Synthesis of Multisubstituted Triphenylenes and Phenanthrenes by Cascade Reaction of o-Iodobiphenyls or (Z)-β-Halostyrenes with o-Bromobenzyl Alcohols through Two Sequential C-C Bond Formations Catalyzed by a Palladium Complex

Article abstract of DOI:10.1021/acs.joc.5b01693

o-Bromobenzyl alcohol has been developed as a novel annulating reagent, bearing both nucleophilic and electrophilic substituents, for the facile synthesis of polycyclic aromatic hydrocarbons. A palladium/electron-deficient phosphine catalyst efficiently coupled o-iodobiphenyls or (Z)-β-halostyrenes with o-bromobenzyl alcohols to afford triphenylenes and phenanthrenes, respectively. The present cascade reaction proceeded through deacetonative cross-coupling and sequential intramolecular cyclization. An array of experimental data suggest that the reaction mechanism involves the equilibrium of 1,4-palladium migration.

Full text of DOI:10.1021/acs.joc.5b01693

Article
pubs.acs.org/joc
Synthesis of Multisubstituted Triphenylenes and Phenanthrenes by
Cascade Reaction of o‑Iodobiphenyls or (Z)‑β-Halostyrenes with
o‑Bromobenzyl Alcohols through Two Sequential C−C Bond
Formations Catalyzed by a Palladium Complex
Masayuki Iwasaki,† Yasuhiro Araki,† Shohei Iino,† and Yasushi Nishihara*,†,‡
†Division of Earth, Life, and Molecular Sciences, Graduate School of Natural Science and Technology, Okayama University, 3-1-1
Tsushima-naka, Kita-ku, Okayama 700-8530, Japan
‡ACT-C, Japan Science and Technology Agency, Kawaguchi 332-0012, Japan
S
* Supporting Information
ABSTRACT: o-Bromobenzyl alcohol has been developed as a
novel annulating reagent, bearing both nucleophilic and
electrophilic substituents, for the facile synthesis of polycyclic
aromatic hydrocarbons. A palladium/electron-deficient phos-
phine catalyst efficiently coupled o-iodobiphenyls or (Z)-β-
halostyrenes with o-bromobenzyl alcohols to afford tripheny-
lenes and phenanthrenes, respectively. The present cascade
reaction proceeded through deacetonative cross-coupling and
sequential intramolecular cyclization. An array of experimental
data suggest that the reaction mechanism involves the
equilibrium of 1,4-palladium migration.
terphenyls or stilbenes has been applied to the construction of
triphenylene and phenanthrene skeletons, the substrate scope
has been quite limited due to the harsh reaction conditions.6
Moreover, the preparation of starting materials often requires
multistep syntheses, leading to low overall yields of the target
molecules. Although several synthetic methods have been
reported for triphenylenes7,8 and phenanthrenes9,10 in the past
two decades, a general and convenient synthesis has been
continuously sought to facilitate access to these compounds for
use in materials science. Among these efforts, the synthetic
method using in situ generated arynes developed by Larock and
co-workers represents a reliable strategy for the construction of
PAHs.8b,e The palladium-catalyzed annulation of o-iodobiphen-
yls with arynes proceeds under mild conditions, affording
various triphenylene derivatives. Moreover, (Z)-β-iodostyrenes
undergo annulation with arynes to yield the corresponding
phenanthrenes in good yields. However, preparation of the
aryne precursors, o-trialkylsilylaryl triflates, requires bothersome
treatment: O-silylation of o-bromophenols, metal−halogen
exchange, O- to C- silyl migration, and entrapment of the
phenoxide with triflic anhydride.11 Furthermore, the regiose-
lectivity of the reaction with substituted arynes is totally
uncontrollable.
INTRODUCTION
■
Polycyclic aromatic hydrocarbons (PAHs) have characteristic
optical and electrochemical properties because of their
extended π-conjugated systems, which are some of the most
reliable molecular features for controlling several key behaviors
of organic materials.1 Among them, acene-type PAHs, in which
aromatic rings are arranged linearly, are widely regarded as
promising materials (Figure 1, left).2 However, the problem
Figure 1. Acene- and phenacene-type molecules.
remains that acene-type molecules are unstable when exposed
to air and light, which gives them a short lifespan as organic
functional materials.3 In sharp contrast, phenacene-type PAHs
with aromatic rings arranged in an armchair manner have
attracted much interest as the next generation of practical
organic materials because of their stability (Figure 1, right).4,5
Because a common route to highly substituted phenacene-
type PAHs has yet to be established, developing synthetic
methods for phenacenes is desirable from the viewpoint of
fundamental studies on functional organic materials. Until
recently, although the conventional oxidative cyclization of o-
Received: July 21, 2015
© XXXX American Chemical Society
A
DOI: 10.1021/acs.joc.5b01693
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We report here the development of o-bromobenzyl alcohols
as novel annulating reagents for the synthesis of triphenylenes
and phenanthrenes.12 We show that the palladium/electron-
deficient phosphine-catalyzed cascade reaction of o-iodobi-
phenyls or (Z)-β-halostyrenes with o-bromobenzyl alcohols
provides multisubstituted triphenylenes and phenanthrenes,
respectively. The present reaction involves deacetonative cross-
coupling and subsequent intramolecular cyclization, which
constructs two C−C bonds sequentially.
Table 2. Palladium-Catalyzed Annulation of o-Halobiphenyls
2 with o-Halobenzyl Alcohols 1
a
yield (%)
RESULTS AND DISCUSSION
entry
X1
X2
3a
4
■
1
2
3
4
5
6
Br (1a)
Cl (1b)
I (1c)
Br (2a)
Br (2a)
Br (2a)
OTf (2b)
Cl (2c)
I (2d)
15
<1
2
<1
0
Preparation of o-Halobenzyl Alcohols. We first
designed o-halobenzyl alcohols as novel annulating reagents
that have both nucleophilic and electrophilic moieties.13 In
marked contrast to conventional organometallic annulating
reagents, o-halobenzyl alcohols are quite stable on the benchtop
and can be stored for at least several months. Furthermore, the
present annulating reagents can be prepared by a single-step
synthesis from commercially available acetophenone derivatives
or benzoic esters, as treatment of o-haloacetophenone
derivatives or methyl o-halobenzoates with methylmagnesium
iodide gives the target tertiary alcohols 1 in good yields. As
shown in Table 1, a series of o-halobenzyl alcohols 1a−1g were
33
<1
0
Br (1a)
Br (1a)
Br (1a)
0
0
26
0
a
Determined by 1H NMR analysis of the crude mixture, using
bromoform as an internal standard.
at reflux. The combination of o-bromobenzyl alcohol 1a and o-
bromobiphenyl (2a) gave the target product 3a in 15% yield
(entry 1). Benzochromene 4 was found to be the major
byproduct of this reaction, generated by the homocoupling of
1.13a,c When o-chlorobenzyl alcohol 1b was reacted with 2a,
only a trace amount of 3a was obtained and most of the
unreacted 1b and 2a were recovered (entry 2). The use of o-
iodobenzyl alcohol 1c gave a complex mixture including 2% of
3a and 33% of 4 (entry 3). The reaction of o-biphenylyl triflate
(2b) or the corresponding chloride 2c with 1a did not proceed,
probably due to the low reactivity of 2b and 2c (entries 4 and
5). Finally, the reaction of o-iodobiphenyl (2d) with 1a was
found to be optimal, yielding 3a in 26% yield (entry 6). As
described later, the reaction may proceed by utilizing the
different reaction rates for oxidative addition of iodides and
bromides.
Table 1. Preparation of o-Halobenzyl Alcohols 1
It is additionally notable that the choice of the phosphine
ligand has a significant effect on the efficiency of the reaction
(Table 3). In the absence of a phosphine ligand, almost no
reaction proceeded (entry 2). The yield of 3a slightly increased
with the electron-deficient phosphine (entry 3), while the
Table 3. Ligand Screening
a
entry
ligand
X (mol %)
20
yield (%)
uneventfully obtained by Grignard reaction with methylmagne-
sium iodide. Although any alkyl groups can be installed on the
annulating reagents 1, a methyl group may be ideal because the
acetone formed can easily be removed from the reaction
mixture.
1
2
3
4
5
6
7
8
9
PPh3
none
44
<1
47
35
5
P[3,5-(CF3)2C6H3]3
P(4-MeOC6H4)3
P(OPh)3
20
20
20
20
10
10
10
PnBu3
0
Synthesis of Triphenylenes. We initiated a program to
develop a synthetic method for triphenylene (3a) by the
palladium-catalyzed annulation of o-halobiphenyls 2 with o-
halobenzyl alcohols 1. Initial screening of the leaving groups of
1 and 2 was conducted as shown in Table 2. In a typical
reaction, 1 and 2 (1.2 equiv) were treated with Pd(dba)2 (5
mol %), PPh3 (20 mol %), and Cs2CO3 (2.4 equiv) in toluene
DPPE
<1
0
DPPP
DPPF
0
a
Determined by 1H NMR analysis of the crude mixture, using
bromoform as an internal standard.
B
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Table 4. Reactions of o-Bromobenzyl Alcohol 1a with o-Iodobiphenyls 2
a
b
c
1
Isolated yields based on 2 after silica gel column chromatography. Determined by H NMR analysis. Combined yield of two regioisomers.
C
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electron-rich phosphine dropped the yield (entry 4). Strong
electron-donating ability of the phosphines would not control
the reaction sequence of bromide 1a and iodide 2d with
palladium. Extensive screening of the ligands including
phosphite and trialkylphosphine gave the negative results
(entries 5 and 6). Similar poor yields were observed with some
bidentate phosphines such as DPPE (1,2-bis(diphenyl-
phosphino)ethane), DPPP (1,3-bis(diphenylphosphino)-
propane), and DPPF (1,1′-bis(diphenylphosphino)ferrocene)
(entries 7−9).
Table 5. Reactions of Various o-Bromobenzyl Alcohols 1
with o-Iodobiphenyl (2d)
After exploring the effect of various conditions on the
reaction of 1a with 2d,14 we found the optimum conditions:
PdCl2(NCPh)2 (5 mol %), P[3,5-(CF3)2C6H3]3 (10 mol %),
and Cs2CO3 (2.4 equiv) in toluene. Under these reaction
conditions, 3a was obtained in 81% yield (Table 4, entry 1).
With the optimized conditions in hand, we performed the
annulation of various o-iodobiphenyls 2 with 1a. First of all,
several substitution patterns of 2 were systematically inves-
tigated. In addition to nonsubstituted substrate 2d (entry 1),
not surprisingly, o-iodobiphenyls 2e and 2f with a methyl or
phenyl group at the 4′-position underwent annulation with 1a
to provide the corresponding triphenylenes 3b and 3c (entries
2 and 3). However, substituents at the 2′- or 3′-position on 1
slightly suppressed the formation of triphenylenes 3d and 3e
(entries 4 and 5) by retarding the intramolecular direct
arylation step due to steric congestion. Although the reaction of
2-iodo-3′-methylbiphenyl (2i) proceeded well, a mixture of
regioisomers 3b and 3d was formed because of two possible
reaction sites (entry 6). Conceivably, the reaction occurred
preferentially at the less-hindered C−H bond of 2i to afford 3b
as the major product. Various functional groups were found to
be compatible under the mild reaction conditions, but their
electronic effects on 2 affected yields to some extent. For
example, the substrates 2j−2n with an electron-withdrawing
nitro, trifluoromethyl, fluoro, chloro, or methoxycarbonyl group
reacted effectively with 1a to furnish triphenylenes 3f−3j in
moderate to good yields (entries 7−11). In contrast, the
reaction of o-iodobiphenyl 2o bearing an electron-donating
methoxy group resulted in a slightly decreased yield (entry 12).
The effect of a linker that restricted the rotation along the biaryl
axis prevented the cyclization to form triphenylene 3l (entry
13), probably due to the possible formation of a highly strained
7-membered palladacycle intermediate. The substituents at the
4- and 5-positions of 2q did not interfere with the annulation
with 1a to yield the product 3m in 61% yield (entry 14).
Various o-bromobenzyl alcohols 1 were then subjected to the
annulation of 2d (Table 5). The functional groups on substrate
1 did not impair the efficiency of the reaction, which provided
the corresponding triphenylenes 3k, 3m, and 3n in good yields
(entries 2−4). The substrate does not have to be benzyl
alcohol. Indeed, the naphthalene-containing tertiary alcohol 1g
converted 2d into benzochrysene 3o in 31% yield (entry 5).
The utility of the present synthetic method was clearly
demonstrated by the single-step synthesis of highly fused
PAHs.
a
Isolated yields based on 2d after silica gel column chromatography.
reactivities of 1a and 2d. The subsequent ligand exchange
between A and 1a in the presence of cesium carbonate yields
aryl(alkoxy)palladium intermediate B. Deacetonative β-carbon
elimination8a,15 generating diarylpalladium species C, followed
by reductive elimination, gives the o-bromoterphenyl inter-
mediate 5a, regenerating the starting Pd(0) species. The
formation of intermediate 5a was unambiguously confirmed by
NMR and GC-MS analyses. The generated 5a again undergoes
oxidative addition to Pd(0). Cyclopalladation of o-terphenyl-
palladium bromide D through C−H bond cleavage affords a 7-
membered palladacycle intermediate E.16 Final productive
reductive elimination provides the desired triphenylenes 3a
along with the regeneration of the starting Pd(0) complex. At
the early stage of the reaction, intermediate 5a was accumulated
prior to the formation of the product 3a, which suggests that
intramolecular cyclization could be a rate-determining step.
This hypothesis was supported by the fact that the reactions of
the sterically congested substrates 2g and 2h, or the substrate
2p via a strained palladacycle intermediate, resulted in low
yields (Table 4, entries 3, 5, and 13). It is of note that the same
Scheme 1 shows a plausible reaction mechanism for the
palladium-catalyzed annulation of o-iodobiphenyl (2d) with o-
bromobenzyl alcohol 1a, which is in good agreement with
present and previous experimental observations. Initially,
oxidative addition of 2d to Pd(0) affords arylpalladium iodide
A because of the faster oxidative addition of aryl iodide to
Pd(0) than the bromide 1a. The electron-deficient phosphine
ligand would help the palladium to distinguish the different
D
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Scheme 1. A Plausible Reaction Mechanism for Triphenylene Synthesis
Scheme 2. Control Experiments
starting Pd(0) complex effectively catalyzes two different
reactions, deacetonative coupling and intramolecular cycliza-
tion.
albeit in low yield, predominantly providing triphenylene 3r
(entry 3). However, the selectivity was reversed to give
triphenylene 3s′ as the major product when 2-iodo-3,5-
dimethoxybiphenyl (2q) was employed (entry 4).
The proposed mechanism shown in Scheme 1 was confirmed
by the cyclization of o-bromoterphenyl 5a under the identical
reaction conditions, which gave the target triphenylene 3a
quantitatively (Scheme 2a). However, the reaction mechanism
involving the aryne intermediate generated from 1a cannot be
completely ruled out at this stage. We only know that the
reaction of 1a with 2d in the presence of furan that would trap
the formed aryne with a Diels−Alder reaction did not provide
the adduct 6, but triphenylene 3a in 70% yield (Scheme 2b).17
Although several synthetic methods for triphenylenes have
been reported, access to various substituted triphenylenes
bearing several different functional groups is still challenging
and highly desirable. We could successfully prepare multi-
substituted triphenylenes 3 and 3′ by the annulation of
substituted o-iodobiphenyls 2 with methoxy-bearing o-bromo-
benzyl alcohol 1d (Table 6). The reactions of the electronically
diverse substrates 2j and 2o proceeded smoothly to afford a 1:1
mixture of regioisomers 3 and 3′ in 82% and 48% combined
yields, respectively (entries 1 and 2). On the other hand, the
substrate 2h, congested at the reaction site, reacted with 1d,
A plausible mechanism for the unexpected formation of the
3′ regioisomers is shown in Scheme 3. Triphenylene 3 may be
obtained by the reaction of 1d with the generated arylpalladium
iodide F via intermediate 5. Considering the detailed studies by
Larock and co-workers, we propose that 1,4-palladium
migration from the palladium complex F forms arylpalladium
iodide F′ via a 5-membered palladacycle intermediate.18
Subsequently, the palladium complex F′ couples with 1d to
yield the intermediate 5′, from which an intramolecular
cyclization proceeds to afford triphenylene 3′. In the case of
substrates 2j and 2o, bearing nitro and methoxy groups, a 1:1
mixture of 3 and 3′ regioisomers was obtained probably
because of the rapid equilibrium of 1,4-palladium migration,
which suggests that the electronic properties of o-iodobiphenyls
1 did not influence the regioselectivity of the reaction. Even at
90 °C, the ratio of regioisomers 3p and 3p′ was not changed,
while the product yield was decreased to 8%. This result
indicates that 1,4-palladium migration is rather faster than the
reaction of 1d with F.
E
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group and palladium, which would render the intermediate G′
disfavored. The arylpalladium complex G smoothly reacts with
o-benzyl alcohol 1d to yield triphenylene 3r as the main
product. The interesting preferential formation of triphenylene
3s′ observed in the reaction of 1d with 2q would be also
explained by the above-mentioned steric factor in 1,4-palladium
migration.
Table 6. Synthesis of Multisubstituted Triphenylenes
Synthesis of Phenanthrenes. The successful triphenylene
synthesis led us to examine palladium-catalyzed annulation of o-
halostyrenes 7 with o-bromobenzyl alcohols 1 to afford the
corresponding phenanthrenes. Thus, o-bromobenzyl alcohol 1a
was treated with o-iodostyrene (7a) under the identical
conditions required to obtain triphenylene (Scheme 5).
Unfortunately, our initial attempts gave none of the desired
phenanthrene (8a), although the starting material 7a was
completely consumed. We assumed that the reactive terminal
alkene would undergo undesired reactions such as oligomeriza-
tion and polymerization,19 although no byproducts were
identified. In addition, the reaction of o-bromostyrene did not
afford 8a. Even with o-iodo-α-methylstyrene (7b) suppressing
the interaction between alkene and palladium, only 9% yield of
1
product 8b was observed by H NMR analysis. In spite of
further optimization of the catalytic system, a satisfactory yield
of 8b was not realized.14
Because of the extra high reactivity and limited availability of
o-iodostyrenes, we then turned our attention to the annulation
of (Z)-β-iodostyrenes for the facile synthesis of phenanthrenes.
To our delight, 1-iodo-1,2,2-triphenylethene (9a) smoothly
underwent annulation with o-bromobenzyl alcohol 1a under
PdCl2(NCPh)2/P(p-CF3C6H4)3 catalysis to form the desired
phenanthrene 8c in 28% NMR yield (Table 7, entry 1). Since
the starting iodide 9a was consumed, the less-reactive alkenyl
bromide 9b was then investigated. The sequential C−C bond
formation proceeded well to afford 8c in 81% yield (entry 2).
Finally, the yield was improved to 99% by using 1.4 equiv of 1a
and prolonging the reaction time to 24 h (entries 3 and 4).
With the identified optimal conditions in hand, we aimed at
defining the scope of (Z)-β-halostyrene derivatives 9. As
summarized in Table 8, we were delighted to find that a wide
range of substrates having diverse functional groups and various
substitution patterns were readily transformed to the
a
b
1
Determined by H NMR analysis. Isolated combined yields of two
regioisomers based on 2 after silica gel column chromatography.
In the reaction of o-iodobiphenyl 2h, the predominant
formation of triphenylene 3r was observed, which can be
explained by the steric factor (Scheme 4). During 1,4-palladium
migration, the arylpalladium species G would be favored. The
other intermediate G′ has steric repulsion between a methyl
Scheme 3. Aryl-to-Aryl 1,4-Palladium Migration
F
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Scheme 4. Preferred Equilibrium in 1,4-Palladium Migration Determined by Steric Factor
Scheme 5. Palladium-Catalyzed Annulation of o-
Halostyrenes 7 with o-Bromobenzyl Alcohol 1a
As a small variant of this reaction, the effect of substituents
on the phenyl ring at the β-position to the bromo group in 9
was examined in the reaction with 1a (Table 9). The methoxy-
substituted alkenyl bromide 9m served as a substrate to
produce the expected product 8e in 70% yield along with
phenanthrene 8e′, which may be formed by annulation on the
other side (entry 1). In addition, the reaction of electron-
deficient 9n and 9o also gave a mixture of isomers 8 and 8′
(entries 2 and 3). These results clearly suggest that
alkenylpalladium H formed by oxidative addition of 9 would
undergo E/Z isomerization20 to provide stereoisomer H′, from
which the reaction with 1a afforded the minor product 8′
(Scheme 6). The phenanthrenes 8 and 8′ were unambiguously
determined by spectroscopic analysis, while the dibenzofulvene
derivatives which would be possibly formed by C−H arylation
were not detected in each case probably because of highly
strained skeletons.21a−c
Table 7. Palladium-Catalyzed Annulation of 1-Halo-1,2,2-
triphenylethenes 9 with o-Bromobenzyl Alcohol 1a
a
As shown in Table 10, annulation of 9b with several
annulating reagents 1 proceeded smoothly to provide various
products 8. In addition to nonsubstituted o-bromobenzyl
alcohol 1a giving rise to 8c, the annulating reagents 1e, having
two methoxy groups, and 1f, containing an acetal skeleton,
coupled with 9b to give the corresponding phenanthrenes 8l
and 8m in good yields, respectively (entries 1−3). Notably, o-
bromobenzyl alcohol 1d, bearing one methoxy group, was
employed for the annulation with 9b to afford the expected
phenanthrene 8n in only 14% yield, while the regioisomer 8e′
was mainly formed in a 1:5 ratio (entry 4). Moreover, the
reaction with naphthalene-containing tertiary alcohol 1g did
not give benzophenanthrene 8o, but chrysene derivative 8o′
was obtained in 74% yield as a single product (entry 5).
The unexpected predominant formation of phenanthrene 8e′
can be rationalized as illustrated in Scheme 7. After oxidative
addition of alkenyl bromide 9b, the alkenylpalladium complex I
reacts with o-bromobenzyl alcohol 1d to afford the expected
phenanthrene 8n. On the other hand, 1,4-palladium migration
from I forms arylpalladium complex I′, which reacts with 1d to
afford 8e′.21 During 1,4-palladium migration, thermodynami-
cally more stable I′ may be preferred.22,23 The exclusive
formation of phenanthrene 8o′ strongly supports the 1,4-
palladium migration of alkenylpalladium to arylpalladium.
To gain more insight into the possible equilibrium in 1,4-
palladium migration, the reaction of methoxy-substituted o-
bromobenzyl alcohol 1d with aryl bromide 7c was investigated
under the identical reaction conditions (Scheme 8). Con-
sequently, phenanthrene 8e′ was obtained (55% yield) as the
main product, which is consistent with the annulation of 9b
with 1d. This observation obviously shows that equilibrium
may be rapidly achieved in 1,4-palladium migration. Further
modification of the catalyst system to control the E/Z
isomerization and 1,4-palladium migration was essential for a
selective synthesis.
a
entry
9
1a (equiv)
time (h)
yield (%)
1
2
3
4
9a
9b
9b
9b
1.2
1.2
1.2
12
12
24
24
28
81
85
1.4
99 (88)
a
1
Yields were determined by the H NMR analysis of a crude mixture
using dibenzyl ether as an internal standard. An isolated yield based on
9 after silica gel column chromatography is shown in parentheses.
corresponding phenanthrenes. For example, both electron-
donating and -withdrawing functional groups were equally
tolerated under the reaction conditions, affording the desired
products 8c−8g in good yields (entries 1−5). The present
synthetic method was successfully applied to the synthesis of
highly functionalized phenanthrene 8h, starting from (Z)-β-
bromostyrene 9g bearing one methoxy and two fluoro groups
(entry 6). Moreover, alkenyl bromides 9h and 9k substituted
with alkyl groups were also found to be competent coupling
partners, providing products 8i and 8j in moderate yields
(entries 7 and 10). It is of note that the reactions of the
corresponding alkenyl iodides 9i and 9l gave slightly higher
yields of products 8i and 8j (entries 8 and 11). Electron-
donating alkyl groups on the substrates may retard oxidative
addition to palladium. On the other hand, the reaction of the
corresponding triflate 9j afforded no product 8i, in which a
significant amount of 9j was consumed (entry 9). The relatively
less-hindered cationic palladium species generated from 9j
would undergo the polymerization. Substituents R2 and R3 on
substrate 9 proved to be essential for the efficient synthesis of
phenanthrenes,14 as they can interrupt the undesired
interaction with palladium.19
G
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Table 8. Palladium-Catalyzed Annulation of (Z)-β-Halostyrenes 9 with o-Bromobenzyl Alcohol 1a
a
Isolated yields based on 9 after silica gel column chromatography.
On the basis of the obtained results, we assume that the
reaction of 1a with 9b proceeds as illustrated in Scheme 9. First,
oxidative addition of 9b to the starting Pd(0) provides the
alkenylpalladium species J. In general, oxidative addition of
alkenyl bromides occurred faster than that of aryl bromi-
des.10s,24 The following 1,4-palladium migration from J occurs
smoothly to afford the thermodynamically more stable
arylpalladium intermediate K. As is the case with triphenylene
synthesis (Scheme 1), ligand exchange, β-carbon elimination,
and reductive elimination proceed sequentially to yield aryl
bromide 10 via the intermediates L and M, along with the
regeneration of the Pd(0) complex. Next, the formed aryl
bromide 10 again undergoes oxidative addition to Pd(0),
affording the arylpalladium complex N. Finally, intramolecular
migratory insertion of the alkene, followed by base-assisted
trans-β-hydrogen elimination25 from intermediate O, provides
the desired phenanthrene 8c to accomplish the catalytic cycle.
The possible intermediate 10 was not detected even in the early
H
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Table 9. Palladium-Catalyzed Annulation of (Z)-β-Halostyrenes 9m−9o with o-Bromobenzyl Alcohol 1a
a
yield (%)
entry
R
9
product
8
8′
b
b
b
1
2
3
OMe
F
9m
9n
9o
8e + 8e′
8f + 8f′
70
63
70
24
32
13
b
CF3
8k + 8k′
a
b
1
Isolated yields based on 9 after silica gel column chromatography. Determined by H NMR analysis and the combined yields of two isomers.
Scheme 6. E/Z Isomerization of Alkenylpalladium Species
Table 10. Palladium-Catalyzed Annulation of 1-Bromo-
1,2,2-triphenylethene (9b) with o-Bromobenzyl Alcohols 1
stage of the reaction, which suggests that the deacetonative
coupling of o-bromobenzyl alcohols 1 with (Z)-β-halostyrenes
9 would be the rate-limiting step. This observation is opposite
to the triphenylene synthesis, in which the intramolecular
cyclization is slower than the deacetonative coupling.
To demonstrate the synthetic potential of the products,
oxidative cyclization of 8d was explored. Treatment of 8d with
2,3-dichloro-5,6-dicyanobenzoquinone (DDQ) in the presence
of methanesulfonic acid gave the corresponding cyclized
product 11 in 50% yield (Scheme 10).26 The obtained
dibenzochrysene derivative 11 is well-known to have attractive
fluorescence properties, high quantum yields, small Stokes
shifts, and long-lived excited states.27
CONCLUSIONS
■
In summary, the facile synthesis of phenacene-type PAHs was
achieved by palladium-catalyzed sequential C−C bond
formation. We have developed o-bromobenzyl alcohol as a
new annulating reagent, which facilitates the annulation of o-
iodobiphenyls and (Z)-β-halostyrenes to provide triphenylenes
and phenanthrenes, respectively. This protocol can allow us to
access a variety of highly fused π-conjugated molecules bearing
an array of functional groups. Mechanistic studies have
provided some evidence supporting the equilibrium of 1,4-
palladium migration, which explains the formation of
regioisomers and the selectivity. Further application of
palladium-catalyzed annulation to the synthesis of other
phenacene-type molecules and the development of more
reactive catalysts are currently underway in our laboratory.
a
Isolated yields based on 2 after silica gel column chromatography.
b
c
Determined by 1H NMR analysis. Combined yield of two
regioisomers.
EXPERIMENTAL SECTION
Chemicals. Unless otherwise noted, materials obtained from
commercial suppliers were used without further purification.
■
was warmed to room temperature. After being stirred for 2 h, saturated
ammonium chloride solution (30 mL) was added at 0 °C. The product
was extracted with ethyl acetate (20 mL × 3). The organic layers were
then washed with brine and dried over anhydrous sodium sulfate. After
volatiles were evaporated, silica gel column chromatography (hexane/
ethyl acetate = 5:1) yielded 1a (2.02g, 9.4 mmol, 94% yield).
A Typical Procedure for Preparation of o-Halobenzyl
Alcohols 1: Synthesis of 2-(o-bromophenyl)-2-propanol (1a)
(Table 1). Under an argon atmosphere, methylmagnesium iodide (1.0
M ethereal solution, 24 mL, 24 mmol) was placed in a 100 mL
reaction flask. Ethyl o-bromobenzoate (1.6 mL, 10 mmol) in ether (20
mL) was added dropwise to the Grignard reagent at 0 °C. The mixture
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Scheme 7. Alkenyl-to-Aryl 1,4-Palladium Migration
a
Scheme 8. A Control Experiment
a
Conditions: PdCl2(NCPh)2 (5 mol %), P(4-CF3C6H4)3 (10 mol %), Cs2CO3 (2.4 equiv), toluene, 110 °C, 24 h.
Scheme 9. A Plausible Reaction Mechanism for Phenanthrene Synthesis
126.6, 127.6, 127.7, 128.0, 128.0, 133.2, 133.8, 144.4. Calcd for
C13H13BrO: C, 58.89; H, 4.94%. Found: C, 58.91; H, 4.75%.
o-Halobiphenyls 2a, 2c, and 2d were obtained from commercial
suppliers. Compounds 2b,31 2e−2i,32 2j,33 2k−2o,30 2p,34 and 2q30
were prepared by literature procedures. Spectroscopic data of 2b35 and
2g8e can be found in the literature.
Scheme 10. Oxidative Cyclization of 8d
2-Iodo-4′-methylbiphenyl (2e).32 The title compound was
obtained as a white solid (412 mg, 1.40 mmol, 56%). Mp = 35 °C.
1
IR (KBr): 3049, 1460, 1001, 818, 754 cm−1. H NMR (400 MHz,
CDCl3, rt): δ 2.42 (s, 3H), 7.02 (td, J = 7.6, 1.8 Hz, 1H), 7.24 (s, 4H),
7.29 (dd, J = 7.6, 1.8 Hz, 1H), 7.38 (td, J = 7.6, 1.2 Hz, 1H), 7.95 (dd,
J = 7.6, 1.2 Hz, 1H); 13C{1H} NMR (100 MHz, CDCl3, rt): δ 21.3,
98.8, 128.1, 128.6, 128.6, 129.1, 130.1, 137.4, 139.4, 141.3, 146.6.
Calcd for C13H11I: C, 53.09; H, 3.77%. Found: C, 53.10; H, 3.64%.
2-Iodo-4′-phenylbiphenyl (2f).32 The title compound was
obtained as a white solid (482 mg, 1.35 mmol, 27%). Mp = 97 °C.
A colorless liquid. 1H NMR (300 MHz, CDCl3, rt): δ 1.75 (s, 6H),
7.10 (dt, J = 8.1, 1.5 Hz, 1H), 7.30 (dt, J = 8.1, 1.5 Hz, 1H), 7.58 (dd, J
= 8.1, 1.5 Hz, 1H), 7.67 (dd, J = 8.1, 1.5 Hz, 1H).
o-Halobenzyl alcohols 1b−1g were prepared according to the
above-mentioned procedure. Spectroscopic data of 1a,13a 1b,28 1c,29
1d,30 1e,13a and 1f13a can be found in the literature.
1-Bromo-2-(1-hydroxy-2-propyl)naphthalene (1g). The title
compound was obtained as a colorless liquid (530 mg, 0.200 mmol,
96%). IR (neat) 3424, 2974, 1497, 1315, 1165, 955, 818, 746 cm−1. 1H
NMR (400 MHz, CDCl3, rt): δ 1.89 (s, 6H), 3.08 (s, 1H), 7.50−7.54
(m, 1H), 7.58−7.62 (m, 1H), 7.80−7.87 (m, 3H), 7.45−7.47 (d, J =
8.8 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ 30.1, 74.6, 121.1, 124.8,
1
IR (KBr): 3028, 1460, 997, 843, 754 cm−1. H NMR (400 MHz,
CDCl3, rt): δ 7.05 (td, J = 7.6, 1.9 Hz, 1H), 7.34−7.49 (m, 7H), 7.66−
7.68 (m, 4H), 7.98 (d, J = 7.6 Hz, 1H); 13C{1H} NMR (100 MHz,
CDCl3, rt): δ 98.7, 126.8, 127.3, 127.6, 128.3, 128.9, 129.0, 129.9,
130.3, 139.7, 140.6, 140.8, 143.2, 146.4. Calcd for C18H13I: C, 60.69;
H, 3.68%. Found: C, 60.67; H, 3.66%.
2-Iodo-3′,5′-dimethylbiphenyl (2h). The title compound was
obtained as a colorless liquid (388 mg, 1.26 mmol, 50%). IR (neat):
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1
2914, 1603, 1460, 1014, 851, 756 cm−1. H NMR (400 MHz, CDCl3,
1-Iodo-6H-dibenzo[b,d]pyran (2p). The title compound was
rt): δ 2.38 (s, 6H), 6.96−7.04 (m, 4H), 7.29 (dd, J = 7.6, 1.9 Hz, 1H),
7.37 (td, J = 7.6, 1.2 Hz, 1H), 7.94 (dd, J = 7.6, 1.2 Hz, 1H); 13C{1H}
NMR (100 MHz, CDCl3, rt): δ 21.5, 98.8, 127.2, 128.1, 128.7, 129.3,
130.2, 137.5, 139.5, 144.2, 147.0. Calcd for C14H13I: C, 54.57; H,
4.25%. Found: C, 54.93; H, 4.34%.
2-Iodo-3′-methylbiphenyl (2i). The title compound was
obtained as a colorless liquid (53.4 mg, 0.182 mmol, 12%). IR
(neat): 3049, 1584, 1460, 1012, 754 cm−1. 1H NMR (300 MHz,
CDCl3, rt): δ 2.42 (s, 3H), 7.03 (td, J = 7.7, 1.8, 1H), 7.14−7.23 (m,
3H), 7.29−7.41 (m, 3H), 7.96 (dd, J = 7.7, 1.1 Hz, 1H); 13C NMR (75
MHz, CDCl3) δ 21.6, 98.8, 126.5, 127.9, 128.2, 128.5, 128.8, 130.1,
130.2, 137.7, 139.6, 144.3, 146.9. Calcd for C13H11I: C, 53.09; H,
3.77%. Found: C, 53.35; H, 3.82%.
obtained as a brown liquid (52.7 mg, 0.171 mmol, 11%). IR (neat):
1
2851, 1585, 1423, 1247, 1013, 845, 783 cm−1. H NMR (400 MHz,
CDCl3, rt): δ 4.95 (s, 2H), 6.90 (t, J = 7.9 Hz, 1H), 7.04 (dd, J = 7.5,
1.2, 1H), 7.22 (m, 1H), 7.34 (td, J = 7.5, 1.2, 1H), 7.44 (td, J = 7.5, 1.2
Hz, 1H), 7.68 (dd, J = 7.5, 1.2 Hz, 1H), 8.54 (d, J = 7.9 Hz, 1H);
13C{1H} NMR (100 MHz, CDCl3, rt): δ 69.5, 91.9, 118.0, 124.9,
126.1, 126.9, 127.5, 128.1, 130.1, 130.5, 133.4, 136.1, 156.7. HRMS
(FAB+) Calcd for C13H9IO: 307.9698. Found: 307.9712 [M+].
2-Iodo-5,6-dimethoxybiphenyl (2q). The title compound was
obtained as a white solid (107 mg, 0.315 mmol, 13%). Mp = 110 °C.
1
IR (KBr): 2961, 1487, 1206, 1018, 858, 766 cm−1. H NMR (400
MHz, CDCl3, rt): δ 3.86 (s, 3H), 3.91 (s, 3H), 6.83 (s, 1H), 7.34−7.43
(m, 6H); 13C{1H} NMR (100 MHz, CDCl3, rt): δ 56.1, 56.4, 86.4,
113.1, 121.8, 127.6, 128.1, 129.6, 139.4, 144.2, 148.8, 149.2. Calcd for
C14H13IO2: C, 49.43; H, 3.85%. Found: C, 49.48; H, 3.72%.
2-Iodo-4′-nitrobiphenyl (2j). The title compound was obtained
as a white solid (130 mg, 0.400 mmol, 30%). Mp = 103 °C. IR (KBr):
1
3080, 1597, 1506, 1350, 854, 768 cm−1. H NMR (400 MHz, CDCl3,
A Typical Procedure for Annulation of o-Iodobiphenyls 2
with o-Bromobenzyl Alcohols 1: Synthesis of Triphenylene
(3a) (Table 4, entry 1). Under an argon atmosphere, cesium
carbonate (390 mg, 1.2 mmol), bis(benzonitrile)dichloropalladium
(9.6 mg, 0.025 mmol), and tris{3,5-bis(trifluoromethyl)phenyl}-
phosphine (34 mg, 0.050 mmol) were placed in a 20 mL Schlenk
tube. A solution of o-iodobiphenyl (2d, 140 mg, 0.50 mmol) and 2-(o-
bromophenyl)-2-propanol (1a, 130 mg, 0.60 mmol) in toluene (2.0
mL) was added. The resulting mixture was stirred at 110 °C for 24 h.
The mixture was then cooled to room temperature. Hydrochloric acid
(1 M, 6 mL) was added, and the product was extracted with ethyl
acetate (10 mL × 3). The organic layers were then washed with brine
and dried over anhydrous sodium sulfate. After the volatiles were
evaporated, silica gel column purification with hexane as an eluent
afforded triphenylene 3a (92.4 mg, 0.405 mmol, 81% yield). White
rt): δ 7.11 (td, J = 7.6, 1.7 Hz, 1H), 7.29 (dd, J = 7.6, 1.7 Hz, 1H), 7.44
(td, J = 7.6, 1.1 Hz, 1H), 7.51−7.54 (m, 2H), 7.99 (dd, J = 7.6, 1.1 Hz,
1H), 8.28−8.32 (m, 2H); 13C{1H} NMR (100 MHz, CDCl3, rt): δ
97.5, 123.5, 128.6, 129.9, 130.0, 130.5, 140.0, 144.5, 147.4, 150.5.
Calcd for C12H8INO2: C, 44.33; H, 2.48; N, 4.31%. Found: C, 44.38;
H, 2.40; N, 4.14%.
2-Iodo-4′-(trifluoromethyl)biphenyl (2k). The title compound
was obtained as a colorless liquid (135 mg, 0.389 mmol, 30%). IR
1
(neat): 3051, 1618, 1325, 1128, 840, 760 cm−1. H NMR (400 MHz,
CDCl3, rt): δ 7.08 (td, J = 7.6, 1.7 Hz, 1H), 7.28 (dd, J = 7.6, 1.7 Hz,
1H), 7.42 (td, J = 7.6, 1.2 Hz, 1H), 7.47 (d, J = 8.0 Hz, 2H), 7.69 (d, J
= 8.0 Hz, 2H), 7.98 (dd, J = 7.6, 1.2 Hz, 1H); 13C{1H} NMR (100
1
3
MHz, CDCl3, rt): δ 98.0, 124.2 (q, JC‑F = 270 Hz), 125.0 (q, JC‑F
=
2
3.7 Hz), 128.4, 129.6, 129.9, 129.9 (q, JC‑F = 32.4 Hz) 130.1 139.8,
145.4, 147.7; 19F{1H} NMR (376 MHz, CDCl3, rt): δ −62.6. Calcd for
C13H8F3I: C, 44.85; H, 2.32%. Found: C, 45.25; H, 2.33%.
1
solid. H NMR (300 MHz, CDCl3, rt): δ 7.66−7.69 (m, 6H), 8.66−
8.69 (m, 6H).
Spectroscopic data of 3a,36 3b,8b 3e−3f,8e 3k,8b 3m,8b 3o,37 3q,38
3q′,8f and 3s8e can be found in the literature.
2-Methyltriphenylene (3b). The reaction of 1a with 2e provided
4′-Fluoro-2-iodobiphenyl (2l). The title compound was obtained
as a colorless liquid (457 mg, 1.53 mmol, 79%). IR (neat): 3049, 1605,
1
1512, 1460, 1222, 1001, 835, 758 cm−1. H NMR (400 MHz, CDCl3,
1
the title compound as a white solid (39.5 mg, 0.163 mmol, 65%). H
rt): δ 7.04 (td, J = 7.6, 1.6 Hz, 1H), 7.09−7.13 (m, 2H), 7.27−7.33
NMR (300 MHz, CDCl3, rt): δ 2.62 (s, 3H), 7.50 (d, J = 8.4 Hz, 1H),
7.62−7.67 (m, 4H), 8.45 (s, 1H), 8.55 (d, J = 8.4 Hz, 1H), 8.61−8.67
(m, 4H).
(m, 3H), 7.39 (td, J = 7.6, 1.2 Hz, 1H), 7.95 (dd, J = 7.6, 1.2 Hz, 1H);
2
13C{1H} NMR (100 MHz, CDCl3, rt): δ 98.9, 115.1 (d, JC‑F = 21.4
3
Hz), 128.3, 129.1, 130.2, 131.1 (d, JC‑F = 8.2 Hz), 139.7, 140.3 (d,
2-Phenyltriphenylene (3c). The reaction of 1a with 2f provided
1
4JC‑F = 3.3 Hz), 145.8, 162.5 (d, JC‑F = 245 Hz); 19F{1H} NMR (376
the title compound as a white solid (35.8 mg, 0.118 mmol, 47%). Mp
1
= 182 °C. IR (KBr): 3053, 1491, 746 cm−1. H NMR (400 MHz,
MHz, CDCl3, rt): δ −114.6. Calcd for C12H8FI: C, 48.35; H, 2.70%.
Found: C, 48.46; H, 2.64%.
CDCl3, rt): δ 7.41−7.46 (m, 1H), 7.52−7.57 (m, 2H), 7.65−7.72 (m,
4H), 7.81−7.84 (m, 2H), 7.91 (dd, J = 8.4, 1.8 Hz, 1H), 8.66−8.78
(m, 5H), 8.87 (d, J = 1.8 Hz, 1H); 13C{1H} NMR (125 MHz, CDCl3,
rt): δ 121.9, 123.46, 123.48, 123.48, 123.53, 124.0, 126.5, 127.4, 127.4,
127.4, 127.5, 127.6, 127.7, 129.0, 129.1, 129.7, 129.92, 129.94, 130.2,
130.2, 140.0, 141.3. HRMS (FAB+) Calcd for C24H17: 305.1330.
Found: 305.1331 [M + H]+.
4′-Chloro-2-iodobiphenyl (2m). The title compound was
obtained as a colorless liquid (302 mg, 0.960 mmol, 48%). IR
(neat): 3049, 1595, 1494, 1458, 1092, 1016, 827, 756 cm−1. 1H NMR
(400 MHz, CDCl3, rt): δ 7.05 (td, J = 7.7, 1.6 Hz, 1H), 7.26−7.30 (m,
3H), 7.37−7.42 (m, 3H), 7.96 (dd, J = 7.7, 1.2 Hz, 1H); 13C{1H}
NMR (100 MHz, CDCl3, rt): δ 98.5, 128.36, 128.38, 129.2, 130.1,
130.8, 133.9, 139.8, 142.7, 145.6. Calcd for C12H8ClI: C, 45.82; H,
2.56%. Found: C, 45.90; H, 2.54%.
2-Iodo-4′-methoxycarbonylbiphenyl (2n). The title compound
was obtained as a colorless liquid (114 mg, 0.337 mmol, 57%). IR
(neat): 3051, 2949, 1726, 1610, 1435, 1279, 1113, 754 cm−1. 1H NMR
(400 MHz, CDCl3, rt): δ 3.95 (s, 3H), 7.07 (td, J = 7.8, 1.6 Hz, 1H),
7.29 (dd, J = 7.8, 1.6 Hz, 1H), 7.39−7.43 (m, 3H), 7.97 (dd, J = 7.8,
0.8 Hz, 1H), 8.09−8.11 (m, 2H); 13C{1H} NMR (100 MHz, CDCl3,
rt): δ 52.3, 97.9, 128.4, 129.4, 129.48, 129.52, 129.6, 130.0, 139.8,
145.8, 148.7, 167.0. HRMS (FAB+) Calcd for C14H12IO2: 338.9882.
Found: 338.9861 [M + H]+.
1-Methyltriphenylene (3d). The reaction of 1a with 2g provided
the title compound as a white solid (23.0 mg, 0.095 mmol, 38%). Mp
1
= 96 °C. IR (KBr): 2947, 1431, 752 cm−1. H NMR (400 MHz,
CDCl3, rt): δ 3.07 (s, 3H), 7.53−7.68 (m, 6H), 8.53−8.67 (m, 5H);
13C{1H} NMR (100 MHz, CDCl3, rt): δ 26.8, 121.2, 123.1, 123.4,
123.8, 125.7, 126.4, 126.7, 127.2, 127.4, 128.6, 130.0, 130.5, 130.5,
130.8, 131.1, 131.4, 131.8, 135.5. Calcd for C19H14: C, 94.18; H,
5.82%. Found: C, 93.93; H, 5.88%.
1,3-Dimethyltriphenylene (3e). The reaction of 1a with 2h
provided the title compound as a white solid (17.9 mg, 0.070 mmol,
1
28%). H NMR (300 MHz, CDCl3, rt): δ 2.58 (s, 3H), 3.03 (s, 3H),
2-Iodo-4′-methoxybiphenyl (2o). The title compound was
7.35 (s, 1H), 7.54−7.65 (m, 4H), 8.34 (s, 1H), 8.57−8.65 (m, 4H).
2-Nitrotriphenylene (3f). The reaction of 1a with 2j provided the
title compound as a light-yellow solid (62.9 mg, 0.230 mmol, 92%). 1H
NMR (300 MHz, CDCl3, rt): δ 7.70−7.81 (m, 4H), 8.42 (dd, J = 9.0,
2.4 Hz, 1H), 8.63−8.75 (m, 5H), 9.51 (d, J = 2.4 Hz, 1H).
2-Trifluoromethyltriphenylene (3g). The reaction of 1a with 2k
provided the title compound as a white solid (68.1 mg, 0.230 mmol,
92%). Mp = 110 °C. IR (KBr): 1325, 1115, 754 cm−1. 1H NMR (400
MHz, CDCl3, rt): δ 7.66 (m, 4H), 7.84 (d, J = 8.6 Hz, 1H), 8.61−8.66
obtained as a white solid (270 mg, 0.869 mmol, 35%). Mp = 48 °C.
1
IR (KBr): 3435, 2835, 1609, 1458, 1242, 1034, 827, 760 cm−1. H
NMR (400 MHz, CDCl3, rt): δ 3.87 (s, 3H), 6.95−6.97 (m, 2H), 7.01
(td, J = 7.6, 1.8 Hz, 1H), 7.27−7.31 (m, 3H), 7.37 (td, J = 7.6, 1.2 Hz,
1H), 7.95 (dd, J = 7.6, 1.2 Hz, 1H); 13C{1H} NMR (100 MHz, CDCl3,
rt): δ 55.3, 99.2, 113.3, 128.1, 128.5, 130.2, 130.4, 136.7, 139.5, 146.2,
159.1. Calcd for C13H11IO: C, 50.35; H, 3.58%. Found: C, 50.20; H,
3.34%.
K
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(m, 4H), 8.71 (d, J = 8.6 Hz, 1H), 8.87 (s, 1H); 13C{1H} NMR (100
2H), 8.61 (d, J = 9.2 Hz, 1H), 8.65−8.67 (m, 1H), 8.71−8.76 (m,
2H), 8.92 (dd, J = 8.0, 1.6 Hz, 1H), 8.96 (d, J = 8.0 Hz, 1H).
2-Methoxy-6-nitrotriphenylene (3p) and 3-Methoxy-6-nitro-
triphenylene (3p′). The reaction of 2j with 2d provided a 1:1
mixture of isomers 3p and 3p′ as a yellow solid (62.2 mg, 0.205 mmol,
3
3
MHz, CDCl3, rt): δ 120.78 (q, JC-F = 4.3 Hz), 123.3 (q, JC‑F = 3.0
1
Hz), 123.5, 123.56, 123.58, 123.9, 124.2, 124.8 (q, JC‑F = 271 Hz),
2
127.67, 127.75, 128.2, 128.4, 128.9, 129.0 (q, JC‑F = 32 Hz), 129.1,
4
129.8, 130.2, 130.6, 132.4 (q, JC‑F = 1.3 Hz); 19F{1H} NMR (376
1
82%). IR (KBr): 1614, 1516, 1340, 1229, 741 cm−1. H NMR (400
MHz, CDCl3, rt): δ −62.2. Calcd for C19H11F3: C, 77.02; H, 3.74%.
Found: C, 77.05; H, 3.52%.
MHz, CDCl3, rt): δ 4.05 (s, 3H (minor)), 4.07 (s, 3H (major)), 7.32−
7.37 (m, 1H (major), 1H (minor)), 7.63−7.77 (m, 2H (major), 2H
(minor)), 8.00−8.03 (m, 1H (major), 1H (minor)), 8.34 (dd, J = 9.0,
2.4 Hz, 1H (minor)), 8.41 (dd, J = 9.0, 2.4 Hz, 1H (major)), 8.55−
8.73 (m, 4H (major), 4H (minor)), 9.37−9.40 (m, 1H (major), 1H
(minor)); 13C{1H} NMR (100 MHz, CDCl3, rt): δ 55.5, 55.6, 105.5,
105.6, 116.2, 117.1, 118.2, 118.8, 119.6, 120.6, 122.3, 122.8, 123.4,
123.8, 124.04, 124.04, 124.1, 124.2, 124.9, 125.0, 126.6, 126.8, 127.7,
128.3, 128.8, 129.1, 129.2, 129.7, 129.9, 130.4, 131.0, 131.5, 132.9,
134.4, 145.8, 146.1, 159.1, 159.7. HRMS (FAB+) Calcd for
C19H13NO3: 303.0895. Found: 303.0920 [M+].
2-Fluorotriphenylene (3h). The reaction of 2l with 1a provided
the title compound as a white solid (49.9 mg, 0.203 mmol, 81%). Mp
= 188 °C. IR (KBr): 1616, 1501, 1435, 1192, 758 cm−1. 1H NMR (400
MHz, CDCl3, rt): δ 7.34−7.42 (m, 1H), 7.65−7.70 (m, 4H), 8.27 (dd,
J = 11, 2.6 Hz, 1H), 8.51−8.68 (m, 5H); 13C{1H} NMR (150 MHz,
2
2
CDCl3, rt): δ 108.9 (d, JC‑F = 22.4 Hz), 115.6 (d, JC‑F = 22.4 Hz),
123.2, 123.50, 123.51, 123.6, 125.6 (d, 3JC‑F = 8.7 Hz), 126.4 (d, 4JC‑F
=
4
2.0 Hz), 127.2, 127.4, 127.6, 128.0, 129.1 (d, JC‑F = 3.3 Hz), 129.4,
3
1
129.5, 130.3, 131.9 (d, JC‑F = 8.7 Hz), 162.3 (d, JC‑F = 224 Hz);
19F{1H} NMR (376 MHz, CDCl3, rt): δ −114.3. HRMS (FAB+)
Calcd for C18H11F: 246.0845. Found: 246.0843 [M+].
2,6-Dimethoxytriphenylene (3q) and 3,6-Dimethoxy-
triphenylene (3q′). The reaction of 1d with 2o provided a 1:1
mixture of isomers 3q and 3q′ as a white solid (34.6 mg, 0.120 mmol,
2-Chlorotriphenylene (3i). The reaction of 1a with 2m provided
the title compound as a white solid (32.8 mg, 0.125 mmol, 50%). Mp
= 146 °C. IR (KBr): 1597, 1493, 1429, 1101, 756 cm−1. 1H NMR (400
MHz, CDCl3, rt): δ 6.59 (dd, J = 8.8, 2.0 Hz, 1H), 7.63−7.71 (m, 4H),
8.54−8.59 (m, 4H), 8.62−8.65 (m, 2H); 13C{1H} NMR (150 MHz,
CDCl3, rt): δ 123.2, 123.4, 123.50, 123.50, 123.52, 125.1, 127.56,
127.57, 127.58, 127.64, 128.0, 128.3, 128.8, 129.2, 129.8, 130.3, 131.4,
133.5. HRMS (FAB+) Calcd for C18H11Cl: 262.0549. Found:
262.0563 [M+].
1
48%). H NMR (600 MHz, CDCl3, rt): δ 4.03 (s, 3H (3q)), 4.03 (s,
6H (3q′)), 4.04 (s, 3H (3q)), 7.23 (dd, J = 9.0, 2.4 Hz, 1H (3q)),
7.28−7.30 (m, 1H (3q), 2H (3q′)), 7.57−7.64 (m, 2H (3q), 2H
(3q′)), 7.96−7.97 (m, 1H (3q), 2H (3q′)), 8.05 (d, J = 2.4 Hz, 1H
(3q)), 8.49−8.58 (m, 4H (3q), 4H (3q′)).
2-Methoxy-5,7-dimethyltriphenylene (3r) and 3-Methoxy-
5,7-dimethyltriphenylene (3r′). The reaction of 1d with 2h
provided a 9:1 mixture of isomers 3r and 3r′ as a white solid (20.0
mg, 0.070 mmol, 28%). IR (KBr): 2920, 1609, 1449, 1219, 1043, 760
2-Methoxycarbonyltriphenylene (3j). The reaction of 1a with
2n provided the title compound as a white solid (51.5 mg, 0.180
mmol, 72%). Mp = 171 °C. IR (KBr): 2951, 1716, 1612, 1431, 1261,
1
cm−1. H NMR (400 MHz, CDCl3, rt): δ 2.56 (s, 3H (minor)), 2.57
1
1109, 746 cm−1. H NMR (400 MHz, CDCl3, rt): δ 4.04 (s, 3H),
(s, 3H (major)), 3.00 (s, 3H (minor)), 3.05 (s, 3H (major)), 3.98(s,
3H (major)), 4.03 (s, 3H (minor)), 7.17−7.26 (m, 1H (major), 1H
(minor)), 7.33 (s, 1H (major), 1H (minor)), 7.53−7.60 (m, 2H
(major), 2H (minor)), 8.06−8.07 (m, 1H (major), 1H (minor)), 8.33
(s, 1H (major), 1H (minor)), 8.48−8.58 (m, 3H (major), 3H
(minor)); 13C{1H} NMR (100 MHz, CDCl3, rt): δ 21.6, 21.7, 26.8,
29.8, 55.6, 55.6, 106.3, 112.0, 113.7, 114.2, 116.1, 121.4, 121.6, 122.6,
123.2, 123.8, 124.7, 124.8, 126.3, 127.0, 127.2, 127.4, 128.0, 129.5,
129.8, 129.9, 130.3, 130.5, 131.9, 132.37, 132.38, 132.43, 133.2, 133.3,
134.6, 135.0, 135.28, 135.29, 136.0, 136.0, 157.6, 157.9. HRMS (FAB
+) Calcd for C21H18O: 286.1358. Found: 286.1357 [M+].
7.69−7.73 (m, 4H), 8.27 (dd, J = 8.8, 1.6 Hz, 1H), 8.65−8.71 (m,
4H), 8.75−8.77 (m, 1H), 9.37 (d, J = 1.6 Hz, 1H); 13C{1H} NMR
(100 MHz, CDCl3, rt): δ 52.5, 123.5, 123.6, 123.7, 123.8, 124.2, 125.7,
127.5, 127.6, 127.7, 127.9, 128.5, 128.6, 129.2, 129.67, 129.73, 130.1,
130.9, 133.4, 167.4. HRMS (FAB+) Calcd for C20H14O2: 286.0994.
Found: 286.1019 [M+].
2-Methoxytriphenylene (3k). The reaction of 1a with 2o
provided the title compound as a white solid (32.3 mg, 0.125 mmol,
50%). The reaction of 1d with 2d provided the title compound (53.0
1
mg, 0.205 mmol, 82%). H NMR (300 MHz, CDCl3, rt): δ 4.04 (s,
2,3,6-Trimethoxytriphenylene (3s) and 2,3,7-Trimethoxy-
triphenylene (3s′). The reaction of 1d with 2q provided a 1:2
mixture of isomers 3s and 3s′ as a white solid (43.0 mg, 0.135 mmol,
54%). IR (KBr): 2957, 1614, 1512, 1267, 1202, 1043, 1016, 845, 756
3H), 7.29 (dd, J = 9.0, 2.7 Hz, 1H), 7.56−7.91 (m, 4H), 8.06 (d, J =
2.7 Hz, 1H), 8.55−8.68 (m, 5H).
2H-Phenanthro[1,10,9-cde]chromene (3l). The reaction of 1a
with 2p provided the title compound as a white solid (14.7 mg, 0.058
mmol, 23%). Mp = 122 °C. IR (KBr): 2926, 1597, 1412, 1236, 748
1
cm−1. H NMR (600 MHz, CDCl3, rt): δ 4.01 (s, 3H (minor)), 4.02
1
cm−1. H NMR (400 MHz, CDCl3, rt): δ 5.55 (s, 2H), 7.13 (dd, J =
(s, 3H (major)), 4.09 (s, 3H (minor)), 4.10 (s, 3H (major)), 4.10 (s,
3H (major)), 4.11 (s, 3H (minor)), 7.21 (dd, J = 8.7, 2.7 Hz, 1H
(minor)), 7.25 (dd, J = 9.0, 2.4 Hz, 1H (major)), 7.57−7.65 (m, 2H
(major), 2H (minor)), 7.81−7.83 (m, 1H (major), 2H (minor)), 7.92
(s, 1H (major)), 7.93 (s, 1H (minor)), 8.02 (d, J = 2.4 Hz, 1H
(major)), 8.36 (d, J = 9.0 Hz, 1H (major)), 8.42−8.46 (m, 1H
(major), 1H (minor)), 8.51−8.56 (m, 1H (major), 2H (minor));
13C{1H} NMR (150 MHz, CDCl3, rt): δ 55.57, 55.61, 56.01, 56.03,
56.05, 56.07, 104.1, 104.55, 104.57, 104.60, 105.6, 106.0, 114.2, 116.0,
122.8, 122.9, 123.0, 123.3, 123.5, 123.7, 123.8, 124.41, 124.42, 124.43,
124.7, 125.1, 126.13, 126.15, 126.4, 127.2, 128.5, 128.9, 129.3, 130.0,
130.6, 131.0, 148.7, 149.3, 149.5, 149.6, 158.3, 158.8. HRMS (FAB+)
Calcd for C21H18O3: 318.1256. Found: 318.1247 [M+].
8.4, 1.8 Hz, 1H), 7.32 (dd, J = 8.4, 1.8 Hz, 1H), 7.53−7.69 (m, 4H),
8.17 (d, J = 8.4 Hz, 1H), 8.48 (d, J = 8.4 Hz, 1H), 8.60−8.64 (m, 2H);
13C{1H} NMR (100 MHz, CDCl3, rt): δ 68.2, 113.6, 115.9, 116.9,
122.0, 122.3, 123.3, 123.6, 124.1, 127.5, 127.52, 127.54, 127.6, 128.6,
129.2, 129.5, 129.95, 130.02, 153.5. HRMS (FAB+) Calcd for
C19H12O: 256.0888. Found: 256.0877 [M+].
2,3-Dimethoxytriphenylene (3m). The reaction of 1a with 2q
provided the title compound as a white solid (44.0 mg, 0.153 mmol,
61%). The reaction of 1e with 2d provided the title compound (45.4
1
mg, 0.157 mmol, 63%). H NMR (300 MHz, CDCl3, rt): δ 4.14 (s,
6H), 7.62−7.67 (m, 4H), 8.02 (s, 2H), 8.50−8.53 (m, 2H), 8.66−8.69
(m, 2H).
1
6,6-Dimethyl-6H-dibenzo[b,d]pyran (4). A colorless liquid. H
Triphenyleno[2,3-d]-1,3-dioxole (3n). The reaction of 1f with
2d provided the title compound as a white solid (37.4 mg, 0.137
mmol, 55%). Mp = 260 °C. IR (KBr): 2910, 1502, 1229, 1041, 752
cm−1. 1H NMR (400 MHz, CDCl3, rt): δ 6.14 (s, 2H), 7.60−7.66 (m,
4H), 8.03 (s, 2H), 8.44−8.47 (m, 2H), 8.65−8.67 (m, 2H); 13C{1H}
NMR (100 MHz, CDCl3, rt): δ 101.7, 102.1, 123.2, 123.5, 125.9,
126.6, 127.3, 129.3, 129.9, 148.4. HRMS (FAB+) Calcd for C19H12O2:
272.0837. Found: 272.0854 [M+].
NMR (400 MHz, CDCl3, rt): δ 1.64 (s, 6H), 6.95 (dd, J = 8.0, 1.2 Hz,
1H), 7.03 (dt, J = 7.6, 1.2 Hz, 1H), 7.21−7.26 (m, 2H), 7.28−7.37 (m,
2H), 7.73 (d, J = 7.6 Hz, 2H).
Spectroscopic data of 4 can be found in the literature.39
o-Bromoterphenyl 5a was prepared by literature procedures.40
2-(2-Bromophenyl)biphenyl (5a). The title compound was
obtained as a colorless liquid (204 mg, 0.660 mmol, 66%). IR
1
(neat): 3055, 1462, 1423, 1026, 748, 700 cm−1. H NMR (400 MHz,
Benzo[g]chrycene (3o). The reaction of 1g with 2d provided the
1
title compound as a white solid (21.6 mg, 0.078 mmol, 31%). H
CDCl3, rt): δ 7.06−7.09 (m, 2H), 7.13−7.21 (m, 6H), 7.33−7.35 (m,
NMR (400 MHz, CDCl3, rt): δ 7.60−7.73 (m, 6H), 8.00−8.04 (m,
1H), 7.40−7.54 (m, 4H); 13C{1H} NMR (100 MHz, CDCl3, rt): δ
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Article
124.0, 126.7, 126.9, 127.0, 127.8, 128.3, 128.5, 129.6, 130.2, 130.9,
132.3, 132.6, 139.8, 141.1, 141.2, 142.5. Calcd for C18H13Br: C, 69.92;
H, 4.24%. Found: C, 69.77; H, 4.30%.
(Z)-β-Halostyrenes 9c, 9d, 9f, and 9g were prepared according to
the above-mentioned procedure.
1-Bromo-1-(4-methylphenyl)-2,2-diphenylethene (9c). The
title compound was obtained as a white solid (112 mg, 0.306 mmol,
31%). 1H NMR (400 MHz, CDCl3, rt): δ 2.29 (s, 3H), 6.96−7.00 (m,
4H), 7.07−7.10 (m, 3H), 7.21 (d, J = 8.0 Hz, 2H), 7.29−7.34 (m,
1H), 7.35−7.41 (m, 4H).
o-Iodostyrenes 7a41 and 7b42 were prepared by literature
procedures and showed the identical spectroscopic data reported in
the literature.
Preparation of (E/Z)-1-(2-Bromophenyl)-1,2-diphenylethene
((E/Z)-7c).43 Under an argon atmosphere, benzyltriphenylphospho-
nium bromide (2.69 g, 6.2 mmol) and potassium tert-butoxide (696
mg, 6.2 mmol) were placed in a 50 mL Schlenk tube. A solution of 2-
bromobenzophenone (261 mg, 1.0 mmol) in toluene (5 mL) was then
added. The reaction mixture was vigorously stirred at reflux for 70 h.
The mixture was filtrated through a pad of Celite, which was washed
with ethyl acetate. The reaction mixture was poured into water (12
mL), and the product was extracted with ethyl acetate (40 mL × 3).
The combined organic layers were dried over anhydrous sodium
sulfate. After concentration in vacuo, purification by silica gel column
chromatography (hexane/ethyl acetate = 40:1) afforded (E/Z)-7c
(183 mg, 0.546 mmol, 55%) as a 1:1 mixture of E/Z isomers.
A colorless liquid. IR (neat): 3078 (w), 3022 (m), 1599 (w), 1445
(m) cm−1. 1H NMR (600 MHz, CDCl3, rt): δ 6.69 (s, 1H), 7.01 (d, J
= 8.4 Hz 1H), 7.02 (s, 1H), 7.13−7.25 (m, 17H), 7.29−7.36 (m, 8H),
7.61 (d, J = 7.8 Hz, 1H), 7.68 (d, J = 8.4 Hz, 1H); 13C{1H} NMR (100
MHz, CDCl3, rt): δ 123.6, 124.6, 126.8, 127.2, 127.3, 127.5, 127.7,
128.0, 128.2, 128.27, 128.29, 128.5, 128.9, 129.2 (2C), 129.3, 129.4,
129.6, 130.2, 136.96, 137.00, 139.5, 141.1, 141.2, 141.4, 141.9, 144.9,
131.77, 131.78, 132.2, 133.4, 133.5. Calcd for C20H15Br: C, 71.65; H,
4.51%. Found: C, 72.00; H, 4.36%.
1-Bromo-1-(4-methoxyphenyl)-2,2-diphenylethene (9d).
The title compound was obtained as a white solid (144 mg, 0.413
mmol, 41%). 1H NMR (400 MHz, CDCl3, rt): δ 3.77 (s, 3H), 6.70 (d,
J = 7.6 Hz, 2H), 6.95−6.98 (m, 2H), 7.07−7.09 (m, 3H), 7.25 (d, J =
7.6 Hz, 2H), 7.30−7.33 (m, 1H), 7.35−7.40 (m, 4H).
1-Bromo-1-(4-cyanophenyl)-2,2-diphenylethene (9f). The
title compound was obtained as a pale yellow solid (90.3 mg, 0.251
mmol, 50%). Mp 162−163 °C. IR (KBr): 3061 (w), 2226 (w), 1682
1
(w), 1599 (m) cm−1. H NMR (600 MHz, CDCl3, rt):δ 6.93 (d, J =
8.4 Hz, 2H), 7.09−7.16 (m, 3H), 7.33−7.37 (m, 3H), 7.39−7.41 (m,
4H), 7.47 (d, J = 8.4 Hz, 2H); 13C{1H} NMR (100 MHz, CDCl3, rt):
δ 111.4, 118.6, 119.2, 127.8, 128.2, 128.3, 128.4, 129.5, 130.4, 131.2,
131.9, 140.4, 143.0, 145.9, 146.1. Calcd for C21H14BrN: C, 70.01; H,
3.92; N, 3.89%. Found: C, 69.81; H, 3.71; N, 3.76%.
1-Bromo-2,2-di(4-fluorophenyl)-1-(4-methoxyphenyl)-
ethene (9g). The title compound was obtained as a pale yellow solid
(79.9 mg, 0.199 mmol, 40%). Mp 80−82 °C. IR (KBr): 3044 (w),
1
2963 (w), 1655 (w), 1510 (m), 1225 (s), 1028 (s) cm−1. H NMR
(600 MHz, CDCl3, rt): δ 3.78 (s, 3H), 6.72 (d, J = 9.0 Hz, 2H), 6.78
(t, J = 9.0 Hz, 2H), 6.90 (dd, J = 8.4, 5.4 Hz, 2H), 7.06 (t, J = 9.0 Hz,
2H), 7.22 (d, J = 9.0 Hz, 2H), 7.32 (dd, J = 8.4, 5.4 Hz, 2H); 13C{1H}
NMR (150 MHz, CDCl3, rt): δ 55.4, 113.6, 115.1 (d, 2JC‑F = 21.2 Hz),
Preparation of 1-Iodo-1,2,2-triphenylethene (9a).44 Under an
argon atmosphere, magnesium turnings (134 mg, 5.5 mmol) were
placed in a 100 mL reaction flask. A solution of 1-bromo-1,2,2-
triphenylethene (1.68 g, 5.0 mmol) in THF (34 mL) was added. The
mixture was stirred at reflux for 2 h. After the reaction mixture was
cooled to room temperature, iodine (1.52 g, 6.0 mmol) was added.
After being stirred for 30 min at room temperature, the product was
extracted with diethyl ether (40 mL × 3). The combined organic layers
were washed with brine (10 mL) and dried over anhydrous sodium
sulfate. Evaporation, followed by silica gel column chromatography
(hexane/ethyl acetate = 40:1), afforded 9a (1.81 g, 4.74 mmol, 95%).
Pale yellow solid. Mp 118−120 °C. IR (KBr): 3073 (w), 1595 (w),
2
3
115.4 (d, JC‑F = 21.3 Hz), 123.0, 131.6 (d, JC‑F = 8.0 Hz), 131.8,
3
4
132.2 (d, JC‑F = 8.0 Hz), 133.2, 137.3 (d, JC‑F = 3.5 Hz), 139.8 (d,
4JC‑F = 3.5 Hz), 140.7, 159.4, 161.7 (d, 1JC‑F = 246 Hz), 162.2 (d, 1JC‑F
= 246 Hz); 19F{1H} NMR (376 MHz, CDCl3, rt): δ −114.5, −114.0.
Calcd for C21H15BrF2O: C, 62.86; H, 3.77%. Found: C, 63.02; H,
3.66%.
Preparation of (Z)-1-Bromo-1,2-diphenyl-1-hexene (9k).55
Under an argon atmosphere, diphenylacetylene (891 mg, 5.0 mmol)
was placed in a 50 mL Schlenk tube. THF (6 mL) was then added. n-
Butyllithium (1.6 M hexane solution, 3.4 mL, 5.5 mmol) was added
dropwise at −10 °C. The reaction mixture was stirred for 2 h. 1,2-
Dibromoethane (0.57 mL, 6.6 mmol) was added at −78 °C, and the
reaction mixture was stirred for an additional 30 min. After being
cooled to 0 °C, the reaction mixture was poured into saturated
ammonium chloride solution (20 mL) and extracted with diethyl ether
(40 mL × 3). The combined organic layers were washed with brine
(10 mL) and dried over anhydrous sodium sulfate. After the volatiles
were evaporated in vacuo, the product was chromatographed on silica
gel (hexane) to afford 9k (537 mg, 1.70 mmol, 34%).
1
1441 (m) cm−1. H NMR (400 MHz, CDCl3, rt): δ 6.94−6.97 (m,
2H), 7.01−7.05 (m, 3H), 7.09−7.18 (m, 3H), 7.27−7.42 (m, 7H);
13C{1H} NMR (100 MHz, CDCl3, rt): δ 101.7, 127.3, 128.0, 128.1,
128.2, 128.4, 128.8, 129.7, 130.6, 130.7, 140.7, 145.0, 147.6, 150.4.
Calcd for C20H15I: C, 62.84; H, 3.94%. Found: C, 62.89; H, 3.82%.
(Z)-β-Halostyrenes 9b,42 9h,42,45 9i,46 and 9j47 were prepared by
literature procedures. Spectroscopic data of 9b,48 9c,49 9d,50 9h,51 9i,52
and 9j53 can be found in the literature.
White solid. Mp 50−51 °C. IR (KBr): 3076 (w), 2957 (m), 1597
1
(w), 1443 (m) cm−1. H NMR (400 MHz, CDCl3, rt): δ 0.73 (t, J =
Preparation of 1-Bromo-1-(4-fluorophenyl)-2,2-diphenyl-
ethene (9e).54 Under an argon atmosphere, 1,1-dibromo-2,2-
diphenylethene (338 mg, 1.0 mmol), 4-fluorophenylboronic acid
(147 mg 1.05 mmol), tri(2-furyl)phosphine (34.8 mg, 0.15 mmol),
and bis(dibenzylideneacetone)palladium (28.8 mg, 0.05 mmol) were
placed in a 50 mL of Schlenk tube. THF (4.9 mL), diethyl ether (2.1
mL), and a solution of cesium carbonate (652 mg, 2.0 mmol) in water
(2 mL) were then added. The reaction mixture was stirred at reflux for
18 h. The product was extracted with ethyl acetate (30 mL × 3). The
combined organic layers were washed with brine (10 mL) and dried
over anhydrous sodium sulfate. Evaporation, followed by silica gel
column chromatography (hexane/ethyl acetate = 80:1), afforded 9e
(157 mg, 0.444 mmol, 44%).
7.2 Hz, 3H), 1.11−1.28 (m, 4H), 2.33 (t, J = 7.2 Hz, 2H), 7.30−7.36
(m, 4H), 7.38−7.44 (m, 6H); 13C{1H} NMR (100 MHz, CDCl3, rt):
δ 13.9, 22.4, 30.4, 36.0, 118.9, 127.3, 128.2, 128.3, 128.4, 128.5, 129.1,
141.0, 142.7, 143.7. Calcd for C18H19Br: C, 68.58; H, 6.07%. Found:
C, 68.60; H, 5.98%.
Preparation of (Z)-1-Iodo-1,2-diphenyl-1-hexene (9l).56
Under an argon atmosphere, lithium granules (694 mg, 100 mmol)
were placed in a 50 mL Schlenk tube. THF (24 mL) and
trimethylstannyl chloride (1.99 g, 10 mmol) were added. The reaction
mixture was vigorously stirred at 0 °C for 12 h. The resulting dark
green solution was transferred via a syringe to a 20 mL Schlenk tube,
and the volatiles were removed in vacuo. Hexane (18.2 mL) and
diphenylacetylene (1.60 g, 9 mmol) were added at 0 °C. After the
reaction mixture was stirred at 0 °C for 3 h, 1-iodobutane (1.14 mL, 10
mmol) was added at 0 °C. The reaction mixture was allowed to warm
to room temperature and stirred for an additional 3 h. The volatiles
were removed in vacuo. To the reaction mixture were added
dichloromethane (40 mL) and iodine (4.57 g, 18 mmol). After
being stirred at room temperature for 2 h, the reaction mixture was
poured into saturated sodium thiosulfate aqueous solution (20 mL).
Orange solid. Mp 113−114 °C. IR (KBr): 3059 (w), 1647 (w),
1491 (m) cm−1. 1H NMR (600 MHz, CDCl3, rt):δ 6.88 (t, J = 9.0 Hz,
2H), 6.96−6.99 (m, 2H), 7.08−7.13 (m, 3H), 7.30−7.41 (m, 7H);
2
13C{1H} NMR (150 MHz, CDCl3, rt): δ 115.2 (d, JC‑F = 21.9 Hz),
3
121.0, 127.3, 127.8, 128.1, 128.4, 129.6, 130.4, 132.3 (d, JC‑F = 8.1
4
1
Hz), 137.3 (d, JC‑F = 3.5 Hz), 141.0, 143.7, 144.1, 162.1 (d, JC‑F
=
248 Hz); 19F{1H} NMR (376 MHz, CDCl3, rt): δ −113.0. Calcd for
C20H14BrF: C, 68.01; H, 3.99%. Found: C, 67.80; H, 3.91%.
M
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The product was extracted with dichloromethane (40 mL × 3). The
combined organic layers were washed with brine (20 mL) and dried
over sodium sulfate. After concentration in vacuo, purification by silica
gel column chromatography (hexane) afforded 9l (1.66 g, 4.59 mmol,
51%).
Hz); 19F{1H} NMR (376 MHz, CDCl3, rt): δ −62.8. Calcd for
C21H14BrF3: C, 62.55; H, 3.50%. Found: C, 62.50; H, 3.34%.
Typical Procedure for Palladium-Catalyzed Annulation of
(Z)-β-Bromostyrenes 9 with o-Bromobenzyl Alcohols 1: Syn-
thesis of 9,10-Diphenylphenanthrene (8c) (Table 7, entry 4).
Under an argon atmosphere, cesium carbonate (196 mg, 0.60 mmol),
bis(benzonitrile)dichloropalladium (4.8 mg, 0.0125 mmol), and tris(4-
trifluoromethylphenyl)phosphine (11.7 mg, 0.025 mmol) were placed
in a 20 mL Schlenk tube. Toluene (1.0 mL), 1-bromo-1,2,2-
triphenylethene (9b, 83.8 mg, 0.25 mmol), and 2-(o-bromophenyl)-
2-propanol (1a, 75.3 mg, 0.35 mmol) were added. The resulting
mixture was stirred at 110 °C for 24 h. The mixture was then cooled to
room temperature. Hydrochloric acid (1 M, 3 mL) was added, and the
product was extracted with dichloromethane (10 mL × 3). The
organic layers were dried over anhydrous sodium sulfate. After the
volatile was evaporated, silica gel column purification with hexane as
an eluent and the sequential bulb-to-bulb distillation afforded 9,10-
diphenylphenanthrene 8c (71.9 mg, 0.22 mmol, 88% yield).
White solid. Mp 67−68 °C. IR (KBr): 3051 (w), 2959 (m), 1597
1
(w), 1441 (m) cm−1. H NMR (400 MHz, CDCl3, rt): δ 0.71 (t, J =
7.2 Hz, 3H), 1.11−1.26 (m, 4H), 2.33 (t, J = 7.2 Hz, 2H), 7.24−7.30
(m, 2H), 7.33−7.44 (m, 8H); 13C{1H} NMR (100 MHz, CDCl3, rt):
δ 13.9, 22.3, 30.6, 35.5, 97.6, 127.4, 127.8, 128.3, 128.36, 128.39, 128.7,
144.4, 146.2, 150.4. Calcd for C18H19I: C, 59.68; H, 5.29%. Found: C,
59.35; H, 5.16%.
Preparation of (E)-1-Bromo-2-(4-methoxyphenyl)-1,2-
diphenylethene (9m).43 Under an argon atmosphere, lithium
granules (174 mg, 25 mmol) were placed in a 50 mL Schlenk tube.
THF (7.5 mL) and trimethylstannyl chloride (498 mg, 2.5 mmol)
were added, and the reaction mixture was vigorously stirred at 0 °C for
12 h. The resulting dark green solution was transferred via a syringe to
a 50 mL Schlenk tube, and the volatiles were removed in vacuo.
Hexane (4 mL) and diphenylacetylene (401 mg, 2.25 mmol) were
added at 0 °C. After the reaction mixture was vigorously stirred at 0 °C
for 3 h, zinc chloride (0.50 M THF solution, 5 mL, 2.5 mmol) was
added, and the reaction mixture was allowed to warm to room
temperature. After stirring for 30 min, 4-iodoanisole (553 mg, 2.36
mmol), tris(dibenzylideneacetone)dipalladium(0)-chloroform (116
mg, 0.1125 mmol), and SPhos (185 mg, 0.45 mmol) were added at
0 °C. The reaction mixture was then allowed to warm gradually to
room temperature with continuous stirring over 12 h. The reaction
mixture was poured into water (20 mL) and extracted with
dichloromethane (40 mL × 3). The combined organic layers were
washed with brine (10 mL) and dried over sodium sulfate. The
volatiles were removed in vacuo. Under an argon atmosphere, the
crude product was placed in a 50 mL Schlenk tube. Dichloromethane
(25 mL) and N-bromosuccinimide (712 mg, 4.0 mmol) were then
added. After being stirred at room temperature for 2 h, the reaction
mixture was poured into saturated sodium thiosulfate solution (20
mL). The product was extracted with dichloromethane (40 mL × 3).
The combined organic layers were washed with brine (20 mL) and
dried over sodium sulfate. After concentration in vacuo, purification by
silica gel column chromatography (hexane/ethyl acetate = 10:1)
afforded 9m (248 mg, 0.679 mmol, 30%).
1
White solid. H NMR (300 MHz, CDCl3, rt): δ 7.14−7.28 (m,
10H), 7.47−7.52 (m, 2H), 7.55−7.58 (m, 2H), 7.64−7.70 (m, 2H),
8.82 (d, J = 8.4 Hz, 2H).
Spectroscopic data of 8a,57 8b,58 8c,59 8d,60 8e,10l 8i,58 8e′,10j 8k,10q
8l,8b 8n,10r 8o′,10j and 1159 can be found in the literature.
9-Phenyl-10-(4-methylphenyl)phenanthrene (8d). The reac-
tion of 1a with 9c provided the title compound as a white solid (105.2
1
mg, 0.305 mmol, 100%). H NMR (400 MHz, CDCl3, rt): δ 2.31 (s,
3H), 7.04 (s, 4H), 7.17−7.28 (m, 5H), 7.48 (t, J = 8.0 Hz, 2H), 7.53−
7.59 (m, 4H), 7.66 (t, J = 8.0 Hz, 2H), 8.81 (d, J = 8.0 Hz, 2H).
9-(4-Methoxyphenyl)-10-phenylphenanthrene (8e). The re-
action of 1a with 9d provided the title compound as a white solid
(69.9 mg, 0.194 mmol, 97%). 1H NMR (400 MHz, CDCl3, rt): δ 3.79
(s, 3H), 6.79 (d, J = 8.4 Hz, 2H), 7.07 (d, J = 8.4 Hz, 2H), 7.15−7.28
(m, 5H), 7.46−7.69 (m, 6H), 8.81 (d, J = 8.4 Hz, 2H).
9-(4-Fluorophenyl)-10-phenylphenanthrene (8f). The reac-
tion of 1a with 9e provided the title compound as a white solid (66.4
mg, 0.191 mmol, 95%). Mp 254−256 °C. IR (KBr): 3065 (w), 1506
(m) cm−1. 1H NMR (400 MHz, CDCl3, rt): δ 6.95 (t, J = 8.8 Hz, 2H),
7.10−7.16 (m, 4H), 7.20−7.29 (m, 3H), 7.48−7.57 (m, 4H), 7.66−
7.71 (m, 2H), 8.82 (d, J = 8.8 Hz, 2H); 13C{1H} NMR (150 MHz,
2
CDCl3, rt): δ 114.8 (d, JC‑F = 21.0 Hz), 122.6, 122.7, 126.6, 126.7,
126.7, 126.8, 126.9, 127.7, 127.9, 128.0, 130.2 (2C), 131.1, 131.9,
132.0, 132.7 (3JC‑1F, J = 7.8 Hz), 135.6 (d, 4JC‑F = 3.5 Hz), 136.2, 137.8,
139.6, 161.6 (d, JC‑F = 244 Hz); 19F{1H} NMR (376 MHz, CDCl3,
rt): δ −116.1. HRMS (FAB+): Calcd for C26H17F: 348.1314. Found:
348.1328 [M]+.
White solid. Mp 94−95 °C. IR (KBr): 3055 (w), 2951 (w), 1508
(m), 1254 (s), 1032 (s) cm−1. 1H NMR (400 MHz, CDCl3, rt): δ 3.71
(s, 3H), 6.60 (d, J = 7.6 Hz, 2H), 6.87 (d, J = 7.6 Hz, 2H), 7.15−7.23
(m, 3H), 7.31−7.42 (m, 7H); 13C{1H} NMR (100 MHz, CDCl3, rt):
δ 55.2, 113.4, 121.2, 127.6, 127.9, 128.2, 128.3, 129.7, 130.5, 131.8,
133.5, 141.5, 143.2, 144.2, 158.6. Calcd for C21H17BrO: C, 69.05; H,
4.69%. Found: C, 68.94; H, 4.34%.
9-(4-Cyanophenyl)-10-phenylphenanthrene (8g). The reac-
tion of 1a with 9f provided the title compound as a white solid (48.1
mg, 0.135 mmol, 68%). Mp 222−223 °C. IR (KBr): 3065 (w), 2228
1
(m), 1607 (m) cm−1. H NMR (400 MHz, CDCl3, rt): δ 7.07−7.10
(Z)-β-Halostyrenes 9n and 9o were prepared according to the
above procedure.
(m, 2H), 7.19−7.26 (m, 5H), 7.39 (d, J = 8.4 Hz, 1H), 7.47−7.55 (m,
5H), 7.68 (t, J = 8.0 Hz, 2H), 8.79 (d, J = 8.4 Hz, 1H), 8.81 (d, J = 8.4
Hz, 1H); 13C{1H} NMR (150 MHz, CDCl3, rt): δ 110.6, 119.1, 122.7,
122.9, 126.9, 127.0, 127.08, 127.12, 127.15, 127.2, 128.0, 128.1 (2C),
130.2, 130.3, 130.9, 131.6 (2C), 132.0, 135.4, 137.6, 138.8, 145.1.
Calcd for C27H17N: C, 91.24; H, 4.82 N, 3.94%. Found: C, 90.85; H,
4.83 N, 3.88%.
(E)-1-Bromo-2-(4-fluorophenyl)-1,2-diphenylethene (9n).
The title compound was obtained as a pale yellow solid (404 mg,
1.14 mmol, 51%). Mp 88−89 °C. IR (KBr): 3055 (w), 1603 (w), 1504
(m) cm−1. 1H NMR (400 MHz, CDCl3, rt): δ 6.76 (t, J = 7.6 Hz, 2H),
6.92 (dd, J = 7.6, 5.2 Hz, 2H), 7.18−7.22 (m, 3H), 7.30−7.42 (m,
2
7H); 13C{1H} NMR (100 MHz, CDCl3, rt): δ 115.0 (d, JC‑F = 21.4
3-Fluoro-9-(4-fluorophenyl)-10-(4-methoxyphenyl)phenan-
threne (8h). The reaction of 1a with 9g provided the title compound
as a white solid (56.0 mg, 0.141 mmol, 71%). Mp 231−232 °C. IR
Hz), 122.4 (d, 5JC‑F = 1.1 Hz), 127.9, 128.2, 128.3, 128.4, 129.6, 130.4,
132.2 (d, 3JC‑F = 8.0 Hz), 137.1 (d, 4JC‑F = 3.5 Hz), 141.1, 142.6, 143.7,
1
161.7 (d, JC‑F = 246 Hz); 19F{1H} NMR (376 MHz, CDCl3, rt): δ
1
(KBr): 3038 (w), 2938 (w), 1497 (m), 1219 (s), 1034 (s) cm−1. H
−114. 6. Calcd for C20H14BrF: C, 68.01; H, 3.99%. Found: C, 68.02;
NMR (400 MHz, CDCl3, rt): δ 3.81 (s, 3H), 6.81 (d, J = 8.8 Hz, 2H),
6.96 (t, J = 8.8 Hz, 2H), 7.03 (d, J = 8.8 Hz, 2H), 7.10 (dd, J = 8.8, 5.2
Hz, 2H), 7.21−7.26 (m, 1H), 7.50−7.55 (m, 2H), 7.61 (d, J = 8.4,
1H), 7.67 (t, J = 8.4 Hz, 1H), 8.40 (dd, J = 11.2, 2.4 Hz, 1H), 8.65 (d,
J = 8.4 Hz, 1H); 13C{1H} NMR (100 MHz, CDCl3, rt): δ 55.3, 107.8
H, 3.85%.
(E)-1-Bromo-2-(4-trifluoromethylphenyl)-1,2-diphenyl-
ethene (9o). The title compound was obtained as a pale yellow solid
(595 mg, 1.48 mmol, 33%). Mp 119−121 °C. IR (KBr): 3055 (w),
1616 (w), 1337 (m) cm−1. 1H NMR (400 MHz, CDCl3, rt): δ 7.13 (d,
J = 8.0 Hz, 2H), 7.25−7.28 (m, 2H), 7.35−7.48 (m, 10H); 13C{1H}
(d, 2JC‑F = 22.2 Hz), 113.4, 114.9 (d, 2JC‑F = 21.1 Hz), 115.6 (d, 2JC‑F
=
5
23.2 Hz), 122.8, 126.7, 127.4, 128.1, 128.8 (d, JC‑F = 1.3 Hz), 129.6
1
4
3
3
NMR (100 MHz, CDCl3, rt): δ 124.10 (q, JC‑F = 271 Hz), 124.12,
(d, JC‑F = 4.1 Hz), 130.0 (d, JC‑F = 8.8 Hz), 131.5, 131.8 (d, JC‑F
=
3
2
3
4
125.0 (q, JC‑F = 3.8 Hz), 128.1, 128.4, 128.5, 128.6, 129.0 (q, JC‑F
=
8.4 Hz), 132.1, 132.6 (d, JC‑F = 7.8 Hz), 132.7, 135.5 (d, JC‑F = 3.5
32.4 Hz), 129.6, 130.3, 130.7, 140.6, 142.3, 143.2, 144.8 (q, 4JC‑F = 1.3
Hz), 136.1 (d, JC‑F = 1.2 Hz), 136.7 (d, JC‑F = 1.8 Hz), 158.3, 161.6
5
5
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DOI: 10.1021/acs.joc.5b01693
J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Article
1
1
(d, JC‑F = 245 Hz), 161.7 (d, JC‑F = 244 Hz); 19F{1H} NMR (376
MHz, CDCl3, rt): δ −115.9, −114.3. Calcd for C27H18F2O: C, 81.80;
H, 4.58%. Found: C, 81.68; H, 4.28%.
4.16 (s, 3H), 6.92 (s, 1H), 7.15−7.26 (m, 10H), 7.43 (t, J = 8.4 Hz,
1H), 7.55 (d, J = 8.4 Hz, 1H), 7.63 (t, J = 8.4 Hz, 1H), 8.14 (s, 1H),
8.65 (d, J = 8.4 Hz, 1H).
9-Methyl-10-phenylphenanthrene (8i). The reaction of 1a with
9i provided the title compound as a white solid (46.0 mg, 0.171 mmol,
69%). 1H NMR (400 MHz, CDCl3, rt): δ 2.47 (s, 3H), 7.31−7.61 (m,
8H), 7.66−7.72 (m, 2H), 8.15−8.18 (m, 1H), 8.74 (d, J = 7.6 Hz,
1H), 8.78−8.80 (m, 1H).
5,6-Diphenylphenanthro[2,3-d][1,3]dioxole (8m). The reac-
tion of 1f with 9b provided the title compound as a orange solid (69.3
mg, 0.185 mmol, 74%). Mp 234−235 °C. IR (KBr): 3022 (w), 2924
1
(w), 1458 (m), 1244 (m), 1038 (m) cm−1. H NMR (400 MHz,
CDCl3, rt): δ 6.07 (s, 2H), 6.91 (s, 1H), 7.12−7.26 (m, 10H), 7.43 (t,
J = 8.4 Hz, 1H), 7.53 (d, J = 8.4 Hz, 1H), 7.62 (t, J = 8.4 Hz, 1H), 8.16
(s, 1H) 8.59 (d, J = 8.4 Hz, 1H); 13C{1H} NMR (150 MHz, CDCl3,
rt): δ 100.8, 101.5, 105.6, 122.4, 125.9, 126.3, 126.45, 126.51, 126.7,
127.7, 127.8, 128.0, 128.5, 129.8, 131.1, 131.27, 131.29, 135.9, 137.1,
139.8, 140.0, 147.7, 148.0. HRMS (FAB+): Calcd for C27H18O2:
374.1307. Found: 374.1318 [M]+.
9-Butyl-10-phenylphenanthrene (8j). The reaction of 1a with
9l provided the title compound as a white solid (46.0 mg, 0.148 mmol,
59%). Mp 113−114 °C. IR (KBr): 3069 (w), 2955 (m), 1491 (m)
1
cm−1. H NMR (300 MHz, CDCl3, rt): δ 0.81 (t, J = 7.2 Hz, 3H),
1.24−1.36 (m, 2H), 1.56−1.65 (m, 2H), 2.82−2.87 (m, 2H), 7.30−
7.33 (m, 3H), 7.38−7.60 (m, 5H), 7.64−7.70 (m, 2H), 8.14−8.18 (m,
1H), 8.73 (d, J = 8.4 Hz, 1H), 8.78−8.81 (m, 1H); 13C{1H} NMR
(100 MHz, CDCl3, rt): δ 13.9, 23.3, 30.4, 33.2, 122.4, 123.2, 125.4,
125.8, 126.2, 126.4, 126.9, 127.2, 127.7, 128.5, 129.4, 130.4, 130.5,
131.1, 132.6, 135.0, 136.9, 140.6. HRMS (FAB+): Calcd for C24H22:
310.1722. Found: 310.1745 [M]+.
3-Methoxy-9,10-diphenylphenanthrene (8n) and 2-Me-
thoxy-9,10-diphenylphenanthrene (8e′). The reaction of 1d
with 9b provided a 1:5 mixture of isomers 8n and 8e′ as a white
solid (76.6 mg, 0.213 mmol, 85%). The reaction of 1d with 7c
provided a 1:3 mixture of isomers 8n and 8e′ as a white solid (65.9
mg, 0.183 mmol, 73%).
9-(4-Methoxyphenyl)-10-phenylphenanthrene (8e) and 3-
Methoxy-9,10-diphenylphenanthrene (8e′). The reaction of 1a
with 9m provided a 3:1 mixture of isomers 8e and 8e′ as a white solid
(84.9 mg, 0.236 mmol, 94%).
1
3-Methoxy-9,10-diphenylphenanthrene (8n). H NMR (600
MHz, CDCl3, rt): δ 3.72 (s, 3H), 6.95 (d, J = 3.0 Hz, 1H), 7.13−7.26
(m, 10H), 7.31 (dd, J = 9.0 Hz, 2.4 Hz, 1H), 7.42 (t, J = 7.2 Hz, 1H),
7.53 (d, J = 8.4 Hz, 1H), 7.62−7.66 (m, 1H), 8.70−8.74 (m, 2H).
9-(4-Methoxyphenyl)-10-phenylphenanthrene (8e). 1H NMR
(400 MHz, CDCl3, rt): δ 3.79 (s, 3H), 6.79 (d, J = 8.4 Hz, 2H), 7.07
(d, J = 8.4 Hz, 2H), 7.15−7.29 (m, 5H), 7.46−7.69 (m, 6H), 8.81 (d, J
= 8.0 Hz, 2H).
1
2-Methoxy-9,10-diphenylphenanthrene (8e′). H NMR (600
MHz, CDCl3, rt): δ 4.05 (s, 3H), 7.13−7.26 (m, 11H), 7.47−7.50 (m,
2H), 7.56 (d, J = 8.4 Hz, 1H), 7.62−7.66 (m, 1H), 8.18 (d, J = 2.4 Hz,
1H), 8.70−8.74 (m, 1H).
1
3-Methoxy-9,10-diphenylphenanthrene (8e′). H NMR (400
MHz, CDCl3, rt): δ 4.05 (s, 3H), 7.12−7.29 (m, 11H), 7.46−7.69 (m,
4H), 8.18 (d, J = 2.4 Hz, 1H), 8.73 (d, J = 8.4 Hz, 1H).
11,12-Diphenylchrysene (8o′). The reaction of 1g with 9b
provided the title compound as a white solid (57.4 mg, 0.151 mmol,
60%). 1H NMR (300 MHz, CDCl3, rt): δ 7.00−7.29 (m, 10H), 7.38−
7.60 (m, 5H), 7.68−7.73 (m, 1H), 7.91 (dd, J = 8.1, 1.2 Hz, 1H), 8.04
(d, J = 9.0 Hz, 1H), 8.87 (t, J = 9.3 Hz, 2H).
9-(4-Fluorophenyl)-10-phenylphenanthrene (8f) and 3-Fluo-
ro-9,10-diphenylphenanthrene (8f′). The reaction of 1a with 9n
provided a 2:1 mixture of isomers 8f and 8f′ as a white solid (82.5 mg,
0.237 mmol, 95%). IR (KBr): 3055 (w), 1506 (m) cm−1. Calcd for
C26H17F: C, 89.63; H, 4.92%. Found: C, 89.41; H, 4.72%.
2-Methyldibenzo[g,p]chrysene (11). The title compound was
1
obtained as a white solid (16.3 mg, 0.0476 mmol, 50%). H NMR
1
9-Fluorophenyl-10-phenylphenanthrene (8f). H NMR (400
(400 MHz, CDCl3, rt): δ 2.66 (s, 3H), 7.47 (d, J = 8.4 Hz, 1H), 7.60−
7.70 (m, 6H), 8.50 (s, 1H), 8.59 (d, J = 8.4 Hz, 1H), 8.68−8.72 (m,
6H).
MHz, CDCl3, rt): δ 6.96 (t, J = 8.8 Hz, 2H), 7.11−7.18 (m, 4H),
7.20−7.31 (m, 3H), 7.49−7.60 (m, 4H), 7.67−7.72 (m, 2H), 8.83 (d, J
= 8.0 Hz, 2H).
3-Fluoro-9,10-diphenylphenanthrene (8f′). 1H NMR (400
MHz, CDCl3, rt): δ 7.11−7.18 (m, 4H), 7.20−7.31 (m, 7H), 7.49−
7.60 (m, 3H), 7.67−7.72 (m, 1H), 8.43 (dd, J = 11.2, 2.8 Hz, 1H),
8.68 (d, J = 8.4 Hz, 1H); 13C{1H} NMR (100 MHz, CDCl3, rt): δ
ASSOCIATED CONTENT
■
S
* Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.joc.5b01693.
2
2
107.7 (d, JC‑F = 22.1 Hz), 115.6 (d, JC‑F = 23.1 Hz), 122.8, 126.6,
5
126.7, 126.8, 127.4, 127.78, 127.81, 128.1, 128.8 (d, JC‑F = 1.5 Hz),
129.5 (d, 4JC‑F = 4.1 Hz), 130.4 (d, 3JC‑F = 8.8 Hz), 131.1, 131.2, 131.8
More detailed results of palladium-catalyzed reactions
and 1H, 13C{1H}, and 19F{1H} NMR spectra for products
(PDF)
3
4
5
(d, JC‑F = 8.4 Hz), 132.4, 136.6 (d, JC‑F = 2.4 Hz), 137.0 (d, JC‑F
=
1.3 Hz), 139.4, 139.5, 161.7 (d, JC‑F = 241 Hz); 19F{1H} NMR (376
1
MHz, CDCl3, rt): δ −114.3.
9-Phenyl-10-[4-(trifluoromethyl)phenyl]phenanthrene (8k).
The reaction of 1a with 9o provided the title compound as a white
solid (138.5 mg, 0.348 mmol, 70%). 1H NMR (400 MHz, CDCl3, rt):
δ 7.14 (d, J = 8.4 Hz, 2H), 7.20−7.30 (m, 5H), 7.44−7.58 (m, 6H),
7.70 (t, J = 8.4 Hz, 2H), 8.826 (d, J = 8.4 Hz, 1H), 8.834 (d, J = 8.4
Hz, 1H).
AUTHOR INFORMATION
■
Corresponding Author
*E-mail: ynishiha@okayama-u.ac.jp.
Notes
3-Trifluoromethyl-9,10-diphenylphenanthrene (8k′). The
reaction of 1a with 9o provided the title compound as a white solid
(26.3 mg, 0.0660 mmol, 13%). Mp.164−165 °C. IR (KBr): 3075 (w),
The authors declare no competing financial interest.
1
1489 (m) cm−1. H NMR (400 MHz, CDCl3, rt): δ 7.13−7.16 (m,
ACKNOWLEDGMENTS
■
4H), 7.20−7.28 (m, 6H), 7.35−7.61 (m, 2H), 7.67 (s, 2H), 7.73 (t, J =
8.0 Hz, 1H), 8.82 (d, J = 8.0 Hz, 1H), 9.07 (s, 1H); 13C{1H} NMR
(100 MHz, CDCl3, rt): δ 120.1 (q, 3JC‑F = 4.3 Hz), 122.6 (q, 3JC‑F = 3.3
This work was partly supported by a Grant-in-Aid for Scientific
Research (KAKENHI) (No. 26810060) from JSPS. The
Foundation for Interaction in Science & Technology, Japan,
is acknowledged for financial support. The authors gratefully
thank Ms. Megumi Kosaka and Mr. Motonari Kobayashi
(Department of Instrumental Analysis, Advanced Science
Research Center, Okayama University) for performing
elemental analyses, and the SC-NMR Laboratory (Okayama
University) for the NMR spectral measurements.
1
Hz), 122.7, 124.8 (q, JC‑2F = 271 Hz), 126.9, 127.0, 127.2, 127.6,
127.85, 127.94, 128.2 (q, JC‑F = 32 Hz), 128.3, 128.8, 129.7, 129.9,
130.9, 131.1, 132.3, 134.0, 136.8, 139.0, 139.1, 139.6; 19F{1H} NMR
(376 MHz, CDCl3, rt): δ −62.0. HRMS (FAB+): Calcd for C27H17F3:
398.1282. Found: 398.1311 [M]+.
2,3-Dimethoxy-9,10-diphenylphenanthrene (8l). The reaction
of 1e with 9b provided the title compound as a white solid (86.4 mg,
1
0.221 mmol, 89%). H NMR (400 MHz, CDCl3, rt): δ 3.72 (s, 3H),
O
DOI: 10.1021/acs.joc.5b01693
J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Article
(i) Catellani, M.; Motti, E.; Baratta, S. Org. Lett. 2001, 3, 3611.
(j) Wang, C.; Rakshit, S.; Glorius, F. J. Am. Chem. Soc. 2010, 132,
14006. (k) Fukutani, T.; Hirano, K.; Satoh, T.; Miura, M. J. Org. Chem.
2011, 76, 2867. (l) Matsumoto, A.; Ilies, L.; Nakamura, E. J. Am. Chem.
Soc. 2011, 133, 6557. (m) Nagata, T.; Hirano, K.; Satoh, T.; Miura, M.
J. Org. Chem. 2014, 79, 8960. For reaction of biphenylenes with
alkynes, see: (n) Schaub, T.; Backes, M.; Radius, U. Organometallics
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