Site-Selective Iron(III) Chloride-Catalyzed Arylation of 4-Aryl-4-methoxy-2,5-cyclohexadienones for the Synthesis of Polyarylated Phenols

Article abstract of DOI:10.1002/adsc.201600577

The iron(III) chloride-catalyzed Friedel–Crafts arylation of 4-aryl-4-methoxy-2,5-cyclohexadienones, which were easily prepared by the phenyliodine(III) diacetate (PIDA)-mediated oxidation of 4-arylphenols in methanol, proceeded site-selectively to form meta-terphenyl (2,4-diarylphenol) derivatives in good yields. The subsequent PIDA-mediated oxidation and iron(III) chloride-catalyzed Friedel–Crafts arylation of the resulting products gave the corresponding 2,4,6-triarylphenol derivatives. The present method provides useful highly substituted polyarylated compounds. (Figure presented.).

Full text of DOI:10.1002/adsc.201600577

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DOI: 10.1002/adsc.201600577
Very Important Publication
Site-Selective Iron(III) Chloride-Catalyzed Arylation of 4-Aryl-4-
methoxy-2,5-cyclohexadienones for the Synthesis of Polyarylated
Phenols
Yoshinari Sawama,a,* Masahiro Masuda,a Ryosuke Nakatani,a Hiroki Yokoyama,a
Yasunari Monguchi,a Toshifumi Dohi,b Yasuyuki Kita,b and Hironao Sajikia,*
a
Gifu Pharmaceutical University, 1-25-4 Daigaku-nishi, Gifu 501-1196, Japan
Fax : (+81)-58-230-8109; e-mail: sawama@gifu-pu.ac.jp or sajiki@gifu-pu.ac.jp
College of Pharmaceutical Sciences, Ritsumeikan University, 1-1-1 Nojihigashi, Kusatsu, Shiga, 525-8577, Japan
b
Received: June 2, 2016; Revised: September 13, 2016; Published online: && &&, 0000
Supporting information for this article can be found under: http://dx.doi.org/10.1002/adsc.201600577.
Abstract: The iron(III) chloride-catalyzed Friedel–
Crafts arylation of 4-aryl-4-methoxy-2,5-cyclohexa-
dienones, which were easily prepared by the phe-
nyliodine(III) diacetate (PIDA)-mediated oxidation
of 4-arylphenols in methanol, proceeded site-selec-
tively to form meta-terphenyl (2,4-diarylphenol) de-
rivatives in good yields. The subsequent PIDA-
mediated oxidation and iron(III) chloride-catalyzed
Friedel–Crafts arylation of the resulting products
gave the corresponding 2,4,6-triarylphenol deriva-
tives. The present method provides useful highly
substituted polyarylated compounds.
cause of their low waste production and the fact that
they are promoted by relatively strong acidic condi-
tions. Because 4-phenyl-4-hydroxy-2,5-cyclohexadi-
AHCTUNGTREGUNeNN none derivatives generally undergo the dienone-
phenol rearrangement in the presence of acidic re-
agents to form phenol derivatives,[4] the acid-catalyzed
coupling of 4-phenyl-4-hydroxy-2,5-cyclohexadienones
with unactivated arenes to construct terphenyls has
not yet been achieved. The ortho-arylation of phenol
derivatives[5,6] and direct oxidative aromatic coupling[7]
represent powerful tools for the construction of vari-
ous aromatic compounds and were actively investigat-
Keywords: Friedel–Crafts reaction; iron catalysts;
polyarenes; regioselectivity; terphenyls
Polyarenes having contiguous arene-arene bonds are
widely used in various scientific fields; in particular,
meta-terphenyl[1] and 1,3,5-triarylbenzene[2] are useful
building blocks for various functional materials, phar-
maceuticals and ligands used in organic chemistry.
Thus, the development of novel and efficient synthetic
methods for highly functionalized aromatic com-
pounds with reduced waste is strongly desired. 4-
Phenyl-4-hydroxy-2,5-cyclohexadienone
derivatives
(Scheme 1) are easily prepared by the phenyliodi-
ne(III) diacetate (PIDA)-mediated oxidation of the
corresponding 4-phenylphenols [e.g., 4-methoxy
(1a),[3a,b] 4-hydroxy (2),[3f,g,h,i] and 4-acetoxy (3)[3c,d] de-
rivatives are prepared in the presence of MeOH, H2O
and AcOH, respectively] and are unique synthetic
precursors of various aromatic compounds.[3] Friedel–
Crafts reactions using unactivated arenes as nucleo-
Scheme 1. FeCl3-catalyzed site-selective arylation of 4-
philes are regarded as environmentally friendly be- phenyl-4-hydroxy-2,5-cyclohexadione derivatives (1a).
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Table 1. Optimization of the model reaction conditions.[a]
ed; thus, a chemoselective stepwise synthetic method
is expected to be useful for providing novel aromatic
systems. Reactions using inexpensive and versatile
iron catalysts are accompanied by the generation of
neutral waste materials, such as methanol, and are
therefore regarded as clean. Recently, we revealed
that FeCl3 efficiently activates various benzylic posi-
tions,[8] and several FeCl3-catalyzed transformations
including Friedel–Crafts reactions[8e,g,i,j] were reported.
Methyl ethers derived from secondary and tertiary
benzylic alcohols were also effectively activated by
FeCl3 to generate benzylic cation intermediates, via
elimination of the methoxy group, which were cou-
pled with nucleophiles, such as an azide ion, allylic
moiety, or cyanide ion.[8f] Herein, we report a new ef-
ficient synthetic method for meta-terphenyl deriva-
tives starting from 4-aryl-4-methoxy-2,5-cyclohexa-
dione (1) by the FeCl3-catalyzed site-selective nucleo-
philic substitution of arenes via elimination of the
benzylic methoxy group. The generated meta-terphen-
yls were easily transformed into 1,3,5-triarylbenzene
derivatives by subsequent PIDA-mediated oxidation
and a second FeCl3-catalyzed Friedel–Crafts aryla-
tion.
Entry
Solvent
X
Time [min]
Yield [%]
1
2
3
4
5
6
7
8
(CH2Cl)2
CH2Cl2
CH3NO2
toluene
CH3CN
MeOH
THF
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
1.5
1.5
1.5
1.5
1.5
1.5
1.5
3
45
45
45
240
45
240
240
45
45
45
39
39
51
34
59
no reaction
no reaction
72
70
70
86
0
9[b]
10
11[b]
12[b,c]
3
10
10
10
60
60
[a]
The reaction was carried out in a 0.2M solution unless
otherwise noted.
0.075M solution in CH3CN.
[b]
[c]
10 mol% of H2O was added.
4-Phenyl-4-hydroxy-2,5-cyclohexadienone deriva-
tives (1a, 2 and 3) consist of an a,b-unsaturated car- to 3:1 in CH3CN (0.2M) resulted in a higher yield of
bonyl group and a tertiary benzylic alcohol moiety at 4a due to the suppression of the simultaneous and un-
the g-position (Scheme 1). The coupling reaction of desired dienone-phenol rearrangement (entry 8);
the 4-methoxy derivative (1a) with 1,3,5-trimethoxy- however, a further increase (10:1) did not have any
benzene (1.5 equiv.) in (CH2Cl)2 (0.2M) at room tem- significant effect (entry 10). It is noteworthy that the
perature proceeded to afford the corresponding meta- use of 10 equiv. of 1,3,5-trimethoxybenzene in a less
terphenyl (4a, a-adduct) in a perfectly regioselective concentrated solution (0.075M in CH3CN) significant-
manner; on the other hand, the reactions of 2 and 3 ly improved the reaction efficiency to give 4a in high
resulted in a complex mixture or did not proceed at yield (86%) (entries 10 vs. 11), whereas the concentra-
all (Scheme 1). Presumably, FeCl3 regioselectively ac- tion effect was not observed when using 3 equiv. of
tivates the benzylic methoxy group of 1a to form a cat- 1,3,5-trimethoxybenzene (entries 8 vs. 9). Similar ten-
ionic intermediate (B) via A. B is subsequently dencies were also found for other solvents [CH3NO2,
trapped by the electron-rich arene at the sterically ac- (CH2Cl)2, and toluene] and substrates (see the Sup-
cessible a-position, and the following isomerization porting Information); however, the reason for this is
(aromatization) leads to the formation of product not clear at this point. The desired product (4a) was
4a.[9] Although FeCl3 can also activate the a,b-unsatu- not obtained in the presence of H2O (10 mol%),
rated carbonyl group by coordination with the car- clearly indicating that the reaction was catalyzed by
bonyl oxygen (C), the subsequent nucleophilic attack FeCl3 and the HCl generated in situ from FeCl3 and
of the arene is probably prevented by the steric hin- H2O was ineffective.[10]
drance at the g-position.
Next, the scope of 4-aryl-4-methoxy-2,5-cyclohexa-
The reactivity was strongly dependent on the sol- dienone derivatives (1) and arenes was investigated
vent and concentration of the reaction mixture (Table 2). Substrates bearing a para-methoxyphenyl
(Table 1). The FeCl3 (10 mol%)-catalyzed Friedel– or para-bromophenyl substituent at the 4-position
Crafts arylation of 1a with 1.5 equiv. of 1,3,5-trime- were efficiently transformed into corresponding the
thoxybenzene proceeded smoothly in CH3CN (0.2M) meta-terphenyl derivatives (4b and 4c, respectively).
(entry 5), whereas the use of (CH2Cl)2, CH2Cl2, Substrates with a meta- or ortho-tolyl substituent at
CH3NO2, or toluene resulted in lower yields (en- the 4-position also underwent the desired FeCl3-cata-
tries 1–4), and the use of MeOH and THF resulted in lyzed Friedel–Crafts arylation to give the correspond-
no reaction (entries 6 and 7). Similar results were ob- ing meta-terphenyls (4d and 4e, respectively). More-
tained when TMSOTf or AuCl3 were used as Lewis over, other arene nucleophiles, namely, 1,3-dimeth-
acids in CH3CN (58% yields in both cases). Increasing
ACHTUNGTRENoNGNU xybenzene, anisole, 1,3-dimethoxy-5-bromobenzene
the ratio of 1,3,5-trimethoxybenzene to 1a from 1.5:1 and 1-methoxynaphthalene, could be applied to the
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Table 2. Scope of substrates and arenes.[a]
step provided highly functionalized phenols (9c and
9d) bearing different aromatic substituents at the 2-,
4-, and 6 positions (Scheme 2).
Finally, the effect of the 4-aryl substituent of sub-
strates 1 on the synthesis of meta-terphenyls was in-
vestigated. 4-Methoxy-4-methyl-2,5-cyclohexadienone
(10a) was found to be less reactive under the opti-
mized reaction conditions, and the biaryl b-adduct
(11) was generated in 81% yield within 24 h by the
1,4-addition of the a,b-unsaturated carbonyl moiety
(Scheme 3, top).[13] The non-benzylic methoxy group
is not sufficiently reactive to form a coordination in-
termediate with FeCl3,[8f] and the formation of the
corresponding a-adduct is therefore quite difficult.
The p-toluenesulfonic acid-catalyzed reaction of 10a
[a]
The reaction was carried out using 10 mol% of FeCl3 and
10 equiv. of arene in CH3CN (0.075M).
A mixture of regioisomers (ortho:para=1:2) was ob-
tained.
[b]
present reaction to form the corresponding meta-ter- using indole derivatives as nucleophiles has also been
phenyl products (4f–i) in moderate to excellent yields. reported by Fan et al.; however, the reaction was
The reaction of 1,3-dimethoxybenzene and 1-bromo- completely regioselective, giving only the b-adduct
3,5-dimethoxybenzene occurred at the more electron- (no a-adduct was observed).[14] These results clearly
rich and sterically accessible positions to afford 4f indicated that the 4-aryl group of substrates 1 is es-
and 4h, respectively. Substrate 5, prepared by the sential for the regioselectivity at the a-position. Addi-
PIDA-mediated oxidation of 4-methyl-1-hydroxy- tionally, the FeCl3-catalyzed coupling of 4-(2-hydr-
naphthalene in MeOH, was converted into the de-
sired naphthalene-benzene linked biaryl a-adduct 6a
as a main product (76% yield), accompanied by small
amounts of the b-adduct 6b (20% yield) [Eq. (1)].
The carbonyl moiety of 5 was activated by the neigh-
boring aromatic ring, which facilitated the side reac-
tion, i.e., the 1,4-addition of the a,b-unsaturated car-
bonyl moiety. Moreover, an annulation reaction oc-
curred between 1 (R=H or Br) and benzofuran to
provide the corresponding heterocyclic products (7a
and 7b) [Eq. (2)].[11,12]
The meta-terphenyl derivatives, 4a and 4c were
transformed into the corresponding 4-aryl-4-methoxy-
2-(2,4,6-trimethoxyphenyl)-2,5-cyclohexadienone de-
rivatives (8a and 8b).[11] These compounds served as
key substrates for a second FeCl3-catalyzed arylation,
which proceeded smoothly at the sterically accessible
6-position to form 2,4,6-triarylphenol derivatives (9a–
Scheme 2. Subsequent PIDA-oxidation of 2 in MeOH and
the second arylation for the synthesis of the 2,4,6-triarylphe-
d). The use of different nucleophilic arenes in each nols.
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in CH3CN (3.0 mL, 0.075M) was added FeCl3 (0.015 mmol),
and the mixture was stirred at room temperature under
argon. After being stirred until the reaction was completed,
the mixture was quenched with H2O and extracted with
CH2Cl2. The combined organic layers were dried over
Na2SO4 and concentrated under vacuum. The residue was
purified by silica-gel column chromatography to give the
arylated product.
Acknowledgements
This work was partially supported by Grand-in-Aid for
Young Scientists (B) from the Japan Society for the Promo-
tion of Science (JSPS) and Takeda Science Foundation.
Scheme 3. Effect of alkyl substituents at the g-position.
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ACHTUNGTRENNUNGoxyethyl)-4-methyl-2,5-cyclohexadienone (10b) with
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In conclusion, we have developed an efficient syn-
thetic method for highly functionalized meta-terphen-
yl derivatives by the FeCl3-catalyzed Friedel–Crafts
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6 Site-Selective Iron(III) Chloride-Catalyzed Arylation of 4-
Aryl-4-methoxy-2,5-cyclohexadienones for the Synthesis of
Polyarylated Phenols
Adv. Synth. Catal. 2016, 358, 1 – 6
Yoshinari Sawama,* Masahiro Masuda, Ryosuke Nakatani,
Hiroki Yokoyama, Yasunari Monguchi, Toshifumi Dohi,
Yasuyuki Kita, Hironao Sajiki*
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