Palladium-catalyzed annulation of 1,2-diborylalkenes and -arenes with 1-bromo-2-[(Z)-2-bromoethenyl]arenes: A modular approach to multisubstituted naphthalenes and fused phenanthrenes

Article abstract of DOI:10.1002/asia.201200132

(Z)-1,2-Diaryl-1,2-bis(pinacolatoboryl)ethenes underwent double-cross-coupling reactions with 1-bromo-2-[(Z)-2-bromoethenyl]arenes in the presence of [Pd(PPh₃)₄] as a catalyst and 3 M aqueous Cs₂CO₃ as a base in THF at 80 °C. The double-coupling reaction gave multisubstituted naphthalenes in good to high yields. Annulation of 1,2-bis(pinacolatoboryl)arenes with bromo(bromoethenyl)arenes in the presence of a catalyst system that consisted of [Pd₂(dba)₃] (dba=dibenzylideneacetone) and 2-dicyclohexylphosphino-2′,6′- dimethoxybiphenyl (SPhos) under the same conditions produced fused phenanthrenes in good to high yields. The first annulation coupling occurred regiospecifically at the bromoethenyl moiety. This procedure is applicable to the facile synthesis of polysubstituted anthracenes, benzothiophenes, and dibenzoanthracenes through a double annulation pathway by using the corresponding dibromobis[(Z)-2-bromoethenyl]benzenes as diboryl coupling partners. Copyright

Full text of DOI:10.1002/asia.201200132

DOI: 10.1002/asia.201200132
Palladium-Catalyzed Annulation of 1,2-Diborylalkenes and -Arenes with
1-Bromo-2-[(Z)-2-bromoethenyl]arenes: A Modular Approach to
Multisubstituted Naphthalenes and Fused Phenanthrenes
Masaki Shimizu,*[a] Yosuke Tomioka,[a] Ikuhiro Nagao,[a] Tsugumi Kadowaki,[a] and
Tamejiro Hiyama[a, b]
Abstract: (Z)-1,2-Diaryl-1,2-bis(pinaco-
latoboryl)ethenes underwent double-
cross-coupling reactions with 1-bromo-
2-[(Z)-2-bromoethenyl]arenes in the
the presence of a catalyst system that
consisted of [Pd2A(dba)3] (dba=dibenzy-
curred regiospecifically at the bromoe-
thenyl moiety. This procedure is appli-
cable to the facile synthesis of polysub-
stituted anthracenes, benzothiophenes,
CTHUNGTRENNUNG
lideneacetone) and 2-dicyclohexylphos-
phino-2’,6’-dimethoxybiphenyl (SPhos)
under the same conditions produced
fused phenanthrenes in good to high
yields. The first annulation coupling oc-
presence of [Pd
N
and
dibenzoanthracenes
through
and 3m aqueous Cs2CO3 as a base in
THF at 808C. The double-coupling re-
action gave multisubstituted naphtha-
lenes in good to high yields. Annula-
tion of 1,2-bis(pinacolatoboryl)arenes
with bromo(bromoethenyl)arenes in
a double annulation pathway by using
the corresponding dibromobis[(Z)-2-
bromoethenyl]benzenes as diboryl cou-
pling partners.
Keywords: annulation
· arenes ·
boron · cross-coupling · palladium
2
À
Introduction
which are highly efficient methods for forming C
G
AHCTUNGTRENNUNG
(sp2) bonds, remains unexplored for the synthesis of multi-
Multisubstituted naphthalene moieties are often found in
biologically active substances.[1] Conceptually, there are two
strategies for their synthesis: 1) the incorporation of sub-
stituents into a naphthalene core and 2) the construction of
a naphthalene ring by using a substituted benzene precursor.
The latter strategy is more-attractive from the viewpoint of
possible substitution patterns and substituent variation be-
cause functionalized naphthalene precursors are less readily
available than substituted benzene derivatives and the reac-
tive sites on a naphthalene core are primarily governed by
pre-existing functional-group orientations.[2] Although a vari-
ety of synthetic approaches have been developed that use
the second strategy,[3] transition-metal-catalyzed annulation/
cyclization reactions based on the cross-coupling reactions
of organometallic reagents and organic (pseudo)halides,
substituted naphthalenes from functionalized benzene pre-
cursors.[4]
Polycyclic aromatic hydrocarbons (PAHs), such as
picene,[5]
AHCTUNGTRENNUNG
dibenz
[a,h]anthracene,[6]
and
dibenz-
[a,j]anthracene,[7] which contain fused phenanthrene groups,
have recently been used as key components in functional or-
ganic materials (Scheme 1). For example, thin films of
picene have exhibited excellent p-type transistor properties
in
air.[5a]
Bis(diphenylamino)-substituted
dibenz-
AHCTUNGTRENNUNG
[a] Prof. Dr. M. Shimizu, Y. Tomioka, Dr. I. Nagao, T. Kadowaki,
Prof. Dr. T. Hiyama
Department of Material Chemistry
Graduate School of Engineering
Kyoto University, Kyoto University Katsura
Nishikyo-ku, Kyoto 615-8510 (Japan)
Fax : (+81)75-383-2445
E-mail: m.shimizu@hs2.ecs.kyoto-u.ac.jp
Homepage: http://www.npc05.kuic.kyoto-u.ac.jp/npc05/Home.html
[b] Prof. Dr. T. Hiyama
Current address:
Research & Development Initiative, Chuo University
1-13-27, Kasuga, Bunkyo-ku, Tokyo 112-8551 (Japan)
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/asia.201200132.
Scheme 1. Functional materials that contain benzene-fused phenanthrene
moieties.
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quantum yield and stable towards two-step oxidation.[6b]
DibenzACHTUNGTRENNUNG[a,j]anthracene-based macrocycles have been report-
dibromoethenyl)arenes[13] and the designed annulation, if
feasible, could serve as a concise synthetic route to multi-
substituted naphthalenes and fused phenanthrenes
(Scheme 2). Herein, we report the palladium-catalyzed ben-
zannulation of 1 with 2 leading to PAHs of type 3.
ed to form J-aggregates in thin films and have exhibited ex-
cellent luminescence quantum efficiency in the annealed
films.[7] The development of an efficient synthesis would ac-
celerate the discovery of superior optoelectronic materials
based on p-conjugated systems of fused phenanthrenes be-
cause synthetic routes to the fused phenanthrene frame-
works are limited.[8]
A palladium-catalyzed double-cross-coupling reaction of
1,2-diborylalkenes and -arenes (1) with 2,2’-dibromobiaryl
compounds has recently been developed as a straightforward
route to functionalized PAHs, such as phenanthrenes, triphe-
Results and Discussion
The reaction of (Z)-1,2-bis(pinacolatoboryl)stilbene (1a)[14]
and 1-bromo-2-[(Z)-2-bromoethenyl]benzene (2a) was ini-
tially examined as a model reaction. Representative results
are summarized in Table 1. The reaction catalyzed by
nylenes, dibenzoACHTUNGTRENNUNG[g,p]chrysenes, and their thiophene ana-
logues (Scheme 2a).[9] The application of an annulative
Table 1. Palladium-catalyzed double-cross-coupling reaction of 1a with
2a.[a]
Entry Catalyst (mol%)
Base Concentration
T
Yield
[m][b]
[8C] [%][c]
1
2
3
4
5
6
[Pd
[Pd
[Pd
[Pd
[Pd
[Pd
[Pd
U
60
60
60
60
80
80
53
59
62
85
99
99
7[d]
8
80 91[e]
A
U
80
99
9
10
G
E
80
80
95
70
ACHTUNGTRENNUNG
[a] Reaction conditions: 1a (0.06 mmol), 2a (0.05 mmol), [Pd] catalyst,
3m aqueous base (0.30 mmol), THF, 48 h; [b] approximate molar concen-
1
tration of 2a; [c] yield estimated by H NMR spectroscopy by using 1,3,5-
trimethoxybenzene as an internal standard; [d] reaction conditions: 1a
(1.2 mmol), 2a (1.0 mmol), [PdACTHNUTRGEN(UNG PPh3)4] (25 mmol), 3m aqueous Cs2CO3
(6.0 mmol), THF (40 mL), 808C, 48 h; [e] yield of isolated product;
[f] SPhos=2-dicyclohexylphosphino-2’,6’-dimethoxybiphenyl.
5 mol% [PdACTHNUGTRNEUNG(PPh3)4] in the presence of 3m aqueous K2CO3
Scheme 2. The palladium-catalyzed double-cross-coupling reactions of
1,2-bis(pinacolatoboryl)alkenes and -arenes, and the molecular structures
of diboryl reagents 1.
or K3PO4, optimal bases in the annulation of 1a with 2,2’-di-
bromobiaryls[9], in THF at 608C gave 1,2-diphenylnaphtha-
lene (3aa) in 53% and 59% yield, respectively (Table 1, en-
tries 1 and 2). The use of 3m aqueous Cs2CO3 as the base
(Table 1, entry 3) resulted in a slightly higher yield of 3aa,
and some oligomeric products were formed. The yield in-
creased significantly when the molar concentration of 1a
was decreased from 0.05m to 0.025m in the presence of 3m
aqueous Cs2CO3 to suppress oligomer formation (Table 1,
entry 4). Furthermore, the annulation reaction proceeded
quantitatively at 808C (Table 1, entry 5). Under the same
strategy based on the double-cross-coupling reaction of
1 with 1-bromo-2-(bromomethyl)arenes as electrophiles has
allowed the convenient synthesis of functionalized indenes
and fused fluorenes (Scheme 2b).[10] The attention was fo-
cused on 1-bromo-2-[(Z)-2-bromoethenyl]arenes (2) as the
coupling partners for enhancing the synthetic value of the
palladium-catalyzed double-cross-coupling strategy by using
1 for the preparation of PAHs.[11] The dibromides (2) were
readily obtained by transition-metal-catalyzed trans-selective
coupling reactions[12] or by the reduction of 1-bromo-2-(2,2-
conditions, the amount of [Pd
2.5 mol% (Table 1, entries 6 and 7). A catalyst system that
consisted of [Pd2A(dba)3] and 2-dicyclohexylphosphino-2’,6’-
ACHTUNGTREN(NNUG PPh3)4] could be reduced to
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Annulation of 1-Bromo-2-[(Z)-2-bromoethenyl]arenes
dimethoxybiphenyl (SPhos) was also effective (Table 1,
oxidative addition of the bromine–ethenyl bond in 2 to a pal-
ladium(0) atom preferentially underwent smooth transmeta-
lation with 1 (for details of the catalytic cycle, see below)
over a double-bond isomerization in the styryl moiety (1,3-
migration of a palladium atom). The synthesis of quinoline
3ag was achieved by using bromo(2-bromoethenyl)pyridine
2g as the coupling partner for 1a. Dimethoxy-substituted di-
borylstilbene (1b) was reacted with 2a to give 3ba in excel-
lent yield. On the other hand, under the same conditions,
the reaction of trifluoromethyl-substituted diborylstilbene
1c with 2a resulted in a low yield (14%) of compound 3ca.
Most of 1c and 2a were recovered; therefore, the low yield
was ascribed to the low reactivity of 1c in the first coupling
reaction, which might have originated from the electron-
withdrawing effect of the trifluoromethyl group. However,
the yield of 3ca was increased to 74% on replacing [Pd-
entry 8).[15] [PdCl
CHTUNGTRENNUNG(dppf)] (dppf=1,1’-bis(diphenylphosphi-
2A
no)ferrocene) exhibited similar catalytic activity, but [Pd-
ACHTUNGTRENNUNG(PtBu3)2] was less effective (Table 1, entries 9 and 10).
The scope of the annulation reactions of diborylalkenes
1a–1c[14] with various dibromides (2) was studied under the
optimized conditions shown in Table 1, entry 7 and
Scheme 3. Fluoro-substituted bromo(2-bromoethenyl)ben-
A
2ACHTUNGTRENNUNG(dba)3]
Next, the double-cross-coupling reaction of 1,2-diborylar-
enes 1d–1i[9,10,16] with 2 was scrutinized with the aim of es-
tablishing a new synthetic method for the formation of
fused phenanthrenes. The conditions that were used in the
reactions of diborylalkenes 1a–1c were applied to the reac-
tion between 1d and 2a. The expected product (3da) was
only obtained in 42% yield. On the other hand, annulation
by using the [Pd2ACTHNUTRGNE(UNG dba)3]/SPhos catalyst system was quite ef-
fective, thereby yielding 3da in 91% yield (Scheme 4). The
scope of the annulation reaction using 1d–1i was confirmed
with the aid of a catalyst system that consisted of [Pd2ACHTUNGTRENNUNG(dba)3]
and SPhos. Diborylbenzene 1d reacted with 2 f to give 9-
styrylphenanthrene 3df in 81% yield. The double-cross-cou-
pling reactions of dimethoxy- and dimethyl-substituted di-
borylbenzenes 1e and 1 f with 2a also proceeded efficiently
Scheme 3. The palladium-catalyzed double-cross-coupling reaction of 1,2-
diborylalkenes 1a–1c with 2.
zene 2b reacted with 1a to give 3ab in 70% yield. The
double-cross-coupling reaction with 2c, in which a sterically
demanding trimethylsilyl group was substituted at the gemi-
nal position of the bromine atom on an ethenyl moiety, pro-
ceeded smoothly to produce 3ac in 74% yield. Triarylated
naphthalenes 3ad and 3ae were obtained in high yields
from the reactions of 1a with dibromostyrenes 3d and 3e,
respectively. The production of 3ae in high yield indicated
that the chlorine moiety tolerated the reaction conditions.
Styryl-substituted bromo(bromoethenyl)benzene 2 f under-
went annulation to give 3af in 69% yield, which implied
that an alkenylpalladium complex that was generated by the
Scheme 4. The palladium-catalyzed double-cross-coupling reaction of 1,2-
diborylarenes 1d–1i with 2.
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to give 3ea and 3 fa in good to high yields, respectively. Ben-
zo[g]chrysenes 3ga and 3ha were synthesized in high yields
from diborylphenanthrenes 1g and 1h, respectively. Further-
more, diboryldithienobenzene 1i was applicable to the pres-
ent annulation conditions, thereby giving rise to 3ia in 84%
yield.
To further demonstrate the high synthetic value of the
double-cross-coupling strategy, a double annulation was car-
ried out by using dibromobis(2-bromoethenyl)arenes 2h–2l
as the coupling partners of 1 (Scheme 5). The reaction of
1,4-dibromo-2,5-bis(2-bromo-2-silylethenyl)benzene 2h with
3 fi and dibenzoACHTGUNTERNNU[G a,j]anthracene 3 fj were synthesized in good
yields from the reactions of 1 f with 1,4-dibromo-2,5-bis(bro-
moethenyl)benzene 2i and 1,3-dibromo-4,6-bis(bromoethe-
nyl)benzene 2j, respectively. Thus, the fusion mode of two
benzene rings onto anthracene was easily tuned by changing
the substitution pattern of the two bromine atoms and the
two bromoethenyl moieties on the benzene ring. Moreover,
the double annulation of 1,8-dibromo-2,7-bis(bromoethe-
nyl)phenanthrene (2k) and 3,4-dibromo-2,5-bis(bromoethe-
nyl)thiophene (2l) with 1b gave 1,2,11,12-tetraarylated
picene 3bk and 3,4,5,6-tetraarylated benzothiophene 3bl, re-
spectively, in good-to-excellent yields. The substitution pat-
terns in these PAHs are difficult to obtain by other synthetic
methods.
1a was efficiently catalyzed by [PdACHTNUTRGEN(UNG PPh3)4] in the presence
of 3m aqueous Cs2CO3 in THF at 808C in a similar manner
to the reaction of 2c to give multisubstituted anthracene
3ah in 64% yield. Each annulation reaction was roughly es-
To gain a mechanistic insight, 2a was treated with one
À
timated to proceed in 80% yield. Dibenzo
N
molar equivalent of phenylboronic pinacol ester (Ph Bpin)
in the presence of [PdACHTNUGTRNEUGN(PPh3)4] (2.5 mol%) and 3m aqueous
Cs2CO3 (6 equiv) in THF at 808C (Scheme 6). The sole
À
Scheme 6. Cross-coupling reaction of 2a with Ph Bpin. Reaction condi-
tions: [Pd(PPh3)4] (2.5 mol%), 3m aqueous Cs2CO3 (6 equiv), THF, 808C,
G
48 h.
product was cis-stilbene derivative 4, which was obtained in
À
76% yield. The reaction with two molar equivalents of Ph
Bpin gave diphenylated product 6 in 87% yield along with
the mono-coupled product (4) in 8% yield. In either case,
no formation of bromoethenyl-substituted biphenyl 5 was
observed. These results clearly indicated that the first cou-
pling reaction took place chemoselectively with the alkenyl
À
C Br functionality, which was consistent with the prece-
dents for the palladium-catalyzed amination/carbonylation
of bromo(2-bromoethenyl)arenes.[16]
A plausible catalytic cycle for this annulation reaction is
shown in Scheme 7 (based on the results shown in
Scheme 6), with diborylstilbenes 1a–1c representing the 1,2-
À
diboryl reagents. The oxidative addition of an alkenyl C Br
bond of 2 to a palladium(0) complex took place selectively
to give alkenylpalladium bromide 7. Diboryl reagents 1 and
7 underwent transmetalation with the aid of a hydroxide ion
to generate a bisACTHNUTRGNEUNG(alkenyl)palladium complex (8). Reductive
elimination of the alkenyl groups of 8 gave the initial cou-
pling product (9) and a palladium(0) complex. Oxidative ad-
dition of 9 to a palladium(0) complex produced arylpalladi-
um bromide (10), which underwent intramolecular transme-
talation, thereby giving rise to a seven-membered palladacy-
cle (11). Finally, the annulated product (3) was released
from 11 through reductive elimination along with the regen-
eration of a palladium(0) complex. In this annulation reac-
Scheme 5. The palladium-catalyzed double-annulation reaction of dibro-
mobis(bromoethenyl)arenes Reagents and reaction conditions: a) 1a
(2.4 equiv), 2h (1 equiv), [Pd
(12 equiv), THF, 808C; b) 1 f (2.4 equiv), 2i or 2j (1 equiv), [Pd
(5 mol%), SPhos (20 mol%), 3m aqueous Cs2CO3 (12 equiv), THF,
608C; c) 1b (2.4 equiv), 2k or 2l (1 equiv), [Pd2A(dba)3] (5 mol%), SPhos
(40 mol%), 3m aqueous Cs2CO3 (12 equiv), THF, 808C.
ACHTUNGTRENNUNG
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Annulation of 1-Bromo-2-[(Z)-2-bromoethenyl]arenes
(300 MHz) and 400 (400 MHz) spec-
trometers. The 1H NMR chemical
shifts are expressed in parts per mil-
lion downfield of tetramethylsilane
(TMS) as an internal standard (d=
0 ppm) or CHCl3 (d=7.26 ppm). Split-
ting patterns are indicated as s (sin-
glet), d (doublet), t (triplet), q (quar-
tet), m (multiplet). 13C NMR spectra
were measured on Varian Mercury 300
(75 MHz) and 400 (100 MHz) spec-
trometers with TMS as an internal
standard (d=0 ppm) or CHCl3 (d=
77.0 ppm). 19F NMR spectra were
measured on a Varian Mercury 300
(282 MHz) spectrometer with CFCl3
as an internal standard (d=0 ppm).
Chemical shifts are given in parts per
million downfield of an internal stan-
dard. IR spectra were recorded on
a Shimadzu FTIR-8400 spectrometer.
GCMS analysis was performed on
a
JEOL JMS-700 spectrometer by
electron ionization at 70 eV. Elemental
analysis was carried out on
YANAKO MT2 CHN CORDER
Scheme 7. Plausible catalytic cycle.
a
machine at the Elemental Analysis
Center of Kyoto University. TLC anal-
ysis were performed by means of Merck Kieselgel 60 F254 and column
chromatography was carried out by using Merck Kieselgel 60 (230–400
mesh). Preparative HPLC was carried out with a Japan Analytical Indus-
try Co., Ltd, LC-908 chromatograph by using a JAIGEL-1H and À2H
GPC columns. THF was passed through two packed columns of neutral
alumina and copper oxide under a nitrogen atmosphere before use. All
reactions were carried out under an argon atmosphere.
tion, oligomeric/polymeric products were observed in some
cases. In other words, intermolecular cross-coupling reac-
tions of 9 and/or 10 occurred. These results were in stark
contrast to the fact that no oligomers/polymers formed in
the annulation of 1 with 2,2’-dibromobiaryls (Scheme 2a);
moreover, intermolecular reactions of 12 and 13 were com-
pletely suppressed (Scheme 7).[9] Based on these differences,
the by-production of oligomers/polymers may be ascribed to
less steric hindrance around the Bpin and Br ([Pd]Br) groups
of 9 and 10.
Representative Procedure for the Palladium-Catalyzed Double-Cross-
Coupling Reaction of 1 with 2
[PdACHTUNGRTNEUNG(PPh3)4] (58 mg, 0.05 mmol), 1a (0.52 g, 1.2 mmol), 2a (0.26 g,
1.0 mmol), and 3m aqueous Cs2CO3 (2.0 mL, 6.0 mmol) was added to
a Schlenk tube (80 mL). The tube was then capped with a rubber
septum, evacuated, and purged with argon. The evacuation–purge opera-
tion was repeated twice. THF (40 mL) was added to the mixture at RT.
The mixture was stirred at room temperature for 5 min and heated at
808C for 48 h, before cooling to RT and diluting with EtOAc (20 mL).
The resulting solution was washed with saturated aqueous NH4Cl solu-
tion (20 mL) and the aqueous layer was extracted with EtOAc (3ꢁ
40 mL). The combined organic layer was washed with saturated aqueous
NaCl solution (20 mL), dried over anhydrous MgSO4, and concentrated
in vacuo. The residue was purified by column chromatography on silica
gel (n-hexane) to give 1,2-diphenylnaphthalene as a colorless solid (3aa;
0.28 g, 99% yield).
Conclusions
We have developed a palladium-catalyzed double cross-cou-
pling reaction of 1,2-diaryl-1,2-diborylethenes and 1,2-dibor-
ylarenes with 1-bromo-2-[(Z)-2-bromoethenyl]arenes, which
gives naphthalene and phenanthrene derivatives in good to
high yields. Annulation proceeds via intermolecular cou-
pling of the diboryl reagents with the bromoethenyl moiety
and the subsequent intramolecular coupling of the remain-
ing boron functionality and bromoarene moiety. The
straightforward and high-yielding synthesis of extended
PAHs such as dibenzoanthracenes and picene derivatives
was also demonstrated by carrying out a double annulation
using dibromobis(bromoethenyl)arenes as the coupling part-
ners of the diboryl reagents.
6-Fluoro-1,2-diphenylnaphthalene (3ab)
Yield: 70%; colorless solid; Rf =0.13 (n-hexane/EtOAc, 40:1);
1
m.p.: 133.1–134.08C; H NMR (400 MHz, CDCl3): d=7.12–7.22 (m, 8H),
7.28–7.34 (m, 3H), 7.53 (dd, J=9.5, 2.6 Hz, 1H), 7.61 (d, J=8.6 Hz, 1H),
7.67 (dd, J=9.5, 5.5 Hz, 1H), 7.87 ppm (d, J=8.6 Hz, 1H); 13C NMR
(100 MHz, CDCl3): d=110.7 (d, JACTHNUGTRENNUG(C,F)=20.7 Hz), 116.2 (d, JACHTUNGTRENNUNG(C,F)=
24.5 Hz), 126.1, 126.7 (d, J=5.4 Hz), 126.8, 127.5, 127.8, 129.3, 129.4 (d,
J=8.4 Hz), 129.6, 129.9, 133.5 (d, J=8.4 Hz), 137.6 (d, J=13.0), 138.6,
141.5, 159.1, 161.5 ppm; 19F NMR (282 MHz, CDCl3): d=À116.2 ppm;
IR (KBr): n˜ =1541, 1506, 873, 702, 579 cmÀ1; MS (EI): m/z (%): 300 (3)
[M+2]+, 299 (23) [M+1]+, 298 (100) [M]+, 283 (10); elemental analysis
calcd (%) for C22H15F: C 88.56, H 5.07; found: C 88.51, H 5.14.
Experimental Section
General
Melting points were determined by using a Yanagimoto Micro Point Ap-
paratus. 1H NMR spectra were measured on Varian Mercury 300
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(3,4-Diphenylnaphthalen-2-yl)trimethylsilane (3ac)
MS (EI): m/z (%): 281 (24) [M+1]+, 279 (100) [M]+; HRMS (EI): calcd
for C22H16: 280.1252 [M]+; found: 280.1243.
Yield: 74%; colorless solid; Rf =0.20 (n-hexane); m.p.: 161.3–162.18C;
1H NMR (400 MHz, CDCl3): d=0.04 (s, 9H), 7.04–7.22 (m, 10H), 7.35–
7.52 (m, 3H), 7.92 (d, J=8.1 Hz, 1H), 8.15 ppm (s, 1H); 13C NMR
(100 MHz, CDCl3): d=0.8, 125.5, 126.1, 126.2, 126.5, 126.8, 127.3, 127.9,
130.9, 131.7, 132.7, 134.8, 137.4, 137.8, 139.2, 142.2, 143.6 ppm; IR (KBr):
n˜ =1246, 893, 848, 837, 752, 700 cmÀ1; MS (FAB): m/z 354 (6) [M+2]+,
353 (23) [M+1]+, 352 (73) [M]+, 337 (100), 321 (45); elemental analysis
calcd (%) for C25H24Si: C 85.17, H 6.86; found: C 85.05, H 6.88.
2,13-Dimethoxybenzo[g]chrysene (3ha)
Yield: 83%; colorless solid; Rf =0.13 (n-hexane/EtOAc, 20:1);
m.p.: 146.7–147.68C; 1H NMR (400 MHz, CDCl3): d=4.06 (s, 3H), 4.07
(s, 3H), 7.28 (dd, J=9.0, 2.8 Hz, 1H), 7.34 (dd, J=9.0, 2.8 Hz, 1H), 7.54–
7.63 (m, 2H), 7.93 (d, J=8.4 Hz, 1H), 7.99 (dd, J=8.4, 1.6 Hz, 1H), 8.02
(d, J=2.8 Hz, 1H), 8.04 (d, J=2.8 Hz, 1H), 8.52 (d, J=9.0 Hz, 1H), 8.58
(d, J=9.0 Hz, 1H), 8.84 (d, J=9.6 Hz, 1H), 8.87 ppm (d, J=9.6 Hz, 1H);
13C NMR (100 MHz, CDCl3): d=55.8, 105.9, 106.3, 114.7, 116.2, 120.8,
124.4, 124.5, 125.60, 125.65, 126.0, 126.1, 127.0, 128.3, 128.4, 130.3, 131.2,
132.2, 133.3, 158.3, 158.9 ppm; IR (KBr): n˜ =3055, 3001, 2963, 2922, 2831,
1610, 1466, 1456, 1377, 1238, 1213, 1026, 835, 812, 754 cmÀ1; MS (EI): m/z
(%): 340 (4) [M+2]+, 339 (27) [M+1]+, 338 (100) [M]+; HRMS (EI):
calcd for C24H18O2: 338.1307 [M]+; found: 338.1305.
3-(4-Chlorophenyl)-1,2-diphenylnaphthalene (3ae)
Yield: 84%; colorless solid; Rf =0.45 (n-hexane/EtOAc, 40:1);
1
m.p.: 197.8–198.48C; H NMR (400 MHz, CDCl3): d=6.82–6.90 (m, 2H),
6.94–7.00 (m, 3H), 7.08–7.18 (m, 6H), 7.20–7.28 (m, 3H), 7.38–7.44 (m,
1H), 7.50–7.55 (m, 1H), 7.59 (d, J=8.4 Hz, 1H), 7.92 (s, 1H), 7.94 ppm
(d, J=8.1 Hz, 1H); 13C NMR (100 MHz, CDCl3): d=126.1, 126.4, 126.6,
126.7, 127.1, 127.3, 127.8, 128.0, 128.1, 128.9, 131.4, 131.5, 131.6, 132.3,
132.6, 132.8, 138.0, 138.7, 139.4, 169.6, 139.9, 140.6 ppm; IR (KBr): n˜ =
1489, 1090, 1013, 893, 827, 750, 698 cmÀ1; MS (EI): m/z 394 (2) [M+4]+,
393 (10) [M+3]+, 392 (35) [M+2]+, 391 (32) [M+1]+, 390 (100) [M]+;
HRMS (EI): calcd for C28H19Cl: 390.1175 [M]+; found: 390.1186.
Phenanthro[1,2-b:4,3-b’]dithiophene (3ia)
Yield: 84%; yellow solid; Rf =0.13 (n-hexane); 1H NMR (400 MHz,
CDCl3): d=7.64–7.70 (m, 3H), 7.76 (d, J=5.5 Hz, 1H), 7.82–7.88 (m,
2H), 7.90–7.95 (m, 2H), 8.03 (dd, J=7.9, 1.3 Hz, 1H), 8.19 (d, J=8.6 Hz,
1H), 9.28 ppm (dd, J=8.6, 0.7 Hz, 1H); 13C NMR (100 MHz, CDCl3):
d=122.1, 122.8, 123.3, 123.6, 125.7, 126.0, 126.10, 126.13, 127.1, 127.34,
129.2, 129.7, 132.4, 132.6, 133.5, 134.4, 136.5 ppm; IR (KBr): n˜ =1541,
810, 717, 555 cmÀ1; MS (EI): m/z (%): 292 (11) [M+2]+, 291 (22) [M+1]+,
290 (100) [M]+, 245 (15); elemental analysis calcd (%) for C18H10S2:
C 74.45, H 3.47; found: C 74.38, H 3.60.
(E)-1,2-Diphenyl-3-styrylnaphthalene (3af)
Yield: 69%; orange solid; Rf =0.13 (n-hexane); m.p.: 193.5–194.58C;
1H NMR (400 MHz, CDCl3): d=6.94 (d, J=16.0 Hz, 1H), 7.07–7.38 (m,
17H), 7.48–7.52 (m, 2H), 7.96 (d, J=8.4 Hz, 1H), 8.26 ppm (s, 1H);
13C NMR (100 MHz, CDCl3): d=123.8, 126.0, 126.37, 126.44, 126.5,
126.8, 127.4, 127.47, 127.51, 127.9, 128.3, 128.6, 129.8, 131.0, 131.1, 132.2,
132.9, 134.8, 137.6, 138.5, 139.0, 139.2, 139.6 ppm; IR (KBr): n˜ =1597,
1489, 1447, 1375, 1323, 1260, 1074, 1028, 963, 887, 845, 762, 747, 702,
691 cmÀ1; MS (EI): m/z (%): 383 (32) [M+1]+, 382 (100) [M]+; HRMS
(EI): calcd for C30H22: 382.1722 [M]+; found: 382.1730.
Representative Procedure for the Double-Annulation Reaction of 1 with 2
[PdACHTNUGRTNEUNG(PPh3)4] (7.2 mg, 6.3 mmol), 1a (0.26 g, 0.60 mmol), and 2h (0.15 g,
0.25 mmol) were placed in a screw-topped test tube. The tube was then
capped with a rubber septum, evacuated for 5 min, and purged with
argon. The evacuation–purge cycle was repeated twice. THF (20 mL) and
3 m aqueous Cs2CO3 (1.0 mL, 3.0 mmol) were added to the mixture at
RT. After stirring at RT for 5 min, the solution was heated at 808C for
48 h. The reaction mixture was diluted with CH2Cl2 (10 mL) and filtered
through a pad of celite. The filtrate was concentrated under vacuum and
the residue was washed with MeOH to give 1,2,5,6-tetraphenyl-3,7-bis(-
trimethylsilyl)anthracene as a yellow solid (3ah; 0.10 g, 64% yield). Rf =
0.73 (n-hexane/EtOAc/CH2Cl2, 3:1:1); M.p.:>4008C; 1H NMR
(400 MHz, CDCl3): d=0.00 (s, 18H), 7.06–7.21 (m, 14H), 7.22–7.32 (m,
6H), 8.07 (s, 2H), 8.11 ppm (s, 2H); 13C NMR (100 MHz, CDCl3): d=
À10.0, 114.7, 115.2, 115.8, 116.4, 119.8, 119.9, 120.0, 120.2, 125.0, 126.2,
126.7, 128.4, 131.3, 131.4 ppm; IR (KBr): n˜ =1246, 985, 854, 839, 698,
418 cmÀ1; MS (EI): m/z (%): 629 (7) [M+3]+, 628 (23) [M+2]+, 627 (58)
[M+1]+, 626 (100) [M]+, 523 (18); elemental analysis calcd (%) for
C44H42Si2: C 84.29, H 6.75; found: C 84.03, H 6.68.
7,8-Diphenylquinoline (3ag)
Yield: 55%; colorless solid; Rf =0.43 (n-hexane/EtOAc, 4:1);
m.p.: 145.8–146.58C; 1H NMR (400 MHz, CDCl3): d=7.12–7.32 (m,
10H), 7.40 (dd, J=8.2, 4.2 Hz, 1H), 7.66 (d, J=8.4 Hz, 1H), 7.89 (d, J=
8.4 Hz, 1H), 8.21 (dd, J=8.2, 1.6 Hz, 1H), 8.94 ppm (dd, J=4.2, 1.6 Hz,
1H); 13C NMR (100 MHz, CDCl3): d=120.6, 126.4, 126.6, 127.1, 127.3,
127.5, 127.6, 129.0, 129.9, 131.7, 135.7, 137.9, 138.8, 141.4, 141.8, 146.8,
150.4 ppm; IR (KBr): n˜ =3055, 1489, 835, 761, 754, 704 cmÀ1; MS (EI):
m/z (%): 238 (1) [M+2]+, 282 (10) [M+1]+, 281 (57) [M]+, 280 (100)
[MÀ1]+, 204 (11); elemental analysis calcd (%) for C21H15N: C 89.65,
H 5.37; found: C 89.56, H 5.46.
1,2-Bis(4-methoxyphenyl)naphthalene (3ba)
Yield: 95%; colorless solid; Rf =0.13 (n-hexane/EtOAc, 40:1);
m.p.: 162.4–162.88C; 1H NMR (400 MHz, CDCl3): d=3.78 (s, 3H), 3.84
(s, 3H), 6.72–6.78 (m, 2H), 6.84–6.89 (m, 2H), 7.06–7.14 (m, 4H), 7.36–
7.42 (m, 1H), 7.44–7.49 (m, 1H), 7.55 (d, J=8.6 Hz, 1H), 7.69 (d, J=
8.4 Hz, 1H), 7.86–7.92 ppm (m, 2H); 13C NMR (100 MHz, CDCl3): d=
55.19, 55.23, 113.0, 113.3, 125.3, 126.0, 126.6, 127.2, 127.7, 128.3, 131.0,
131.2, 132.2, 132.5, 132.9, 134.4, 136.9, 137.9, 157.7, 158.0 ppm; IR (KBr):
n˜ =1608, 1514, 1242, 1179, 1032, 819, 748 cmÀ1; MS (EI): m/z (%): 342
(6) [M+2]+, 341 (41) [M+1]+, 340 (100) [M]+, 309 (3); elemental analysis
calcd (%) for C24H20O2: C 84.68, H 5.92; found: C 84.39, H 5.76.
2,3,9,10-Tetramethylbenzo[k]tetraphene (3 fi)
Purified by recrystallization from MeOH. Yield: 69%; yellow solid; Rf =
0.13 (n-hexane); m.p.: 358.0–358.78C; 1H NMR (400 MHz, CDCl3): d=
2.51 (s, 6H), 2.60 (s, 6H), 7.74–7.90 (m, 4H), 7.88 (d, J=9.0 Hz, 2H),
8.61 (s, 2H), 9.08 ppm (s, 2H); 13C NMR (100 MHz, CDCl3): d=20.0,
21.0, 109.7, 115.5, 118.8, 121.6, 123.2, 126.4, 128.4, 128.5, 128.7, 130.3,
130.5, 135.8, 135.9 ppm; IR (KBr): n˜ =1749, 1684, 1558, 1541, 1506, 1456,
891, 667, 418 cmÀ1; MS (EI): m/z (%): 336 (12) [M+2]+, 335 (30) [M+1]+,
334 (100) [M]+; HRMS (EI): calcd for C26H22: 334.1722 [M]+; found:
334.1713.
(E)-9-Styrylphenanthrene (3df)
Yield: 81%; colorless solid; Rf =0.18 (n-hexane); m.p.: 116.0–117.08C;
1H NMR (400 MHz, CDCl3): d=7.24 (d, J=15.2 Hz, 1H), 7.31–7.35 (m,
1H), 7.42–7.45 (m, 1H), 7.60–7.73 (m, 6H), 7.89 (d, J=15.2 Hz, 1H),
7.93 (d, J=7.6 Hz, 1H), 7.98 (s, 1H), 8.27 (d, J=8.0 Hz, 1H), 8.68 (d, J=
8.0 Hz, 1H), 8.68 (d, J=8.0 Hz, 1H), 8.76 ppm (d, J=8.8 Hz, 1H);
13C NMR (100 MHz, CDCl3): d=122.5, 123.1, 124.55, 124.64, 126.3,
126.5, 126.67, 126.74, 126.8, 127.8, 128.7, 128.8, 130.2, 130.4, 130.8, 131.8,
2,3,11,12-Tetramethylbenzo[m]tetraphene (3 fj)
Purified by column chromatography on silica gel (n-hexane/EtOAc,
15:1). Yield: 79%; yellow solid; Rf =0.50 (n-hexane/EtOAc, 15:1);
m.p.: 260.6–262.28C; 1H NMR (400 MHz, CDCl3): d=2.52 (s, 6H), 2.66
(s, 6H), 7.62–7.69 (m, 4H), 7.78 (d, J=8.8 Hz, 2H), 8.30 (s, 1H), 8.76 (s,
2H), 9.92 ppm (s, 1H); 13C NMR (100 MHz, CDCl3): d=20.1, 20.8,
115.5, 123.1, 125.9, 126.4, 127.1, 128.4, 128.76, 128.85, 130.3, 130.4, 135.7,
135.9 ppm; IR (KBr): n˜ =1749, 1716, 1541, 1506, 1456, 889, 871, 441,
418 cmÀ1; MS (EI): m/z (%): 336 (4) [M+2]+, 335 (28) [M+1]+, 334 (100)
132.1, 134.0, 137.6 ppm; IR (KBr): n˜ =1497, 1449, 961, 737, 721, 689 cmÀ1
;
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www.chemasianj.org
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Chem. Asian J. 0000, 00, 0 – 0
ÝÝ These are not the final page numbers!

Annulation of 1-Bromo-2-[(Z)-2-bromoethenyl]arenes
[M]+, 303 (7); HRMS (EI): calcd for C26H22: 334.1722 [M]+; found:
334.1720.
ki, Y. Maniwa, Y. Kubozono, Nature 2010, 464, 76–79; f) N. Kawasa-
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K. Ogawa, R. Eguchi, S. Oikawa, H. Gohda, A. Fujiwara, Y. Kubo-
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1,2,11,12-Tetrakis(4-methoxyphenyl)picene (3bk)
Purified by recrystallization from MeOH. Yield: 63%; yellow solid;
1H NMR (400 MHz, CDCl3): d=3.79 (s, 6H), 3.85 (s, 6H), 6.72 (d, J=
8.0 Hz, 8H), 6.90–6.95 (m, 8H), 7.14 (s, 2H), 7.59 (d, J=8.0 Hz, 2H),
7.94–7.99 (m, 4H), 8.78 ppm (d, J=9.2 Hz, 2H); IR (KBr): n˜ =1608,
1518, 1506, 1246, 1176, 1032, 827 cmÀ1; MS (FAB): m/z (%): 704 (17)
[M+2]+, 703 (52) [M+1]+, 702 (100) [M]+, 351 (9); HRMS (EI): calcd for
C50H38O4: 702.2770 [M]+; found: 702.2774.
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Purified by column chromatography on silica gel (n-hexane/EtOAc, 4:1).
Yield: 90%; yellow solid; Rf =0.36 (n-hexane/EtOAc, 4:1); m.p.:>
4008C; 1H NMR (400 MHz, CDCl3): d=3.66 (s, 6H), 3.73 (s, 6H), 6.17–
6.30 (m, 8H), 6.60–6.74 (m, 8H), 7.31 (d, J=8.4 Hz, 2H), 7.78 ppm (d,
J=8.4 Hz, 2H); 13C NMR (100 MHz, CDCl3): d=55.0, 55.1, 112.8, 112.9,
120.8, 129.8, 130.8, 131.0, 132.8, 134.0, 134.6, 138.0, 138.4, 139.5, 157.1,
157.6 ppm; IR (KBr): n˜ =1608, 1514, 1290, 1248, 1179, 1030, 829,
596 cmÀ1; MS (EI): m/z (%): 611 (4) [M+3]+, 610 (16) [M+2]+, 609 (43)
[M+1]+, 608 (100) [M]+. HRMS (EI): Calcd for C40H32O4S: 608.2021
[M]+; found: 608.2027.
Acknowledgements
This work was supported by a Grant-in-Aid for Creative Scientific Re-
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Science and Technology, Japan and The Asahi Glass Foundation (M.S.).
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Received: February 10, 2012
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FULL PAPERS
A class apart: Bromo(bromoetheny-
l)arenes are a new class of electro-
philes that successfully undergo palla-
dium-catalyzed double-cross-coupling
reactions with 1,2-diborylalkenes and
-arenes. This straightforward, modular
approach is suitable for the formation
of multisubstituted polycyclic aromatic
hydrocarbons, such as naphthalenes,
anthracenes, and fused phenanthrenes.
Cross-Coupling Reactions
Masaki Shimizu,* Yosuke Tomioka,
Ikuhiro Nagao, Tsugumi Kadowaki,
Tamejiro Hiyama
&&&& — &&&&
Palladium-Catalyzed Annulation of
1,2-Diborylalkenes and -Arenes with
1-Bromo-2-[(Z)-2-bromoethenyl]ar-
enes: A Modular Approach to Multi-
substituted Naphthalenes and Fused
Phenanthrenes
Chem. Asian J. 2012, 00, 0 – 0
ꢀ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemasianj.org
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