Synthesis of triphenylene derivatives by Pd-catalyzed Suzuki coupling/intramolecular C–H activation between arylboronic acids and dibromobiphenyls

Article abstract of DOI:10.1016/j.tetlet.2018.11.052

An efficient and regioselective synthesis of functionalized triphenylenes via palladium-catalyzed Suzuki-Miyaura coupling and subsequent intramolecular C–H activation between arylboronic acids and dibromobiphenyls was developed. This methodology showed excellent atomic economy and regiospecificity as well as synthetic feasibility of unsymmetrical triphenylenes.

Full text of DOI:10.1016/j.tetlet.2018.11.052

Accepted Manuscript
Synthesis of triphenylene derivatives by Pd-catalyzed Suzuki coupling/intra-
molecular C-H activation between arylboronic acids and dibromobiphenyls
Jingxuan Tu, Gaoqiang Li, Xiaoqian Zhao, Feng Xu
PII:
S0040-4039(18)31399-6
https://doi.org/10.1016/j.tetlet.2018.11.052
TETL 50437
DOI:
Reference:
Tetrahedron Letters
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Revised Date:
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17 November 2018
20 November 2018
Please cite this article as: Tu, J., Li, G., Zhao, X., Xu, F., Synthesis of triphenylene derivatives by Pd-catalyzed
Suzuki coupling/intramolecular C-H activation between arylboronic acids and dibromobiphenyls, Tetrahedron
Letters (2018), doi: https://doi.org/10.1016/j.tetlet.2018.11.052
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Tetrahedron Letters
Synthesis of triphenylene derivatives by Pd-catalyzed Suzuki coupling/intramolecular
C-H activation between arylboronic acids and dibromobiphenyls
Jingxuan Tu , Gaoqiang Li  Xiaoqian Zhao and Feng Xu
Key Laboratory of Macromolecular Science of Shaanxi Province, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi'an, Shaanxi
710062, P. R. China
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
An efficient and regioselective synthesis of functionalized triphenylenes via palladium-catalyzed
Suzuki-Miyaura coupling and subsequent intramolecular C-H activation between arylboronic
acids and dibromobiphenyls was developed. This methodology showed excellent atomic
economy and regiospecificity as well as synthetic feasibility of unsymmetrical triphenylenes.
Available online
2009 Elsevier Ltd. All rights reserved.
Keywords:
Annulation
Cascade reaction
Palladium
Boron
Polycyclic aromatic hydrocarbons
triphenylenes.10 Greaney et al developed the synthesis of
triphenylenes via Pd-catalyzed [2+2+2] trimerisation of benzyne
Introduction
As the result of the advances in organic electronics such as
light emitters, semiconductors, liquid crystals, and solar cells,
polycyclic aromatic hydrocarbons(PAHs) has been regarded as
one of the most important groups of compounds in the field of
material science due to their superior optical, electronic and self-
assembling properties.1 Hence, efficient synthetic methods for
producing functionalized PAHs are undoubtly valuable to
accelerate the developments of PAHs-based functional materials.
Triphenylenes are the most often synthesized and widely studied
due to their unique electronic, biological and liquid crystal
properties2,3 as well as the applications for organic light-emitting
diodes.4 However, it is still a great challenge for the construction
of triphenylene nucleus because the carbon-carbon bonds used
for fusion of the phenyl ring can only be constructed one by one.5
In 1998, Guitián and co-workers firstly reported a Pd-catalyzed
cyclotrimerization of arynes to produce triphenylenes.6 Since
then, a variety of triphenylene derivatives were prepared with the
similar strategy using o-trimethylsilylaryl triflates as aryne
precursors.7-8 The drawbacks such as the high price of o-
trimethylsilylaryl triflates and the only successful synthesis of
symmetrical triphenylenes somehow hinder its more application.
In 2006, Larock et al reported a Pd-catalyzed annulation of
arynes with 2-halobiaryls, which can be utilized to prepare
unsymmetrical triphenylenes.9 Kim et al found a Pd-mediated
generation of aryne from methyl 2-bromobenzoates, which
using cheap benzoic acid11 as well as 2-bromophenylboronic
esters12 as benzyne precursors. Besides these excellent aryne
approaches, other important protocols were also developed for
triphenylene synthesis in recent years. For example, Miura and
co-workers found that o-dibromobenzenes could undergo Pd-
mediated decarbonylative cross-coupling with o-phenyl benzyl
alcohols to prepare triphenylenes.13 The Nishihara group
disclosed
a
palladium-catalyzed cascade reaction of o-
iodobiphenyls with o-bromobenzyl alcohols to form
triphenylene.14 Zhang and co-workers reported the palladium-
catalyzed annulations of 2-iodobiphenyls and iodobenzenes to
access functionalized triphenylenes.15 Diaryliodonium salts were
also available to react with o-halobenzoic acids or bromoarenes
to construct triphenylenes.16 Moreover, photochemical methods
were also developed to generate triphenylene backbones in very
high yields.17 Although these methods significantly expanded the
substrate scope for triphenylenes synthesis, to lack
regioselectivity and the formation of a mixture of regioisomers
were the major problem especially for the generation of highly
functionalized triphenylenes including unsymmetrical ones,
which generally play especially important roles in material
science.
Recently, the transition-metal catalyzed cross-coupling
reactions of organometals with organic halides provided an
efficient access to regio- and stereospecific C-C bonds
underwent
a
Pd-mediated [2+2+2] cycloaddition to give
———
 Corresponding author. e-mail: gqli@snnu.edu.cn; fengxu@snnu.edu.cn

2
Tetrahedron
formation.18 And thus, the step-wise double cross-coupling
8) revealed that strong inorganic base (KOH, entry 5) and organic
reactions of organodimetallic reagents and dihalides afforded a
straightforward and efficient method for highly functionalized
triphenylenes synthesis. King et al reported the uncatalyzed
reaction of [Zr(2,2'-biphenyldiyl)3][Li·(THF)4]2, as an equivalent
of 1,4-dimetal reagent with o-dihalobenzenes to form
triphenylenes in 2006.19d Shimizu et al developed the double
cross-coupling of 9-stannafluorenes, a 1,4-dimetal equivalent,
with o-dibromoarene for triphenylene synthesis.20c In 2011,
Shimizu reported a palladium-catalyzed double cross-coupling
reaction of 1,2-dimetal reagent, o-diborylbenzene with 2,2’-
dibromobiphenyl to synthesize triphenylene.21d Nevertheless,
either 1,4-dimetal reagents or 1,2-dimetal reagents were
generally prepared from the corresponding dihalogenated
compounds and up to date only limited these reagents and their
equivalents such as diboryl reagent,21 distannyl reagent,20
base
(DABCO, 1,4-Diazabicyclo[2.2.2]octane, entry 6) were ineffective
in this transformation.
Table 1. Optimization of the reaction conditionsa
Entry [Pd]
[L]
Base
Yield(%)b
18
1c
2d
3e
4
Pd(OAc)2
PPh3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
KOH
Pd(OAc)2
PPh3
Trace
16
dilithium
reagent,22
zirconacycles,19
platinacycles,23
Pd(OAc)2
PPh3
nickelacycles24 were developed and successfully applied in
transition-metal catalyzed annulation reactions. Considering the
wider availability and cheaper price of mono-metallic reagents,
to develop an efficient annulation process to prepare PAHs such
as triphenylene derivatives using mono-metal reagents instead of
dimetal reagents will undoubtly be more atom-economic and
appealing.
Pd(OAc)2
PPh3
33
5
Pd(OAc)2
PPh3
Trace
6
Pd(OAc)2
PPh3
DABCO n.r.
7
Pd(OAc)2
PPh3
K2CO3
22
8
Pd(OAc)2
PPh3
K3PO4
17
9
Pd(PPh3)4
PPh3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
17
For this consideration, we designed the annulations between
10
11
12
13
14
15
16
17
18
19
20
Pd2(dba)3
PPh3
14
PdCl2
PPh3
Trace
30
Pd(PPh3)2Cl2
Pd(PhCN)2Cl2
Pd(PCy3)2Cl2
Pd(PCy3)2Cl2
Pd(PCy3)2Cl2
Pd(PCy3)2Cl2
Pd(PCy3)2Cl2
Pd(PCy3)2Cl2
PPh3
PPh3
18
PPh3
40
PCy3
X-phosf
Xantphosg
S-phosh
32
21
Trace
58
P(4-MeOPh)3 Cs2CO3
75
Pd[P(4-MeOPh)3]2Cl2 P(4-MeOPh)3 Cs2CO3
Pd(PCy3)2Cl2 P(4-MeOPh)3 Cs2CO3
35
21i
84
a
Scheme1. Design of synthesis of triphenylene via Suzuki-Heck
type cascade.
Reaction conditions: 1a (0.6 mmol), 2a (0.5 mmol), [Pd] (5 mol%),
Ligand (5.5 mol%), Base (3.0 equiv.), Solvent (5.0 mL), 24h. b Isolated
yield. c Using toluene as solvent. d Using DMF as solvent. e Using THF as
f
arylboronic acids and 2,2'-dibromobiphenyls to construct the
triphenylene backbone (Scheme 1). In the reaction, the arylboronic
acid 1 firstly underwent Suzuki-Miyaura cross-coupling reaction
with dibromobiphenyl 2a and gave an intermediate I with a
remaining CAr-Br bond. The intermediate I subsequently formed an
intermediate II via oxidative addition with Pd0 catalyst.
Consequently, an intramolecular C-H activation and reductive
elimination process finally generated the triphenylene 3.
solvent. X-phos: 2-(dicyclohexyl-phosphino)-2',4',6'-triisopropyl-1,1'-
g
biphenyl.
xanthene.
Xantphos: 9,9-dimethyl-4,5-bis(diphenylphosphi-no)-
S-phos: 2-dicyclohexylphos-phino-2',6'-dimethoxy-1,1'-
h
biphenyl. i [Pd] (10 mol%), Ligand (11 mol%).
Further examination of various palladium species and phosphine
ligands was then carried out. Pd0 catalysts such as Pd(PPh3)4 and
Pd2(dba)3 showed lower catalytic ability than Pd(OAc)2 in this
cascade process (entries 9 and 10). The performance of other PdII
catalysts such as PdCl2, Pd(PPh3)2Cl2, Pd(PhCN)2Cl2, and
Pd(PCy3)2Cl2 were next evaluated (entries 11-14). Pd(PCy3)2Cl2
showed the best catalytic ability and the yield of 2-nitrotriphenylene
was increased to 40% (entry 14). Further screening of the phosphine
ligands revealed that PCy3 and X-Phos exhibited lower efficiency
and Xantphos was completely ineffective. S-phos showed positive
activity and the yield was increased to 58% (entry 18). The P(4-
MeOPh)3 was the best ligand in this transformation, finally
improving the yield to 75%. And thus, Pd[P(4-MeOPh)3]2Cl2 was
next selected to perform the transformation. A sharply decreased
yield of 3a was observed (entry 20), which indicated the role of each
phosphine in the catalytic cycle was completely different and the
details were unclear. By further increasing the amounts of
Result and discussion
An initial attempt to construct triphenylene backbone was
performed from 4-nitrophenylboronic acid and 2,2'-dibromobiphenyl
2a using Pd(OAc)2, PPh3, and Cs2CO3 in toluene at reflux.
Gratifyingly, 2-nitrotriphenylene was successfully isolated in 18%
yield (Table 1, entry 1). For PAHs synthesis, high reaction
temperature was generally favorable to the cyclization. Nevertheless,
only trace product was monitored in this cascade process when DMF
was utilized as solvent at reflux (Table 1, entry 2).
The effects of THF and 1,4-dioxane as solvents were also
investigated and the yield was improved to 33% in 1,4-dioxane at
reflux (Table 1, entry 4). The screening of bases (Table 1, entries 5-

Pd(PCy3)2Cl2 and P(4-MeOPh)3 into 10 mol% and 11 mol%
respectively, the isolated yield of desired 2-nitrotriphenylene was
finally enhanced to 84% (entry 21).
in this procedure. Although sterically hindered 2-methylboronic acid
performed the annualtion with 2,2'-dibromobiphenyl 2a affording the
desired product 3b’ in 31% yield, the yield was successfully
improved to 52% when 2 equivaluents of 2-methylphenylboronic
acid were used. The substituted dibromobiphenyl, 4,4,5,5-
tetramethyl-2,2'-dibromobiphenyl 2b also exhibited good reactivity
and smoothly conducted the annulations with arylboronic acids to
generate the corresponding triphenylenes (3n-3s).
With the optimal reaction conditions in hand, we next investigated
the substrate scope of the cascade annulation process (Table 2).
Table 2. Synthesis of triphenylenesa,b
The dibenzochrysene (DBC) is a twisted polycyclic aromatic
Scheme2. Preparation of dibenzochrysene.
hydrocarbon. Its derivatives can be applied to the preparation of
sensors, nonlinear optical and liquid-crystalline materials, etc. The
preparation of parent dibenzochrysene and its derivatives generally
requires multistep syntheses.25 In our previous work, we reported a
highly efficient approach to 9,10-diaryl substituted phenanthrenes,
which could be converted to dibenzochrysenes via the Scholl
reaction using CuCl2 and AlCl3 as an oxidant.26 With present
developed methodology, when 9-phenanthrylboronic acid was
directly utilized to react with 2,2'-dibromobiphenyls, one-step
synthesis of dibenzochrysenes was realized (Scheme 2).
Furthermore, this transformation showed high regioselectivity, only
9,10-cylized product was found and no 1,9-cyclized product was
observed.
To further investigate the regioselectivity of this cyclization
Table 3. Synthesis of triphenylenes with meta-substituted
arylboronic acida
Entry 1(R)
Time(h)
24
Yieldb
a Reaction conditions: 1 (0.6mmol), 2 (0.5mmol), Pd(PCy3)2Cl2 (10
mol%), P(4-MeOPh)3 (11 mol%), Cs2CO3 (3.0 equiv.), 1,4-dioxane (5
mL). b Isolated yield. c 2.0 equiv. aryboronic acids were used.
1
2
3
4
5
1u(NO2)
57%(3a’)
1v(CH3)
1w(F)
36
37%(3b+3b’;1:1.4)
38%(3f’)
24
Phenylboronic acids with a para-substitutent such as methyl(1b),
fluoro(1f), chloro(1g), cyano(1h), CF3(1i) and ester(1l and 1m) all
smoothly performed the cascade cyclization with 2,2'-
dibromobiphenyl 2a to produce the functionalized unsymmetric
triphenylenes in moderate to high yields. Phenylboronic acids with
electron-withdrawing groups were more reactive and gave higher
yields. Meaningfully, the halo substituents such as fluoro (3f and 3j)
and chloro (3g and 3k) on the benzene ring were well tolerated. The
triphenylenes containing halo atoms are very useful for they can be
easily further derivatized by means of simple coupling strategies and
the likes. The 1-naphthylboronic acid (1d) and 2-biphenylboronic
acid (1e) also effectively underwent the cascade coupling reactions
with 2,2'-dibromobiphenyl 2a to afford sterically hindered
triphenylenes. Moreover, no isomers of 1,8-cyclized product of 1-
napthylboronic acid and 2,2'-cyclized product of 2-biphenylboronic
acid were observed, which indicated that these two transformations
showed excellent regioselectivity. Sterically demanding ortho-
substituted phenylboronic acids (1b’ and 1e) were also well tolerated
1x(Cl)
24
41%(3g’)
1y(CF3)
24
32%(3i+3i’;1:1.1)
a Reaction conditions: 1 (0.6mmol), 2 (0.5mmol), Pd(PCy3)2Cl2 (10
mol%), P(4-MeOPh)3 (11 mol%), Cs2CO3 (3.0 equiv.), 1,4-dioxane (5
mL). b Isolated yield. c 2.0 equiv. aryboronic acids were used.
strategy, arylboronic acids with a meta-substituent were then tested
to perform the cascade cyclization with 2,2'-dibromobiphenyl 2a
(Table 3). For meta-substituted arylboronic acids, there generally
might produce two regioisomeric mixtures, triphenylene 3 and
triphenylene 3'. To our surprise, arylboronic acids with meta-
substitutents such as nitro(1u), fluoro(1w) and chloro(1x) showed
excellent regiospecificity. Only sterically more hindered
triphenylenes 3' cyclized between C1 and C2 of arylboronic acids
were produced and no cyclized triphenylenes 3 between C1 and C6
of arylboronic acids were found, which indicated that the steric effect
was not the major factor to determine the regioselectivity. When 3-
methylphenylboronic acid 1v and 3-trifluoromethylphenylboronic

4
Tetrahedron
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acid 1y were used to react with 2,2'-dibromobiphenyl 2a
respectively, a regioisomeric mixture was generated. 1,6-Cyclized
triphenylene and 1,2-cyclized triphenylene were produced and could
not be isolated by silica chromatography since they own completely
same retention factor value. The HNMR analysis showed the ratio
of 3b to 3b' was 1:1.4 and the ratio of 3i to 3i' was 1:1.1. The reason
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In conclusion, we have developed a highly efficient palladium-
catalyzed cascade annulations from 2,2'-dibromobiphenyls and
arylboronic acids for the synthesis of various functionalized
triphenylenes. This is the first case that mono-metallic reagents were
used to prepare triphenylenes. Compared with the previous double
couplings of dimetallic reagents with dihaloarenes, this methodology
showed very excellent atomic economy and reduction of synthesis
cost. Compared with the conventional cyclotrimerization of arynes,
the present strategy showed high regioselectivity and the synthetic
feasibility of unsymmetrical triphenylenes. For some meta-
substituted arylboronic acids, this cyclization process showed
excellent regiospecificity. This methodology also provides a highly
efficient and low-cost approach to dibenzochrysene derivatives
starting from simple, commercially available reactants in one step.
Further studies on the application of the present annualtion strategy
for the preparation of other functional material are in progress.
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Acknowledgments
We are grateful for the financial support from the National Natural
Science Foundation of China (21302117 and 21572123), the Natural
Science Foundation of Shaanxi Province (2018JM2049) and
Fundamental Research Funds for the Central Universities
(GK201603047 and GK201601003).
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Highlights
 mono-metallic reagents were firstly used to
prepare triphenylenes
 excellent atomic economy and regioselectivity
 the synthetic feasibility of unsymmetrical
triphenylenes.
 an efficient and low-cost approach to
dibenzochrysene derivatives
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Synthesis of triphenylene derivatives by Pd-
catalyzed Suzuki coupling/intramolecular C-
H activation between arylboronic acids and
dibromobiphenyls
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Jingxuan Tu, Gaoqiang Li, Xiaoqian Zhao and Feng Xu
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