were dried over 4 Å MS for at least 24 h
prior to use. Ethereal solvents were stored over solid KOH for 24 h,
then refluxed over and distilled from sodium-benzophenone. MeOH
was stored over 3 Å MS for 48 h prior to use. Flash chromatography
was carried out on silica gel 60 (40–63 μm). NMR spectra were re-
corded on Bruker Avance 400 MHz and Bruker Avance II 600 MHz
spectrometers at r.t. unless otherwise stated. IR spectra were record-
ed on a Perkin-Elmer Spectrum One FT-IR spectrometer with a dia-
mond UATR sampling accessory. Absorptions are reported as values in
cm–1 followed by the relative intensity: s = strong, m = medium,
w = weak. Melting points were measured on a Buchi B-545 instru-
ment. Absorption spectra were recorded on a Hitachi U-1900 spectro-
photometer. Emission spectra were recorded on a Hitachi F-7000 lu-
minescence spectrometer; samples were placed in a standard quartz
cuvette with a spectral path length of 10 mm. Spectral measurements
were carried out for solutions of PerBr and 1–3 in MeCN (10–6 M).
Quantum yields were calculated by the reference dye (rhodamine B)
method from the absorbance and the integrated luminescence inten-
sities. HRMS spectra were measured on an Orbitrap Elite instrument.
a Maximum of absorption spectra.
b Maximum of emission spectra (λexc = 250 nm).
c Stokes shift.
d Fluorescence quantum yield.
Figure 7 Emission spectra of donors 1–3 and PerBr in MeCN (10–5 M)
at 20 °C
Bromoperylene (PerBr)
The fluorescence emission properties of perylene and
its derivatives are shown in Figure 7; the quantitative data
are summarized in Table 1. All compounds show intense
photoluminescence in solution; along with this, we ob-
served red-shift fluorescence for all the compounds in com-
parison to perylene. The perylenyl derivatives, except for 1,
exhibit a very similar emission profile, which is close to
perylene and appears as a mirror image of the absorption
spectrum. In the case of 1, we observed a lower resolution
of the vibronic structure in the emission spectra, suggest-
Mixture of Brominated Perylenes
To a suspension of perylene (25.0 g, 100 mmol, 1 equiv) in DMF (1000
mL) a solution of NBS (23.0 g, 130 mmol, 1.3 equiv) in DMF (400 mL)
was added via a syringe pump for 10 h. The obtained mixture was
stirred overnight at r.t. and poured into water (2000 mL). The precipi-
tate obtained was filtered off on a glass frit (G3) and was subsequent-
ly washed with EtOH (100 mL), Et2O (100 mL), and finally with CH2Cl2
(3 × 100 mL). The obtained solid was dried under vacuum, yielding a
mixture of brominated perylenes; yield: 29.8 g (90%); 89% of 3-bro-
moperylene by GC-MS; yellow solid.
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B. A. Guzeev et al.
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Synthesis
Bromoperylene (PerBr) via OctMe2SiPer; Method A
OctMe2SiPer
PerBr from TMSPer
To a solution of TMSPer (1.00 g, 3.08 mmol, 1 equiv) in CH2Cl2 (50
mL), a solution of NBS (0.55 g, 3.08 mmol, 1 equiv) in CH2Cl2 (20 mL)
was added for 15 min at –30 °C. The reaction mixture was stirred
overnight at r.t. The precipitate obtained was filtered off on a glass frit
(G3) and was washed with CH2Cl2 (3 × 10 mL). The obtained solid was
dried in vacuum, yielding PerBr; yield: 1.02 g (quant.); yellow solid.
1H NMR (400 MHz, CDCl3): δ = 8.21 (d, J = 7.5 Hz, 1 H), 8.18 (d, J = 7.5
Hz, 1 H), 8.14 (d, J = 7.5 Hz, 1 H), 8.07 (d, J = 8.4 Hz, 1 H), 7.97 (d,
J = 8.2 Hz, 1 H), 7.74 (d, J = 8.1 Hz, 1 H), 7.69 (d, J = 8.2 Hz, 2 H), 7.56 (t,
J = 8.0 Hz, 1 H), 7.47 (td, J = 7.8, 5.1 Hz, 2 H).
To a suspension of the brominated perylenes (12.4 g, 36.7 mmol, 1
equiv) in anhyd THF (500 mL), 2.5 M nBuLi in hexanes (17.6 mL, 44.1
mmol, 1.2 equiv) was added dropwise at –80 °C. The reaction mixture
was stirred for 1 h at this temperature, and then dimethyl(n-octyl)si-
lyl chloride (9.87 g, 47.7 mmol, 1.3 equiv) was added and the obtained
suspension was stirred overnight at r.t. Thereafter the resulting mix-
ture was carefully poured into water (1000 mL) and the obtained
two-phase mixture was extracted with CH2Cl2 (3 × 200 mL). The com-
bined organic extract was dried over Na2SO4 and then evaporated to
dryness. The residue was purified by flash chromatography (silica gel,
n-hexane/CH2Cl2, 4:1). This procedure gave OctMe2SiPer; yield: 12.2 g
(78%); yellow solid; mp 100.5–100.9 °C.
HRMS: m/z calcd for C20H11Br: 330.0044; found: 330.0017.
Dibutyl 4-Bromophthalate (4)
To a suspension of 4-bromophthalic acid (25.0 g, 102 mmol, 1 equiv)
in toluene (400 mL), nBuOH (100 mL, 1.09 mol, 10 equiv) and H2SO4 (2
mL) were added. The reaction mixture was refluxed using a Dean–
Stark head for 2 h and then cooled to r.t. Thereafter the resulting mix-
ture was carefully poured into water (300 mL), and the obtained two-
phase mixture was extracted with toluene (2 × 100 mL). The com-
bined organic extract was dried over Na2SO4 and then evaporated to
dryness. The residue was purified by vacuum distillation (138–
140 °C, 0.7 mbar) to give 4.
IR (neat): 3048w, 2955w, 2919m, 2851w, 1590w, 1457w, 1383w,
1246m, 1063w, 1002m, 846m, 809s, 763s, 682m cm–1
.
1H NMR (400 MHz, CDCl3): δ = 8.15–8.19 (m, 3 H), 8.12 (d, J = 7.5 Hz, 1
H), 7.95 (d, J = 8.3 Hz, 1 H), 7.64–7.69 (m, 3 H), 7.48–7.52 (m, 1 H),
7.45 (t, J = 7.8 Hz, 2 H), 1.22–1.42 (m, 12 H), 0.99–1.03 (m, 2 H), 0.88
(t, J = 6.9 Hz, 3 H), 0.50 (s, 6 H).
13C NMR (100 MHz, CDCl3): δ = 138.5, 137.5, 134.5, 134.1, 132.2,
131.8, 131.4, 131.2, 128.7, 128.5, 127.9, 127.6, 126.51, 126.49, 126.0,
120.3, 120.1, 119.9, 119.3, 33.6, 31.9, 29.3, 24.1, 22.7, 16.5, 14.1, –1.5.
Yield: 28.0 g (78%); colorless oil.
HRMS: m/z calcd for C30H34Si: 422.2430; found: 422.2448.
IR (neat): 2960m, 2935w, 2874w, 1723s, 1589w, 1254s, 1122s, 1088s,
1068s, 939m, 890w, 838m, 767m, 696w cm–1
.
PerBr from OctMe2SiPer
1H NMR (400 MHz, CDCl3): δ = 7.79 (s, 1 H), 7.61 (m, 2 H), 4.28 (q,
J = 6.5 Hz, 4 H), 1.60–1.78 (m, 4 H), 1.32–1.48 (m, 4 H), 0.86–1.02 (m,
6 H).
13C NMR (150 MHz, CDCl3): δ = 168.4, 168.2, 134.2, 133.6, 131.5,
130.5, 130.3, 125.3, 65.7, 65.5, 30.33, 30.32, 19.0, 13.5.
To a solution of OctMe2SiPer (4.50 g, 10.6 mmol, 1 equiv) in CH2Cl2
(100 mL) a solution of NBS (1.90 g, 10.6 mmol, 1 equiv) in CH2Cl2 (60
mL) was added for 15 min at –30 °C. The reaction mixture was stirred
overnight at r.t. The precipitate obtained was filtered off on a glass frit
(G3) and was washed with CH2Cl2 (3 × 50 mL). The obtained solid was
dried under vacuum, yielding PerBr; yield: 3.56 g (quant.); yellow sol-
id.
HRMS: m/z calcd for C16H21BrO4: 356.0623; found: 356.0591.
Compound 5
To a solution of Ph3P (0.83 g, 3.16 mmol, 0.1 equiv) in anhyd THF (350
mL), Pd(OAc)2 (0.35 g, 1.56 mmol, 0.05 equiv), 4 (11.3 g, 31.6 mmol, 1
equiv), bis(pinacolato)diboron [(BPin)2; 8.84 g, 34.8 mmol, 1.1 equiv],
and KOAc (9.30 g, 94.8 mmol, 3 equiv) were added. The obtained sus-
pension was refluxed for 12 h, then carefully poured into water (500
mL); the obtained two-phase mixture was extracted with Et2O
(3 × 250 mL). The combined organic extract was dried over Na2SO4
and then evaporated to dryness. The residue was purified by flash
chromatography (silica gel, n-hexane/ethyl acetate, 10:1), giving 5.
Bromoperylene (PerBr) via TMSPer; Method B
TMSPer
To a suspension of the brominated perylenes (1.36 g, 4.43 mmol, 1
equiv) in anhyd THF (50 mL), 2.5 M nBuLi in hexanes (1.95 mL, 4.87
mmol, 1.1 equiv) was added dropwise at –80 °C. The reaction mixture
was stirred for 1 h at this temperature; then TMSCl (0.62 mL, 4.87
mmol, 1.1 equiv) was added, and the obtained suspension was stirred
overnight at r.t. Thereafter the resulting mixture was carefully poured
into water (100 mL) and the obtained two-phase mixture was ex-
tracted with CH2Cl2 (3 × 50 mL). The combined organic extract was
dried over Na2SO4 and then evaporated to dryness. The residue was
purified by flash chromatography (silica gel, n-hexane/THF, 4:1). This
procedure gave TMSPer; yield: 0.78 g (54%); yellow solid; mp 181.2–
181.7 °C.
Yield: 9.50 g (85%); yellow viscous oil.
IR (neat): 2961w, 2935w, 2875w, 1724s, 1359s, 1256s, 1099s, 1068s,
964m, 851s, 710m, 669m cm–1
.
1H NMR (400 MHz, CDCl3): δ = 8.10 (s, 1 H), 7.92 (dd, J = 7.7, 1.0 Hz, 1
H), 7.68 (d, J = 7.7 Hz, 1 H), 4.28 (td, J = 6.8, 1.5 Hz, 4 H), 1.63–1.78 (m,
4 H), 1.42 (dq, J = 15.0, 7.5 Hz, 5 H), 1.33 (s, 13 H), 0.94(t, J = 7.3 Hz, 6
H).
13C NMR (150 MHz, CDCl3): δ = 167.7, 167.6, 137.0, 134.8, 134.3,
131.5, 127.9, 84.4, 83.5, 64.2, 65.42, 65.38, 30.5, 30.4, 24.7, 19.0, 13.6.
IR (neat): 3047w, 2952w, 2895w, 1497w, 1247w, 1062w, 1002w,
857m, 824s, 808s, 763s, 666m cm–1
.
1H NMR (400 MHz, CDCl3): δ = 8.15–8.19 (m, 3 H), 8.11 (d, J = 7.4 Hz, 1
H), 7.95 (d, J = 8.2 Hz, 1 H), 7.65–7.69 (m, 3 H), 7.43–7.52 (m, 3 H),
0.51 (s, 9 H).
HRMS: m/z calcd for C22H33BO6: 404.2370; found: 404.2352.
13C NMR (100 MHz, CDCl3): δ = 138.4, 138.1, 134.6, 133.9, 132.3,
131.9, 131.4, 131.2, 128.7, 128.6, 128.2, 128.0, 127.7, 128.6 (overlap-
ping resonances), 126.1, 120.4, 120.2, 120.0, 119.4, 0.2.
Dichloro(methyl)(perylen-3-yl)silane (6)
To a suspension of PerBr (9.43 g, 28.5 mmol, 1 equiv) in anhyd THF
n
(900 mL), 2.5 M BuLi in hexanes (11.4 mL, 28.5 mmol, 1 equiv) was
HRMS: m/z calcd for C23H20Si: 324.1334; found: 324.1346.
added dropwise at –80 °C. The reaction mixture was stirred for 1 h at
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B. A. Guzeev et al.
Paper
Synthesis
this temperature, then trichloro(methyl)silane (14.0 mL, 114 mmol, 4
equiv) was added, and the obtained suspension was stirred overnight
at r.t. Thereafter the resulting mixture was evaporated to dryness, and
the residue was redissolved in toluene (300 mL). The resulting sus-
pension was filtered through a pad of Celite 503 and then evaporated
to dryness. The residue was recrystallized from toluene and the ob-
tained precipitate was filtered off on a glass frit (G3), washed with
cold toluene (3 × 10 mL), and then dried under vacuum yielding 6.
13C NMR (150 MHz, CDCl3): δ = 134.9, 117.5, 67.7, 43.1, 34.2, 28.4,
17.03.
HRMS: m/z calcd for C9H18O2: 158.1307; found: 158.1321.
Compound 9
To a suspension of NaH (12.1 g, 504 mmol, 2.1 equiv) in anhyd THF
(1000 mL), 8 (38.0 g, 240 mmol, 1 equiv) was added dropwise for 10
min at 0 °C. The resulting mixture was stirred at this temperature for
30 min, then MeI (85.2 g, 600 mmol, 2.5 equiv) was added dropwise,
and the reaction mixture was stirred overnight at r.t. Thereafter the
resulting mixture was carefully poured into water (2000 mL), and the
obtained two-phase mixture was extracted with Et2O (3 × 300 mL).
The combined organic extract was dried over Na2SO4 and then evapo-
rated to dryness. This procedure gave 9; yield: 41.4 g (93%); colorless
oil.
Yield: 6.04 g (58%); yellow solid; mp 217.0–217.8 °C.
IR (neat): 2961w, 2935w, 2875w, 1724s, 1359s, 1256s, 1099s, 1068s,
964m, 851s, 710m, 669m cm–1
.
1H NMR (400 MHz, CDCl3): δ = 8.16–8.27 (m, 3 H), 8.14 (dd, J = 7.9, 3.2
Hz, 2 H), 7.93 (d, J = 7.7 Hz, 1 H), 7.70 (d, J = 8.1 Hz, 1 H), 7.73 (d,
J = 8.0 Hz, 1 H), 7.58 (t, J = 7.9 Hz, 1 H), 7.44–7.53 (m, 2 H), 1.24 (s, 3
H).
13C NMR (150 MHz, CDCl3, 55 °C): δ = 135.0, 130.4, 129.6, 129.1 (three
overlapped resonances), 128.5, 128.2, 127.3, 127.2, 126.8, 126.6,
121.5, 120.9, 120.6, 118.9. 6.9. ( Due to the very low solubility of the
compound in CDCl3, even at elevated temperatures, we were not able
to detect all carbons in the 13C NMR spectrum.)
IR (neat): 3075w, 2977w, 2921w, 2875m, 2809w, 1638w, 1459w,
1386w, 1199w, 1108s, 997w, 959w, 910m cm–1
.
1H NMR (400 MHz, CDCl3): δ = 5.75–5.92 (m, 1 H), 4.89–5.10 (m, 2 H),
3.28 (s, 6 H), 3.24 (s, 4 H), 2.09 (d, J = 7.4 Hz, 2 H), 1.77 (spt, 1 H), 0.89
(d, J = 7.0 Hz, 6 H).
13C NMR (150 MHz, CDCl3): δ = 135.7, 116.6, 75.1, 59.0, 43.1, 36.1,
HRMS: m/z calcd for C21H14Cl2Si: 364.0242; found: 364.0261.
30.6, 17.7.
Diethyl 2-Allyl-2-isopropylmalonate (7)
HRMS: m/z calcd for C11H22O2: 186.1620; found: 186.1596.
To a suspension of NaH (6.23 g, 260 mmol, 1.05 equiv) in anhyd THF
(1000 mL), diethyl 2-isopropylmalonate (50.0 g, 247 mmol, 1 equiv)
was added dropwise for 10 min at 0 °C. The resulting mixture was
stirred at this temperature for 30 min, then allyl bromide (31.5 g, 260
mmol, 1.05 equiv) was added dropwise, and the reaction mixture was
stirred overnight at r.t. Thereafter the resulting mixture was carefully
poured into water (2000 mL), and the obtained two-phase mixture
was extracted with Et2O (3 × 300 mL). The combined organic extract
was dried over Na2SO4 and then evaporated to dryness. This proce-
dure gave 7; yield: 58.5 g (97%); colorless oil.
Compound 10
To a solution of 9 (41.4 g, 220 mmol, 1 equiv) and OsO4 (570 mg, 2.2
mmol, 0.01 equiv) in a THF–water mixture (800 mL, 3:1), NaIO4 (100
g, 470 mmol, 2.1 equiv) was added in small portions for 45 min. The
resulting suspension was additionally stirred for 2 h, then filtered
through a pad of Celite 503. The filtrate was extracted with Et2O
(3 × 300 mL) and the combined organic extract was dried over Na2SO4
and then evaporated to dryness. The residue was purified by fraction-
al distillation under reduced pressure. This procedure gave 10; yield:
18.9 g (46%); colorless oil; bp 88 °C/2 mbar.
IR (neat): 3080w, 2980w, 2939w, 2880w, 1724s, 1640w, 1465w,
1369w, 1275m, 1226s, 1136m, 1042s, 918m, 858w cm–1
.
IR (neat): 2963w, 2925w, 2879w, 2812w, 2749w, 1716s, 1462w,
1H NMR (400 MHz, CDCl3): δ = 5.74 (ddt, J = 17.1, 10.0, 7.2 Hz, 1 H),
4.91–5.16 (m, 2 H), 4.17 (q, J = 7.1 Hz, 4 H), 2.64 (d, J = 7.2 Hz, 2 H),
2.30 (spt, J = 6.9 Hz, 1 H), 1.24 (t, J = 7.2 Hz, 6 H), 0.98 (d, J = 6.9 Hz, 6
H).
13C NMR (101 MHz, CDCl3): δ = 170.7, 133.5, 118.1, 61.7, 60.7, 38.1,
31.7, 18.4, 14.1.
1391w, 1199m, 1105s, 963m cm–1
.
1H NMR (400 MHz, CDCl3): δ = 9.76 (t, J = 3.2 Hz, 1 H), 3.36 (s, 4 H),
3.27 (s, 6 H), 2.30 (d, J = 3.2 Hz, 2 H), 1.89 (spt, J = 7.0 Hz, 1 H), 0.87 (d,
J = 7.0 Hz, 6 H).
13C NMR (101 MHz, CDCl3): δ = 202.9, 74.2, 58.9, 45.8, 44.8, 30.4, 17.2.
HRMS: m/z calcd for C10H20O3: 188.1412; found: 188.1422.
HRMS: m/z calcd for C13H22O4: 242.1518; found: 242.1533.
Compound 10a
Compound 8
To a solution of 10 (3.00 g, 16.0 mmol, 1 equiv) in THF (30 mL) and
MeOH (15 mL), NaBH4 (0.90 g, 24.0 mmol, 1.5 equiv) was added in
small portions at r.t. The resulting mixture was stirred overnight, di-
luted with brine, and extracted with Et2O (2 × 30 mL). The combined
organic extract was dried over Na2SO4 and then evaporated to dry-
ness. This procedure gave 10a; yield: 2.60 g (86%); colorless oil.
To a suspension of LAH (27.4 g, 723 mmol, 3 equiv) in anhyd Et2O
(1500 mL), 7 (58.5 g, 241 mmol, 1 equiv) was added dropwise for 1 h
at 0 °C. The reaction mixture was stirred for 4 h at r.t., then carefully
quenched with water (60 mL). The resulting suspension was filtered
through a pad of Celite 503. The organic layer was separated, dried
over Na2SO4, and then evaporated to dryness. This procedure gave 8;
yields 38.0 g (quant.); colorless oil.
IR (neat): 3400w, 2960w, 2922m, 2876m, 2809w, 1460w, 1450w,
1385w, 1198m, 1106s, 1035m, 1011m, 958m cm–1
.
IR (neat): 3349s, 3076w, 2961m, 2935m, 2883m, 1638w, 1440m,
1H NMR (400 MHz, CDCl3): δ = 3.77 (br.s, 1 H), 3.53–3.56 (m, 2 H),
3.21–3.30 (m, 10 H), 1.77–1.88 (m, 1 H), 1.55–1.58 (m, 2 H), 0.79 (d,
J = 7.0 Hz, 6 H).
1388m, 1175w, 1036s, 995s, 911s cm–1
.
1H NMR (400 MHz, CDCl3): δ = 5.74–5.93 (m, 1 H), 4.97–5.16 (m, 2 H),
3.75 (d, J = 10.9 Hz, 2 H), 3.65 (d, J = 10.8 Hz, 2 H), 2.40 (s, 2 H), 2.13 (d,
J = 7.5 Hz, 2 H), 1.83–1.98 (m, 1 H), 0.89 (d, J = 7.0 Hz, 6 H).
13C NMR (100 MHz, CDCl3): δ = 75.0, 59.0, 58.4, 42.3, 35.6, 30.2, 17.0.
HRMS: m/z calcd for C10H22O3: 190.1569; found: 190.1558.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2018, 50, A–I

H
B. A. Guzeev et al.
Paper
Synthesis
Compound 11
precipitate was filtered off on a glass frit (G3), washed with CH2Cl2
(3 × 10 mL), and then dried under vacuum, yielding 1; yield: 11.8 g
(62%); yellow solid; mp 115.9–116.4 °C.
To a solution of 10a (1.50 g, 7.90 mmol, 1 equiv) in CH2Cl2 (35 mL),
Et3N (1.12 g, 11.1 mmol, 1.4 equiv) was added. The resulting mixture
was cooled to 0 °C and MsCl (1.17 g, 10.2 mmol, 1.3 equiv) was added
dropwise and the mixture was stirred for 2 h at the same tempera-
ture. Brine (50 mL) was added to the mixture and the organic layer
was separated, dried over Na2SO4, and then evaporated to dryness.
The residue was redissolved in DMF (30 mL) and KI (3.72 g,
22.0 mmol, 3 equiv) was added in portions. The resulting viscous re-
action mixture was stirred at 65 °C for 20 min, poured into brine
(100 mL), and extracted with hexane (2 × 50 mL). The combined or-
ganic extract was dried over Na2SO4 and then evaporated to dryness.
The residue was purified by flash chromatography (silica gel, n-hex-
ane/Et2O, 5:1). This procedure gave 11; yield: 0.80 g (68%); yellow oil.
IR (neat): 2958w, 2933w, 2873w, 1721s, 1601w, 1280s, 1243s, 1122s,
1069s, 828m, 809s, 766s cm–1
.
1H NMR (400 MHz, CDCl3): δ = 8.21 (m, 4 H), 7.80–7.94 (m, 2 H), 7.59–
7.76 (m, 4 H), 7.36–7.54 (m, 4 H), 4.26–4.43 (m, 4 H), 1.66–1.84 (m, 4
H), 1.37–1.54 (m, 4 H), 0.88–1.05 (m, 6 H).
13C NMR (101 MHz, CDCl3): δ = 167.7, 167.3, 143.8, 137.3, 134.4,
132.9, 132.3, 132.1, 131.4, 131.4, 130.9, 130.6, 130.6, 130.0, 129.1,
128.8, 128.3, 127.9, 127.8, 127.6, 126.8, 126.4, 126.4, 125.0, 120.4,
120.3, 120.3, 119.6, 77.3, 76.7, 65.7, 65.6, 30.6, 30.5, 19.2, 19.1, 13.7,
13.7.
HRMS: m/z calcd for C36H32O4: 528.2301; found: 528.2317.
IR (neat): 2961m, 2930w, 2873m, 2810w, 1466w, 1389w, 1368w,
1200m, 1177m, 1108s, 1072m, 1047m, 965m, 942m, 921m cm–1
.
Compound 2
1H NMR (400 MHz, CDCl3): δ = 3.72–3.81 (m, 2 H), 3.60–3.62 (m, 1 H),
3.52–3.54 (m, 1 H), 3.29 (s, 3 H), 3.25–3.27 (m,2 H), 1.76–1.86 (m, 1
H), 1.57–1.73 (m, 2 H), 0.89 (d, J = 7.0 Hz, 3 H), 0.88 (d, J = 6.9 Hz, 3 H).
13C NMR (100 MHz, CDCl3): δ = 76.2, 74.4, 68.3, 59.1, 50.3, 32.6, 32.0,
18.6, 18.4.
To a solution of 6 (9.00 g, 24.6 mmol, 1 equiv) in toluene (300 mL),
MeOH (18.0 mL) was added dropwise at 0 °C. To the obtained solution
pyridine (4.00 mL, 51.2 mmol, 1 equiv) was added dropwise, and the
reaction mixture was stirred for 6 h at r.t. Thereafter the obtained
suspension was evaporated to dryness, and the residue was extracted
with boiling methylcyclohexane (400 mL). The obtained solution was
evaporated to dryness, yielding 2; yield: 8.05 g (92%); yellow solid;
mp 149.6–149.9 °C.
HRMS: m/z calcd for C9H18O2: 158.1307; found: 158.1319.
Compound 12
To a suspension of PerBr (13.0 g, 39.3 mmol, 1 equiv) in anhyd THF
(500 mL), 2.5 M BuLi in hexanes (16.0 mL, 39.3 mmol, 1 equiv) was
IR (neat): 3048w, 2937w, 2834w, 1591w, 1498w, 1384w, 1256w,
n
1187w, 1067s, 1003w, 811s, 761s, 686m cm–1
.
added dropwise at –80 °C. The reaction mixture was stirred for 1 h at
this temperature, then 10 (8.13 g, 43.2 mmol, 1.1 equiv) was added
dropwise, and the obtained suspension was stirred overnight at r.t.
Thereafter the resulting mixture was carefully poured into water (500
mL), and the obtained two-phase mixture was extracted with CH2Cl2
(3 × 500 mL). The combined organic extract was dried over Na2SO4
and then evaporated to dryness. The residue was purified by flash
chromatography (silica gel, n-hexane/CH2Cl2, 1:1). This procedure
gave 12; yield: 13.0 g (77%); yellow solid; mp 146.8–147.3 °C.
1H NMR (400 MHz, CD2Cl2): δ = 8.18–8.29 (m, 4 H), 8.15 (d, J = 8.3 Hz,
1 H), 7.90 (d, J = 7.4 Hz, 1 H), 7.72 (t, J = 8.2 Hz, 2 H), 7.45–7.60 (m, 3
H), 3.63 (s, 6 H), 0.49 (s, 3 H).
13C NMR (101 MHz, CDCl3): δ = 138.4, 135.6, 134.5, 133.4, 131.6,
131.5, 131.3, 130.9, 128.6, 128.5, 128.3, 127.8, 127.8, 126.9, 126.6,
126.5, 120.7, 120.3, 120.1, 119.3, 50.6, –3.8.
HRMS: m/z calcd for C23H23O2Si: 356.1233; found: 356.1211.
Compound 3
IR (neat): 3452w, 3050w, 2952w, 2896w, 2815w, 1589w, 1386m,
1185w, 1098s, 1063m, 971m, 822m, 766s cm–1
.
To a solution of 12 (13.0 g, 29.5 mmol, 1 equiv) in CH2Cl2 (400 mL),
Et3SiH (23.5 mL, 148 mmol, 5 equiv) was added. To the obtained solu-
tion trifluoroacetic acid (12.0 mL, 148 mmol, 5 equiv) was added
dropwise at –20 °C. The reaction mixture was stirred for 6 h at r.t.
Thereafter the resulting mixture was carefully poured into water (500
mL), and the obtained two-phase mixture was extracted with CH2Cl2
(3 × 300 mL). The combined organic extract was dried over Na2SO4
and then evaporated to dryness. The residue was purified by column
chromatography (silica gel, n-hexane/CH2Cl2, 1:1). This procedure
gave 3; yield: 8.80 g (71%); yellow solid; mp 136.0–136.7 °C.
1H NMR (400 MHz, CDCl3): δ = 8.13–8.30 (m, 4 H), 7.93 (d, J = 8.4 Hz, 1
H), 7.84 (d, J = 7.9 Hz, 1 H), 7.66 (dd, J = 7.8, 5.4 Hz, 2 H), 7.39–7.55 (m,
3 H), 5.51 (d, J = 10.3 Hz, 1 H), 3.59–3.79 (m, 2 H), 3.51 (s, 3 H), 3.36–
3.48 (m, 5 H), 1.96–2.10 (m, 2 H), 1.80 (dd, J = 15.3, 10.4 Hz, 1 H), 0.86
(d, J = 7.0 Hz, 3 H), 0.88 (d, J = 7.0 Hz, 3 H).
13C NMR (150 MHz, CDCl3): δ = 141.8, 134,6, 131.7, 131.4 (three over-
lapped resonances), 129.9, 128.9, 128.5, 127.6, 127.3, 126.5, 126.4,
126.2, 123.4, 123.0, 120.3, 120.1, 119.9, 119.8, 76.1, 73.9, 66.3, 59.2,
59.1, 44.2, 43.1, 31.7, 17.2, 17.0.
IR (neat): 2965w, 2927w, 2869w, 1387m, 1189w, 1098s, 975w, 826m,
HRMS: m/z calcd for C30H32O3: 440.2351; found: 440.2381.
813s, 772s, 756s cm–1
.
1H NMR (400 MHz, CDCl3): δ = 8.05–8.27 (m, 4 H), 7.96 (d, J = 8.4 Hz, 1
H), 7.64 (t, J = 7.6 Hz, 2 H), 7.38–7.56 (m, 3 H), 7.33 (d, J = 7.7 Hz, 1 H),
3.43 (s, 4 H), 3.40 (s, 6 H), 2.94–3.09 (m, 2 H), 1.96 (spt, J = 6.8 Hz, 1
H), 1.64–1.82 (m, 2 H), 0.96 (d, J = 7.0 Hz, 6 H).
13C NMR (101 MHz, CDCl3): δ = 140.0, 134.6, 133.0, 131.6, 131.5,
131.5, 129.2, 129.0, 128.5, 127.5, 127.1, 126.7, 126.5, 126.4, 126.1,
124.0, 120.1, 120.0, 119.9, 119.5, 77.3, 76.7, 75.3, 59.1, 43.0, 33.4,
30.7, 28.0, 17.8.
Compound 1
To a solution of K2CO3 (9.90 g, 71.6 mmol, 2 equiv) in water (600 mL),
PerBr (10.8 g, 32.6 mmol, 1 equiv), 5 (14.5 g, 35.8 mmol, 1.1 equiv),
Pd(PPh3)4 (2.07 g 1.79 mmol, 0.05 equiv) and MeOH (100 mL) were
added. The obtained suspension was refluxed for 10 h, then carefully
poured into water (500 mL), and the obtained two-phase mixture was
extracted with toluene (3 × 350 mL). The combined organic extract
was dried over Na2SO4 and then evaporated to dryness. The residue
was purified by flash chromatography (silica gel, n-hexane/CH2Cl2,
3:1). The obtained oil was triturated with MeOH (30 mL). The formed
HRMS: m/z calcd for C23H23O2Si: 424.2402; found: 424.2431.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2018, 50, A–I

I
B. A. Guzeev et al.
Paper
Synthesis
Crystallographic Data
(9) Groppo, E.; Gallo, E.; Seenivasan, K.; Lomachenko, K. A.;
Sommazzi, A.; Bordiga, S.; Glatzel, P.; Silfhout, R.; Kachatkou, A.;
Bras, W.; Lamberti, C. ChemCatChem 2015, 7, 1432.
(10) Nietzel, S.; Joe, D.; Krumpfer, J. W.; Schellenberger, F.; Alsaygh,
A. A.; Fink, G.; Klapper, M.; Müllen, K. J. Polym. Sci., Part A:
Polym. Chem. 2015, 53, 15.
CCDC-1848244 (3) and CCDC-1848243 (TMS2Per) contain the supple-
mentary crystallographic data for this paper. The data can be ob-
tained free of charge from The Cambridge Crystallographic Data Cen-
tre via www.ccdc.cam.ac.uk/getstructures.
(11) Jang, Y.; Naundorf, C.; Klapper, M.; Müllen, K. Macromol. Chem.
Phys. 2005, 206, 2027.
(12) Settels, V.; Schubert, A.; Tafipolski, M.; Liu, W.; Stehr, V.;
Topczak, A. K.; Pflaum, J.; Deibel, C.; Fink, R. F.; Engel, V.; Engels,
B. J. Am. Chem. Soc. 2014, 136, 9327.
Acknowledgment
The authors greatly appreciate the support of this work by Dr. Nico-
laas H. Friederichs and SABIC Petrochemicals B.V. (The Netherlands).
(13) Li, G.; Zhao, Y.; Li, J.; Cao, J.; Zhu, J.; Sun, X. W.; Zhang, Q. J. Org.
Chem. 2015, 80, 196.
(14) Qiao, Y.; Chen, J.; Yi, X.; Duan, W.; Gao, B.; Wu, Y. Tetrahedron
Lett. 2015, 56, 2749.
Supporting Information
Supporting information for this article is available online at
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