Palladium Catalyzed C-I and Vicinal C-H Dual Activation of Diaryliodonium Salts for Diarylations: Synthesis of Triphenylenes

Article abstract of DOI:10.1021/acs.joc.7b01905

Using the synthetic strategy of palladium-catalyzed dual activation of both C-I and vicinal C-H bonds of diaryliodonium salts, we report an approach for direct diarylations of 2-bromobiphenyls or bromobenzenes. As a result, a wide range of triphenylenes with various substituents have been synthesized in good yields. These triphenylenes are expected to be employed in the "bottom-up" synthesis of functional aromatic molecules in material science.

Full text of DOI:10.1021/acs.joc.7b01905

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Article
Palladium Catalyzed C-I and Vicinal C-H Dual Activation of
Diaryliodonium Salts for Diarylations# Synthesis of Triphenylenes
Xunshen Wu, Jian-Wei Han, and Limin Wang
J. Org. Chem., Just Accepted Manuscript • Publication Date (Web): 24 Nov 2017
Downloaded from http://pubs.acs.org on November 24, 2017
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Palladium Catalyzed C-I and Vicinal C-H Dual
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Activation of Diaryliodonium Salts for Diarylations：
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Synthesis of Triphenylenes
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Xunshen Wu,† Jianwei Han*†‡ and Limin Wang*†
†Key Laboratory for Advanced Materials, Institute of Fine Chemicals, School of
Chemistry & Molecular Engineering, East China University of Science and
Technology, 130 Meilong Road, Shanghai 200237, P. R. China
‡Shanghai–Hong Kong Joint Laboratory in Chemical Synthesis, Shanghai Institute of
Organic Chemistry, The Chinese Academy of Sciences, 345 Lingling Road, Shanghai
200032, China
Email: Jianwei Han – jianweihan@ecust.edu.cn; Limin Wang –
wanglimin@ecust.edu.cn
* Corresponding author
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Abstract
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With the synthetic strategy that palladium catalyzed dual activation of both CꢀI and
vicinal CꢀH bonds of diaryliodonium salts, we reported an approach for direct diarylations of
2ꢀbromobiphenyls or bromobenzenes. As a result, a wide range of triphenylenes with various
substituents has been synthesized in good yields. These triphenylenes are expected to be
employed in the “bottomꢀup” synthesis of functional aromatic molecules in material science.
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Introduction
Polycyclic aromatic hydrocarbons (PAHs) have received much attention because of their
potential use in optoꢀelectrochemical materials.1 Among them, triphenylenes together with
biphenylenes, fluoranthenes and tetraphenylenes were frequently appeared molecular unit in
the preparation of extended πꢀconjugated systems with characteristic optical and
electrochemical properties ((1), Figure 1).2 Furthermore, triphenylene is a fully benzenoid
molecule feathering strictly planar conformation and threeꢀfold rotation axes.3 Considering
this unique structure and property, triphenylene frameworks have been widely used in
bottomꢀup synthesis of postfunctional graphene segments, even largeꢀscale graphene
materials.4 The traditional method in the preparation of triphenylenes was cyclization of
oꢀterphenyls by Scholl reaction, for example, we reported in 2016 that
trifluoromethanesulfonic acids with 2,3ꢀdichloroꢀ5,6ꢀdicyanobenzoquinones as oxidants in
dehydrogenative coupling reaction of 2,2ꢀbis(4ꢀmethylphenyl)biphenyl produced the
corresponding triphenylene derivative in 55% yield.5 However, the scope of triphenylenes by
Scholl reaction was limited because of the harsh conditions.6 Recently, palladium catalyzed
arylative cyclization of oꢀiodobiphenyls, dibenzothiophenes, 9ꢀstannafluorenes, cyclic
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diaryliodonium salts with various substituted benzene derivatives to access triphenylenes was
well recorded ((2), Figure 1).7ꢀ11 For examples, the group of Larock reported the cyclizations
of oꢀiodobiphenyls with benzynes.8 oꢀBromobenzyl alcohols by Nishihara and iodobenzenes
by Zhang et al. were used as annulation partners with oꢀiodobiphenyls in the cyclizations for
producing triphenylenes.9 On the other hand, cyclic diaryl compounds such as
dibenzothiophenes, 9ꢀstannafluorenes and cyclic diaryliodonium salts were employed in the
preparation of triphenylenes by Yorimitsu, Shimizu and Hong reseach groups, respectively.10
Moreover, palladium catalyzed cyclotrimerization of benzynes also afforded triphenylene in
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good yields.11
(1) The conjugated aromatics
triphenylene
biphenylene
(2) The synthesis of triphenylenes
fluoranthene
tetraphenylene
3
" Pd "
" Pd "
" Pd "
I
A,B,C or F
A, D or E
X
X = S, SnMe2, IꢀOTf,
N*
TMS
OTf
B*
Br
Br
I
OH
Br
D
F
C
A
B
E
B*=boric acid group; N*= Amide groups.
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Figure 1. Fully areneꢀfused carbon rings and palladiumꢀcatalyzed methods in
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synthesis of triphenylenes.
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9
In recent years, palladiumꢀcatalyzed arylations using diaryliodonium salts to generate
carbonꢀcarbon bonds have achieved considerable progress.12 Very interestingly, the research
groups of Stuart and Wang independently disclosed in 2016 that diaryliodonium salts can
generate benzynes under severe basic conditions, the resulted intermediates were allowed to
undergo Nꢀarylation of secondary amides and amines or cycloaddition reaction with furan to
support the existence of benzynes.13 In our previous work, we have developed a
palladiumꢀcatalyzed diarylation of coumarins by using diaryliodonium salts in synthesis of
4,5ꢀbenzocoumarins, in which simultaneous cleavage CꢀI and vicinal CꢀH bond of
diaryliodonium salts was discovered to form two new CꢀC bonds.14 Therefore, our initial
strategy towards triphenylenes assumed that palladium catalyzed dual activation of both CꢀI
and vicinal CꢀH bonds of diaryliodonium salts to furnish aryneꢀlike intermediates, which
could further annulate with palladacycles generated from 2ꢀbromobiphenyls for the synthesis
of triphenylenes. As such, in this context, we described herein a feasible method for the
synthesis of triphenylenes via diarylation using diaryliodonium salts (Scheme 1).
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(1) Our previous work
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5
Ar1
H
H
H
6
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8
9
Pd(OAc)2 (10 mol %)
DMF, 100 oC. 24 h
+
Ar2
Ar1
I
X
O
O
R
O
O
R
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(2) Proposed synthetic strategy towards triphenylene
H
I
X
"Pd"
+
Br
Scheme 1. Palladium activation of both CꢀI and vicinal CꢀH bonds of diaryliodonium
salts for the synthesis of triphenylene.
Results and Discussion
We initially started the diarylation of 2ꢀbromobiphenyl 1a using diphenyliodonium salt 2a
in the presence of 5 mol% Pd(OAc)2 as catalyst, a mixture of Na2CO3 and CsOAc in DMF at
o
130 C under argon atmosphere. It was pleasing to find that the desired product 3aa was
obtained in 24% yield after 12 hours (entry 1, Table 1). Examination of the palladium
catalysts showed that Pd(PPh3)4 gave the desired product 3aa in 55% yield with detectable
amounts of 1ꢀphenyltriphenylene (4) as byproduct (entries 1ꢀ4, Table 1). A control reaction by
single base of Na2CO3 or CsOAc caused diminished yield of 16% or no reactivity (entries 5ꢀ6,
Table 1). Various phosphoric ligands including PPh3, P(Cyclohexyl)3, dppf, BINAP, dppe or
nitrogen containing ligands of phenanthroline and 2,2’ꢀbipyridine were screened in the
reaction, unfortunately none of them showed more effective (0ꢀ41% yields, entries 7ꢀ13,
Table 1). Interestingly, we were pleased to find that 1.5 equivalents of diphenyliodonium salt
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2a lead to an increased yield of 68% with only a trace amounts of 1ꢀphenyltriphenylene (4)
(entry 14, Table 1). Subsequently, we found that solvent and base has a significant effect on
this reaction (for details, see the Supporting Information). We also tried to avoid the further
arylation of 3aa to generate 4 by addition of external radical inhibitor such as butylated
hydroxytoluene (BHT) and 2,2,6,6ꢀtetramethylꢀ1ꢀpiperidinyloxy (TEMPO),15 however, the
presence of BHT and TEMPO did not affect the outcome of this reaction, but the formation of
4 was inhibited completely (55ꢀ62%, entries 15ꢀ16, Table 1). The influence of counterꢀanions
of diaryliodonium salts was studied, it was shown that OTf performs better than other
counterꢀanions (BF4, OTs, and PF6) (21ꢀ46% yields, entries 17ꢀ19, Table 1). Finally, a
remarkable fact is that when iodobenzene was used in replacement of diphenyliodonium salt,
only 7% of the desired product 3aa can be obtained under the standard conditions (entry 20,
Table 1).
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Table 1. Reaction Optimizationa
Entry
Catalyst
Base 1
Base 2
Additives
X
Yield of 3aa
(%)b
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
1
2
3
4
5
6
Pd(OAc)2
Pd(dppf)2Cl2
Pd(PPh3)4
Na2CO3
Na2CO3
Na2CO3
Na2CO3
CsOAc
CsOAc
CsOAc
OTf
OTf
OTf
OTf
OTf
OTf
24
38
55
Pd(PPh3)2Cl2
Pd(PPh3)4
CsOAc
41
ꢀ
Na2CO3
trace
16
ꢀ
Pd(PPh3)4
CsOAc
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7
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
CsOAc
CsOAc
CsOAc
CsOAc
CsOAc
CsOAc
CsOAc
CsOAc
CsOAc
CsOAc
CsOAc
CsOAc
CsOAc
CsOAc
PPh3
OTf
OTf
OTf
OTf
OTf
OTf
OTf
OTf
OTf
OTf
BF4
PF6
OTs
ꢀ
19
0
8
Phenanthroline
P(cyclohexyl)3
Dppf
9
18
30
23
0
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BINAP
12
13
14c
15c
16c
17c
18c
19c
20d
2,2’ꢀDipyridyl
DPPE
41
68(65)
62
55
21
32
46
7
ꢀ
Tempo
BQ
ꢀ
ꢀ
ꢀ
ꢀ
aReaction conditions: 1a (0.4 mmol), 2a (0.8 mmol), catalyst (0.02 mmol), base and solvents (8 mL).
bIsolated yield. cWhen 1.5 equiv. of 2a (0.6 mmol) was employed. dWhen iodobenzene was used in place of
2a.
With the optimal conditions established for the synthesis of triphenylenes, we next
examined the substrate scope of various 2ꢀbromobiphenyls in the diarylation with
diphenyliodonium triflate (2a). As shown in Table 2, a broad range of substituents of methyl,
methoxy, halogens, nitro, cyano, ester, trifluoromethyl, formyl or acyl groups on the orthoꢀ,
metaꢀ or paraꢀposition of biphenyls, regardless of their electronic nature, are well tolerated to
the formation of 3. The 2’ꢀmethyl substituted substrate 1b was tested under the standard
condition, which gave the desired product 3ab in 61% yield. When the reaction was carried
out with 3’ꢀsubstituted substrates 1cꢀ1g, the diarylation occurs on the positions with less steric
hindrance to give the corresponding product in good yields (3acꢀ3ag, 36ꢀ81%, Table 2). The
4’ꢀsubstitued substrates were also screened, it was found that the electronic properties of
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groups on the 4’ position of the 2ꢀbromobiphenyls affected reaction significantly. For example,
2ꢀbromobiphenyls with electronꢀwithdrawing (CF3, NO2, CN, CO2Et, CHO) groups gave
3agꢀ3ak in good to excellent yields of 66ꢀ88% (Table 2). However, the 2ꢀbromobiphenyls
with electronꢀdonating groups (Me, OMe) only gave 3ad and 3ac in 52% and 53% yield,
respectively. The 4’ꢀF substituted 1h afford 3ae in poor yield of 21%; 4’ꢀacetyl substituted
substrate gave 3al in 39% yield (Table 2). It was remarkable that 3ꢀtrifulouromethylphenyl
bromide gave only product of 3ag because of the steric hinderance. Additionally,
2ꢀbromobiphenyls with double substituents (Me, OMe) also worked well, which gave the
desired products 3am and 3an in moderate yields (36% of 3am and 42% of 3an, Table 2).
Interestingly, 2ꢀ(2ꢀbromophenyl)naphthalene can also undergo the diarylation in moderate
yield of 49%, thus providing 3ao in high regioselectivity without observation of 1ꢀposition
arylated product. Moreover, it was found that the benzo[g]chrysene (3ap) was synthesized in
22% yield with 1ꢀ(2ꢀbromophenyl)naphthalene as starting material by using this procedure.
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Table 2. Scope of Diverse 2ꢀBromobiphenyls in the Diarylationa,b
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5 mol % Pd(PPh3)4
Na2CO3 (2 eq.)
Br
CsOAc (3 eq.)
Ph2IOTf
DMF, 120 oC, 12 h
R
7
R
8
9
2a
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3
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O
F
3ae
3aa
3ab
3ac
3ad
(51%)
(68%)
(61%)
(81%)
(65%)
CF3
Cl
O
F
3ag
(51%)
3ae
3ad
(53%)
3a
(21%)
3ac
(52%)
f (36%)
CF3
(87%)
NO2
(88%)
CN
COOEt
(66%)
CHO
3ak
(71%)
3ag
3ah
3ai
3aj
(81%)
O
O
O
3al
3am
3an
3ao
3ap
(22%)
(39%)
(36%)
(42%)
(49%)
aReaction conditions: 1 (0.4 mmol), 2a (0.6 mmol), Pd(PPh3)4 (0.02 mmol), Na2CO3 (0.8
mmol), CsOAc (1.2 mmol) and solvents (8 mL) at 130 oC for 12 h. bIsolated yield
Subsequently, the structural diversity of various diaryliodonium salts 2 were examined.
As shown in Table 3, an extensive range of substituted symmetrical and unsymmetrical
diaryliodonium salts, bearing a wide variety of substituent groups, could react with 1a for the
synthesis of the corresponding triphenylenes 3. As can be seen, the electron density of the
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substituents of diaryliodonium salts have an influence on the reaction activity. For the
symmetrical diaryliodonium salts containing electronꢀdonating groups, such as 4ꢀmethoxy,
4ꢀmethyl, 3ꢀmethyl and 3,4ꢀdimethyl substituents, the diarylation occurred smoothly to give
the desired products 3ac, 3ad and 3am in good yields of 47ꢀ90% (entries 1ꢀ4, Table 3).
Whereas the electronꢀwithdrawing diaryliodonium salts bearing fluorine or trifluoromethyl
groups only gave the corresponding products 3ae and 3ag in poor yields of 25ꢀ29% (entries
5ꢀ7, Table 3). No reaction took place with bisꢀ(2,4,6ꢀtrimethylphenyl)iodonium triflate as
arylating reagent (Entry 9, Table 3), which proved that steric factor severely affected the
reactivity. Unsymmetrical arylꢀmesityl iodonium reagents were also employed in the reaction,
it was found that the aryl groups can transfer to the desired product selectively because of the
steric effect. As shown in Table 3, 3ad, 3ba and 3ca were obtained in moderate yields of
42ꢀ60% (entries 9ꢀ11, Table 3). Notably, when unsymmetrical salt of
[(4ꢀMeOC6H4)(4ꢀNO2C6H4)I]OTs was employed in this reaction, 3ac was formed exclusively
in good yield of 81% without observation of the nitryl product 3ah (entry 14, Table 3), which
suggested that electronꢀrich aryl groups favored the transfer of aromatics in this reaction.
Table 3. Scope of Diverse Iodonium Salts in Diarylationa
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Entry
Ar1(Ar2)
X
Product Yield (%)b
1
2
3
4
(4ꢀMeOC6H4)2
(4ꢀMeC6H4)2
OTf
OTf
3ac
3ad
90
52
(3ꢀMeC6H4)2
OTf
OTf
3ad
47
61
(3,4ꢀdiMeC6H4)2
3am
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(3ꢀFC6H4)2
(4ꢀFC6H4)2
OTf
OTf
3ae
3ae
25
29
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7
8
9
BF4
OTf
OTf
7
8
9
(4ꢀCF3C6H4)2
3ag
-
28
n. r.
42
(Mesityl)2
4ꢀMeC6H4
(Mesityl)
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3ad
3ba
3ca
3ac
4ꢀPhC6H4
(Mesityl)
10
11
12
OTf
OTf
OTs
56
60
81
4ꢀPhOC6H4
(Mesityl)
4ꢀMeOC6H4
(4ꢀNO2C6H4)
aReaction conditions: 1a (0.4 mmol), 2 (0.6 mmol), Pd(PPh3)4 (0.02 mmol), Na2CO3 (0.8
mmol), CsOAc (1.2 mmol) and solvents (8 mL) at 130 oC for 12 h. bIsolated yield
To further probe the reactivity of iodonium salts, 1,1'ꢀbiphenylꢀmesityl iodonium triflates
(7) was prepared for the diarylation. Therefore, we tried another pathway to synthesize the
triphenylenes 3 using 7 and bromobenzenes 8 under the standard conditions with the higher
o
temperature of 150 C for a longer time of 24 hours in a purpose for the completely
conversion of 7. To our delight, the desired product 3aa was obtained in 76% yield (Table 4).
Furthermore, several bromobenzene derivatives, bearing both electronꢀdonating (4ꢀmethoxy,
4ꢀmethyl and 3,4ꢀdimethyl) and electronꢀwithdrawing (4ꢀchloro, 4ꢀfluoro, 4ꢀtrifluoromethyl,
3ꢀtrifluoromethyl) groups, were employed in the diarylation reaction with 7 to give the
corresponding products 3 in moderate to good yields (71% of 3ac, 51% of 3ad, 55% of 3am,
70% of 3af and 36% and 69% of 3ag, 75% of 3ae, Table 4). Of note, when 3ꢀmethoxy
bromobenzene was used in this protocol, both 3ac and 3aq were isolated in the yield of 65%
and 32%, respectively.
Additionally, 2ꢀbromoꢀ4'ꢀchloroꢀ4ꢀmethylꢀ1,1'ꢀbiphenyl(5) was used to synthesize
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triphenylenes bearing different substituents on the aromatic rings. As shown in Scheme 2, two
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regioꢀisomers 6a and 6b were formed in 63 % yield in the ratio of 1:1.9 by the H NMR
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spectra (Scheme 2).
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Scheme 2. Palladiumꢀcatalyzed diarylation of 5.
Table 4. Scope of Diverse Biphenyliodonium Salts in Diarylationa,b
aReaction conditions: 7 (0.4 mmol), 8 (0.8 mmol), Pd(PPh3)4 (0.02 mmol), Na2CO3 (0.8 mmol), CsOAc (1.2
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mmol) and solvents (8 mL) at 150 oC for 24 h. bIsolated yield.
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Encouraged by these diarylation results, our attempt was turned to palladiumꢀcatalyzed
9
diarylation
for
the
synthesis
of
and
9,10ꢀdiphenylphenanthrene
diaryliodonium salts
with
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2ꢀbromoꢀ1,1,2ꢀtriphenylethene
(9)
(2a).
2ꢀBromoꢀ1,1,2ꢀtriphenylethene (9) was employed in the protocol under the conditions of
palladium catalysis, the desired product of 10 was afforded in 42% yield at the temperature of
150 oC for 24 hours (Scheme 3).
Scheme 3. Palladiumꢀcatalyzed diarylation of 9 with 2a.
The suggested mechanism for the generation of triphenylene is presented in Figure 2.
Firstly, oxidative addition gives rise to 11 that upon reaction with base forms a cationic
Pdꢀcomplex, which turn by electrophilic aromatic palladation give rise to 12.Then the second
oxidative addition can form the Pd(IV)ꢀcomplex 14. Reductive elimination results in the
formation of the arylpalladium species15. Then the second electrophilic aromatic palladation
takes place to give 16. Then complex 16 undergoes reductive elimination to give the product
and Pd(0) species that enters the catalytic cycle again. When 8a was employed in the reaction,
a similar pathway could have occurred. The palladium(II) species 13 underwent an oxidative
addition and an intramolecular CꢀH activation to afford the palladacycle 14, which then
afforded 3aa in a similar manner.
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Figure 2. Proposed mechanism.
To illustrate the reaction scope for potential utility, we prepared
2ꢀbromoꢀ3',5ꢀdimethoxyꢀ1,1'ꢀbiphenyl (19) in two steps. As shown in Scheme 4,
starting from 1ꢀbromoꢀ3ꢀmethoxybenzene (17), a homocoupling reaction and a further
bromination with
Nꢀbromosuccinimide afforded 18 and 19 in 92% and 96% yield，
respectively. We then conducted the diarylation of 19 by using diphenyliodonium salt
2a, the triphenylene 20 bearing double methoxy substituents was synthesized in 65%
yield under the standard conditions. According to the report by Adachi group,16 20 was
an useful building block which can easily convert to 21 according to the literature.16
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The compound of 21 was used as electron transport materials in the area of organic
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lightꢀemitting diodes (OLEDs).
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Scheme 4. The synthesis towards electron transport material molecule 21.
Conclusion
In summary, we have developed
a
palladiumꢀcatalyzed diarylation of
2ꢀbromobiphenyls with diaryliodonium salts for synthesis of triphenylenes. As such, a wide
range of triphenylenes was synthesized in moderate to excellent yields of 21ꢀ90%. A possible
mechanism involving palladiumꢀaryne complex was proposed. More importantly, this method
was useful in the synthesis of triphenylene based materials. Further studies on the mechanism
and applications of this reaction are also underway in our laboratory.
Experimental Section
1
General Methods. H and 13C spectra were recorded on a Bruker AVANCE 400
spectrometer, operating at 400 MHz for 1H NMR, 100 MHz for 13C NMR. Chemical shifts (δ)
are reported in ppm, and coupling constants (J) are in Hertz (Hz). The following abbreviations
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were used to explain the multiplicities: s = singlet, d = doublet, t = triplet, q = quartet, m =
multiplet, br = broad; Mass spectra were in general recorded on a Waters LCT Premier XE
spectrometer; Column chromatography was performed with silica gel (200ꢀ300 mesh ASTM).
All solvents were dried and/or distilled by standard methods. All reagents were purchased
from commercial sources and used without further purification. The diaryliodonium salts
were synthesized according to the literature procedures.17 Substituted 2ꢀbromobiphenyls were
prepared through the Suzukiꢀcoupling of 1ꢀbromoꢀ2ꢀiodobenzene and arylboronic acid.18
Procedure A : The preparation of triphenylenes from 2-bromobiphenyl :
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Pd(PPh3)4 (0.02 mmol, 0.05 equiv.), Na2CO3 (0.8 mmol, 2 equiv.), CsOAc (1.2 mmol, 3
equiv.) and diphenyliodonium salts (0.6 mmol, 1.5 equiv.) were added to a dried Schlenk tube.
The tube was degassed with argon for three times. Then DMF (8.0 mL) and
2ꢀbromobiphenyls (0.4 mmol, 1 equiv.) were added via a syringe. The mixture was stirred at
o
130 C for 12 h, and then cooled down to room temperature. The reaction mixture was
extracted with EtOAc (20 mL) for 3 times and washed with brine for 2 times. The organic
phase was dried with Na2SO4, filtered and concentrated. The crude products were purified
using flash column chromatography on silica gel to afford the desired product.
Procedure B : The preparation of triphenylenes from biphenyliodonium salts: Pd(PPh3)4
(0.02 mmol, 0.05 equiv.), Na2CO3 (0.8 mmol, 2 equiv.), CsOAc (1.2 mmol, 3 equiv.) and
biphenyliodonium salts (0.4 mmol, 1 equiv.) were added to a dried Schlenk tube. The tube
was degassed with argon for three times. Then DMF (8.0 mL) and aryl bromides (0.8 mmol, 2
equiv.) were added via a syringe. The mixture was stirred at 150 oC for 24 h, and then cooled
down to room temperature. The reaction mixture was extracted with EtOAc (20 mL) for 3
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times and washed with brine for 2 times. The organic phase was dried with Na2SO4, filtered
and concentrated. The crude products were purified using flash column chromatography on
silica gel to afford the desired product.
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Procedure C : The preparation of 9,10-Diphenylphenanthrene:
Pd(PPh3)4 (0.02 mmol, 0.05 equiv.), Na2CO3 (0.8 mmol, 2 equiv.), CsOAc (1.2 mmol, 3
equiv.), diphenyliodonium salts (0.6 mmol, 1.5 equiv.) and 2ꢀbromoꢀ1,1,2ꢀtriphenylethene
(0.4 mmol, 1 equiv.) were added to a dried Schlenk tube. The tube was degassed with argon
for three times. Then DMF (8.0 mL) was added via a syringe. The mixture was stirred at 150
oC for 24 h, and then cooled down to room temperature. The reaction mixture was extracted
with EtOAc (20 mL) for 3 times and washed with brine for 2 times. The organic phase was
dried with Na2SO4, filtered and concentrated. The crude products were purified using flash
column chromatography on silica gel to afford the desired product.
Triphenylene (3aa)19 (White solid, 62 mg, 68% yield for 1a using Procedure A; 69 mg, 76%
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yield for 6a using Procedure B). M. p.: 198ꢀ199 C. H NMR (400 MHz, CDCl3): δ
8.69ꢀ8.64(m, 6H), 7.70ꢀ7.65(m, 6H); 13C NMR (100 MHz, CDCl3): δ 129.8, 127.2, 123.3.
Methyltriphenylene (3ab)9b (White solid, 59 mg, 61% yield using Procedure A). M. p.:
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94ꢀ96 C. H NMR (400 MHz, CDCl3): δ 8.65 (dd, J = 8.0, 1.6 Hz, 1H), 8.63ꢀ8.59 (m, 3H),
8.54 (dd, J = 7.6, 1.6 Hz, 1H), 7.68ꢀ7.51 (m, 6H), 3.07 (s, 3H); 13C NMR (100 MHz, CDCl3)
δ 135.4, 131.6, 131.3, 131.0, 130.7, 130.4, 129.9, 128.5, 127.3, 127.1, 126.6, 126.3, 125.6,
123.6, 123.2, 123.0, 121.0, 26.7.
2-Methoxytriphenylene (3ac).8a (White solid, 84 mg, 81% yield for 1c using Procedure A;
54 mg, 52% yield for 1j using Procedure A; 93 mg, 90% yield for 2a using Procedure A; 84
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mg, 81% yield for 2m using Procedure A; 73 mg, 71% yield for 6b using Procedure B; 67 mg,
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65% yield for 6i using Procedure B). M. p.: 101ꢀ102 C. H NMR (400 MHz, CDCl3): δ
8.67ꢀ8.62 (m, 2H), 8.60ꢀ8.54 (m, 3H), 8.05 (d, J = 2.4 Hz, 1H), 7.69ꢀ7.58 (m, 4H), 7.28 (dd, J
= 9.2, 2.8 Hz, 1H), 4.03 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 158.9, 131.3, 130.2, 129.9,
129.5, 128.8, 127.3, 127.3, 127.1, 126.3, 125.0, 123.8, 123.4, 123.3, 123.3, 122.8, 115.8,
105.8, 55.5.
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2-Methyltriphenylene (3ad).8a (White solid, 63 mg, 65% yield for 1d using Procedure A; 51
mg, 53% yield for 1i using Procedure A; 50 mg, 52% yield for 2b using Procedure A; 45 mg,
47% yield for 2c using Procedure A; 41 mg, 42% yield for 2i using Procedure A; 49 mg, 51%
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yield for 6i using Procedure B). M. p.: 101ꢀ102 C. H NMR (400 MHz, CDCl3): δ 8.68ꢀ8.62
(m, 4H), 8.54(d, J = 8.4 Hz, 1H), 8.45 (s, 1H), 7.69ꢀ7.63 (m, 4H), 7.49 (dd, J = 8.4, 1.2 Hz,
1H), 2.62 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 136.9, 129.9, 129.8, 129.8, 129.7, 129.4,
128.7, 127.5, 127.2, 127.2, 127.1, 127.1, 126.8, 123.3, 123.3, 123.1, 21.9.
2-Fluorotriphenylene (3ae).9b (White solid, 50 mg, 51% yield for 1e using Procedure A; 21
mg, 21% yield for 1h using Procedure A; 25 mg, 25% yield for 2e using Procedure A; 29 mg,
29% yield for 2f using Procedure A; 74 mg, 75% yield for 6h using Procedure B). M. p.:
188ꢀ189 oC. 1H NMR (400 MHz, CDCl3): δ 8.65ꢀ8.53 (m, 4H), 8.51ꢀ8.47 (m, 1H), 8.24 (dd, J
= 11.2, 2.8 Hz, 1H), 7.71ꢀ7.62 (m, 4H), 7.37 (ddd, J = 9.1, 7.8, 2.6 Hz, 1H); 13C NMR (100
MHz, CDCl3) δ 162.2 (d, J = 244.0 Hz), 131.8 (d, J = 8.0 Hz), 130.2, 129.3, 129.3, 129.0 (d, J
= 3.3 Hz), 127.9, 127.4, 127.3, 127.1, 126.3 (d, J = 2.2 Hz), 125.6 (d, J = 8.7 Hz), 123.5,
123.4, 123.4, 123.1, 115.4 (d, J = 22.7 Hz), 108.8 (d, J = 22.2 Hz); 19F NMR (376 MHz,
CDCl3): δ ꢀ114.15 (s,1F).
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2-Chlorotriphenylene (3af).9b (White solid, 38 mg, 36% yield for 1f using Procedure A; 74
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mg, 70% yield for 6e using Procedure B). M. p.: 145ꢀ146 C. H NMR (400 MHz, CDCl3): δ
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8.64ꢀ8.61 (m, 2H), 8.58ꢀ8.52 (m, 4H), 7.71ꢀ7.63 (m, 4H), 7.58 (dd, J = 8.8, 2.0 Hz, 1H); C
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NMR (100 MHz, CDCl3) δ 133.3, 131.2, 130.1, 129.6, 129.1, 128.6, 128.2, 127.8, 127.5,
127.4, 127.4, 124.9, 123.3, 123.2, 123.0.
2-(Trifluoromethyl)triphenylene (3ag).9b (White solid, 60 mg, 51% yield for 1g using
Procedure A; 103 mg, 87% yield for 1k using Procedure A; 33 mg, 28% yield for 2g using
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Procedure A; 43 mg, 36% yield for 6f using Procedure B). M. p.: 109ꢀ111 C. 1H NMR (400
MHz, CDCl3): δ 8.89 (s, 1H), 8.73 (d, J = 8.8 Hz, 1H), 8.68ꢀ8.63 (m, 4H), 7.85 (dd, J = 8.8,
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1.6 Hz, 1H), 7.76ꢀ7.67 (m, 4H); C NMR (100 MHz, CDCl3) δ 132.2 (d, J = 0.9 Hz), 130.4,
130.0, 129.6, 129.0, 128.7, 128.3, 128.1, 127.6, 127.5, 124.1, 123.7, 123.4, 123.4, 123.4,
123.2 (q, J = 3.1 Hz), 120.60 (q, J = 4.4 Hz); 19F NMR (376 MHz, CDCl3): δ ꢀ62.01 (s, 3F).
2-Nitrotriphenylene (3ah).8b (Pale yellow solid, 96 mg, 88% yield using Procedure A). M. p.:
158ꢀ159 oC. 1H NMR (400 MHz, CDCl3): δ 9.33 (d, J = 2.4 Hz, 1H), 8.61ꢀ8.50 (m, 5H), 8.30
(dd, J = 9.2, 2.4 Hz, 1H), 7.76ꢀ7.65 (m, 4H); 13C NMR (100 MHz, CDCl3) δ 146.3, 134.3,
131.0, 130.1, 130.0, 129.2, 128.6, 128.6, 128.1, 127.9, 127.7, 124.4, 124.2, 123.5, 123.4,
120.8, 119.1.
Triphenylene-2-carbonitrile (3ai). 8b (White solid, 82 mg, 81% yield using Procedure A). M.
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p.: 215ꢀ216 C. H NMR (400 MHz, CDCl3): δ 8.89 (d, J = 1.6 Hz, 1H), 8.67ꢀ8.62 (m, 3H),
8.59 (dd, J = 8.0, 1.2 Hz, 1H), 8.56ꢀ8.52 (m, 1H), 7.81 (dd, J = 8.8, 1.6 Hz, 1H), 7.77ꢀ7.67 (m,
4H); 13C NMR (100 MHz, CDCl3) δ 132.9, 130.8, 130.1, 129.9, 128.9, 128.9, 128.4, 128.3,
128.3, 128.1, 127.9, 127.7, 124.2, 123.9, 123.5, 123.5, 123.2, 119.4, 110.5.
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Ethyl triphenylene-2-carboxylate (3aj).20 (White solid, 79 mg, 66% yield using Procedure
A). M. p.: 129ꢀ130 oC. 1H NMR (400 MHz, CDCl3): δ 9.32 (d, J = 1.6 Hz, 1H), 8.73ꢀ8.69 (m,
1H), 8.64ꢀ8.60 (m, 4H), 8.23 (dd, J = 8.4, 1.6 Hz, 1H), 7.71ꢀ7.63 (m, 4H), 4.51 (q, J = 7.2 Hz,
2H), 1.51 (t, J = 7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 166.8, 133.1, 130.6, 129.9,
129.5, 129.5, 129.0, 128.7, 128.2, 127.7, 127.5, 127.4, 127.3, 125.3, 124.0, 123.54], 123.4,
123.3, 61.2, 14.5.
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Triphenylene-2-carbaldehyde (3ak).21 (White solid, 73 mg, 71% yield using Procedure A).
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M. p.: 149ꢀ150 C. H NMR (400 MHz, CDCl3): δ 10.17 (s, 1H), 8.96 (d, J = 1.6 Hz, 1H),
8.62ꢀ8.54 (m, 5H), 8.01 (dd, J = 8.4, 1.6 Hz, 1H), 7.72ꢀ7.62 (m, 4H); 13C NMR (100 MHz,
CDCl3) δ 192.2, 134.5, 134.4, 130.9, 129.9, 129.8, 129.1, 128.8, 128.7, 128.0, 127.6, 127.5,
126.7, 126.1, 124.2, 124.1, 123.4, 123.4, 123.3.
1-(Triphenylen-2-yl)ethan-1-one (3al).20 (White solid, 42 mg, 39% yield using Procedure A).
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M. p.: 152ꢀ153 C. H NMR (400 MHz, CDCl3): δ 9.22 (d, J = 1.6 Hz, 1H), 8.70 (q, J = 3.2
Hz, 1H), 8.66ꢀ8.61 (m, 4H), 8.15 (dd, J = 8.4, 1.6 Hz, 1H), 7.74ꢀ7.65 (m, 4H), 2.78 (s, 3H);
13C NMR (100 MHz, CDCl3) δ 198.0, 135.2, 133.3, 130.7, 130.0, 129.6, 129.5, 128.9, 128.4,
127.8, 127.6, 127.5, 126.2, 124.0, 123.7, 123.4, 123.4, 26.9.
2,3-Dimethyltriphenylene (3am).8b (White solid, 37 mg, 36% yield for 1q using Procedure
A; 62 mg, 61% yield for 2d using Procedure A; 56 mg, 55% yield for 6d using Procedure B).
M. p.: 156ꢀ157 oC. 1H NMR (400 MHz, CDCl3): δ 8.65ꢀ8.62 (m, 4H), 8.40 (s, 2H), 7.66ꢀ7.60
(m, 4H), 2.53 (s, 6H); 13C NMR (100 MHz, CDCl3) δ 136.2, 129.8, 129.5, 127.9, 127.0, 126.6,
123.9, 123.2, 123.0, 20.3.
2,3-Dimethoxytriphenylene (3an). 8a (White solid, 48 mg, 42% yield using Procedure A). M.
p.: 164ꢀ165 oC. 1H NMR (400 MHz, CDCl3): δ 8.68ꢀ8.65 (m, 2H), 8.52ꢀ8.49 (m, 2H), 8.00 (s,
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2H), 7.68ꢀ7.59 (m, 4H), 4.13 (s, 6H); 13C NMR (100 MHz, CDCl3) δ 149.4, 129.5, 129.2,
127.0, 126.3, 124.2, 123.4, 122.8, 104.5, 56.0.
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Benzo[f]tetraphene (3ao).22 (White solid, 49 mg, 49% yield using Procedure A). M. p.:
203ꢀ204 oC. 1H NMR (400 MHz, CDCl3): δ 9.05 (s, 2H), 8.75 (d, J = 6.8 Hz, 2H), 8.56 (d, J =
6.4 Hz, 2H), 8.07 (dd, J = 6.0, 3.2 Hz, 2H), 7.68ꢀ7.62 (m, 4H), 7.57 (dd, J = 6.4, 3.2 Hz, 2H);
13C NMR (100 MHz, CDCl3) δ 127.0, 124.9, 124.8, 123.2, 122.9, 122.4, 122.2, 120.8, 118.4,
118.2, 116.8.
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Benzo[g]chrysene (3ap).22 (White solid, 22 mg, 22% yield using Procedure A). M. p.:
117ꢀ118 oC. 1H NMR (400 MHz, CDCl3): δ 8.96 (d, J = 8.0 Hz, 1H), 8.92 (dd, J = 8.0, 1.2 Hz,
1H), 8.76ꢀ8.70 (m, 2H), 8.68ꢀ8.65 (m ,1H), 8.62 (d, J = 9.2 Hz, 1H), 8.04ꢀ7.99 (m, 2H),
7.74ꢀ7.58 (m, 6H); 13C NMR (100 MHz, CDCl3) δ 133.6, 130.9, 130.2, 120.0, 129.8, 129.5,
129.4, 128.5, 128.2, 128.1, 127.7, 127.4, 127.3, 127.2, 126.7, 126.1, 126.0, 125.9, 123.8,
123.5, 123.2, 120.8.
2-Phenyltriphenylene (3ba).9b (White solid, 68 mg, 56% yield using Procedure A). 185ꢀ186
oC. 1H NMR (400 MHz, CDCl3): δ 8.86 (d, J = 1.2 Hz, 1H), 8.76ꢀ8.73 (m, 1H), 8.71ꢀ8.65 (m,
4H), 7.90 (dd, J = 8.4, 1.6 Hz, 1H), 7.82 (d, J = 7.2 Hz, 2H), 7.70ꢀ7.66 (m, 4H), 7.56 (t, J =
7.6 Hz, 2H), 7.45 (t, J = 7.4 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ 141.2, 139.9, 130.1,
130.1, 129.8, 129.8, 129.6, 129.0, 128.9, 127.6, 127.5, 127.4, 127.3, 127.3, 127., 126.4, 123.9,
123.4, 123.4, 121.8.
2-Phenoxytriphenylene (3ca). (White solid, 77 mg, 60% yield using Procedure A). M. p.:
115ꢀ116 oC. 1H NMR (400 MHz, CDCl3): δ 8.65ꢀ8.55 (m, 4H), 8.44 (dd, J = 8.0, 1.2 Hz, 1H),
8.23 (d, J = 2.4 Hz, 1H), 7.67ꢀ7.57 (m, 4H), 7.42ꢀ7.36 (m, 2H), 7.34 (dd, J = 8.8, 2.4 Hz, 1H),
7.18ꢀ7.11 (m, 3H); 13C NMR (100 MHz, CDCl3) δ 157.4, 156.5, 131.6, 130.2, 129.9, 129.6,
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129.3, 129.2, 127.6, 127.4, 127.2, 126.8, 125.8, 125.3, 123.5, 123.5, 123.4, 123.1 119.2, 118.9,
112.4. HRMS (EI): Calcd. for C24H16O (M+): 320.1201, Found: 320.1203.
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6-chloro-2-methoxy-11-methyltriphenylene
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11-chloro-2-methoxy-6-methyltriphenylene (6). (White solid, 77 mg, 63% yield using
1
Procedure A). H NMR (400 MHz, CDCl3): δ 8.52 (d, J = 8.8 Hz, 1H), 8.49 (d, J = 8.8 Hz,
1H), 8.46 (d, J = 2.0 Hz, 1H), 8.40 (d, J = 8.4 Hz, 1H), 8.30 (s, 1H), 7.88 (d, J = 2.8 Hz, 1H),
7.56 (dd, J = 8.8, 2.2 Hz, 1H), 7.41 (dd, J = 8.4, 1.2 Hz, 1H), 7.27 (dd, J = 9.4, 2.6 Hz, 1H),
1
4.03 (s, 3H), 2.59 (s, 3H); H NMR (400 MHz, CDCl3): δ 8.47 (d, J = 4.0 Hz, 1H), 8.45 (d, J
= 3.2 Hz, 1H), 8.44 (d, J = 2.4 Hz, 1H), 8.40 (d, J = 8.4 Hz, 1H), 8.30 (s, 1H), 7.99 (d, J = 2.4
Hz, 1H), 7.50 (dd, J = 8.6, 1.8 Hz, 1H), 7.46 (dd, J = 5.0, 1.8 Hz, 1H), 7.25 (dd, J = 9.0, 2.6
Hz, 1H), 4.04 (s, 3H), 2.61 (s, 3H). HRMS (EI): Calcd. for C20H15ClO (M+): 306.0811, Found:
306.0812.
1-Methoxytriphenylene (3aq).10a (White solid, 33 mg, 32% yield using Procedure B). M. p.:
o
1
169ꢀ170 C. H NMR (400 MHz, CDCl3): δ 9.68ꢀ9.65 (m, 1H), 8.70ꢀ8.62 (m, 3H), 8.34 (d, J
= 8.0 Hz, 1H), 7.68ꢀ7.57 (m, 5H), 7.21 (d, J = 7.6 Hz, 1H), 4.12 (s, 3H); 13C NMR (100 MHz,
CDCl3) δ 153.7, 127.2, 125.1, 124.9, 124.6, 124.4, 123.9, 122.1, 121.9, 121.9, 121.5, 121.3,
118.8, 118.0, 117.5, 115.2, 110.8, 104.6, 50.7.
9,10-Diphenylphenanthrene (10).23 (White solid, 55 mg, 42% yield using Procedure C). M.
o
1
p.: 238ꢀ239 C. H NMR (400 MHz, CDCl3): δ 8.81 (d, J = 8.4 Hz, 2H), 7.69ꢀ7.64 (m, 2H),
7.58ꢀ7.54 (m, 2H), 7.51ꢀ7.46 (m, 2H), 7.27ꢀ7.14 (m, 10H); 13C NMR (100 MHz, CDCl3) δ
139.6, 137.2, 131.9, 131.1, 130.0, 127.9, 127.6, 126.6, 126.5, 126.4, 122.5.
2,11-Dimethoxytriphenylene (20).10b (White solid, 75 mg, 65% yield using Procedure A). M.
p.: 155ꢀ156 oC. 1H NMR (400 MHz, CDCl3): δ 8.56 (d, J = 8.8 Hz, 2H), 8.52 (dd, J = 6.4, 3.2
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Hz, 2H), 7.96 (d, J = 2.8 Hz, 2H), 7.57 (dd, J = 6.2, 3.4 Hz, 2H), 7.27 (dd, J = 9.2, 2.8 Hz,
2H), 4.02 (s, 6H); 13C NMR (100 MHz, CDCl3) δ 158.8, 130.9, 128.9, 126.3, 125.0, 124.2,
122.8, 115.6, 106.2, 55.5.
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Acknowledgements
The work was supported by the National Nature Science Foundation of China (NSFC
21472213, 21272069), National Key Program (2016YFA0200302, Study on application and
preparation of aroma nanocomposites), the Fundamental Research Funds for the Central
Universities and Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic
Chemistry, Chinese Academy of Sciences.
Supporting Information
The characterization data and copies of 1H, 13C NMR spectra for all products. The Supporting
Information is available free of charge via the internet at http://pubs.acs.org.
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