Journal Pre-proofs

Unusual transformation of 4-hydroxy/methoxybenzylic alcohols via C-C ipso-

substitution reaction using proton-exchanged montmorillonite as media

Xuan Chen, Yangfang Yun, Zezhong Dong, Yu Zhou, Fei Li, Nan Jiang,
Dongyin Chen

PII: S0040-4039(20)31083-2
DOI: https://doi.org/10.1016/j.tetlet.2020.152584
Reference: TETL 152584

To appear in: Tetrahedron Letters

Received Date: 14 August 2020

Revised Date: 7 October 2020
Accepted Date: 18 October 2020

Please cite this article as: Chen, X., Yun, Y., Dong, Z., Zhou, Y., Li, F., Jiang, N., Chen, D., Unusual
transformation of 4-hydroxy/methoxybenzylic alcohols via C-C ipso-substitution reaction using proton-
exchanged montmorillonite as media, Tetrahedron Letters (2020), doi: https://doi.org/10.1016/j.tetlet.
2020.152584

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Graphical Abstract
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Unusual transformation of 4- Leave this area blank for abstract info.

hydroxy/methoxybenzylic alcohols via C-C
ipso-substitution reaction using proton-
exchanged montmorillonite as media
Xuan Chen, Yangfang Yun, Zezhong Dong, Yu Zhou, Fei Li, Nan Jiang* and Dongyin Chen*
R1 R1
R 2O OR2
H-mont on
ati
R 1 OR 2 fic R 1 R1
eri
1 Eth O
H H H Path b R
O H
H 2O
R1 R1
2 OH HCHO R1 OR2
R O R 2O
1 1 Path a
R R C R1
su -C ip
bs
R1 = H, Me, i-Pr, t-Bu titu so R1
tio
R2 = H, Me n
R 2O
R1
 1

Tetrahedron Letters
journal homepage: www.elsevier.com

Unusual transformation of 4-hydroxy/methoxybenzylic alcohols via C-C ipso-

substitution reaction using proton-exchanged montmorillonite as media
Xuan Chena,‡, Yangfang Yuna,‡, Zezhong Donga, Yu Zhoua, Fei Lia, Nan Jianga,* and Dongyin Chena,b,
a Department of Medicinal Chemistry, School of Pharmacy, Nanjing Medical University, Nanjing 211166, China
b State Key Laboratory of Natural Medicines, China Pharmaceutical University, Nanjing 210009, China

———
ACorresponding
R T I C L E I Nauthor.
F O E-mail address: jiangnan@njmu.edu.cn
A B S T R A C(N.
T Jiang), chendongyin@njmu.edu.cn (D. Chen).
‡ These authors contributed equally to this work.
Article history: We present here proton-exchanged montmorillonite-mediated an unusual transformation of 4-
Received hydroxy and 4-methoxybenzylic alcohols to form symmetrical benzylic ethers and
Received in revised form diarylmethanes under mild conditions. Nuclear magnetic resonance spectroscopy and density
Accepted functional theory calculations support a plausible mechanism, which includes a distinctive
Available online aromatic C-C ipso-substitution reaction with a hydroxymethyl group as the C-based leaving
group.
Keywords:
Proton-exchanged montmorillonite 2009 Elsevier Ltd. All rights reserved.
Aromatic C-C ipso-substitution
Benzylic alcohol
Diarylmethane
Density functional theory

1. Introduction polymerization reaction [15]. As part of our ongoing research in

Aromatic carbon-carbon ipso-substitution reaction is a
particular case of electrophilic aromatic substitution (EAS)
reaction [1], which is commonly used to prepare alkyl- [2], vinyl-
[3], alkynyl- [4], biphenyl- [5] and carbonyl- [6] substituted
aromatics. As shown in Scheme 1, the most important
characteristic of this reaction is that a new Ar‒C bonding takes
place upon the attack of a carbon-based electrophile on the
aromatic compound, producing a cyclohexadienyl cation as the
intermediate of EAS along with a new Ar-C bond formation at
the expense of another Ar-C bond [1c]. The most generally used
C-based leaving groups include alkyl [6], carbinol [5], CN [2,4],
carbonyl [3,7] groups in this ipso-substitution reaction. In order to
expand the range of application of this reaction, further studies
are still required to explore the diversity of leaving groups. On
the other hand, almost all these aromatic C-C ipso-substitution
reactions are catalyzed by transition-metal salts [8], Lewis acids [9]
and strong proton acids [10], but heterogeneous solid acid-
mediated this transformation has received very little attention [11].
Therefore, more extensive exploration on this interesting reaction
is a very attractive but challenging task.
X
X E
E -X+
R R R 1a-1c and 1f-1h are rapidly transformed to the corresponding
X = C-based leaving group ( alkyl, carbinol, CN, carbonyl, etc.)
E+ = C-based electrophile
Scheme 1. General mechanism of aromatic C-C ipso-substitution
reaction.
As a heterogeneous solid acid, proton-exchanged
montmorillonites (H-mont) has recently received much attention
due to its successful application in the carbosilylation reaction [12],
nucleophilic substitution reaction [13], addition reaction [14] and
our laboratory, we first reported H-mont-mediated substrate
specific double-bond isomerization [16], selective deprotection of
p-methoxybenzyl esters/ethers [17], and synthesis of heterocycle-
containing diarylmethanes via Friedel–Crafts alkylation reaction
[18]. Herein, we report H-mont-mediated transformation of 4-
hydroxy and 4-methoxybenzylic alcohols to form symmetrical
benzylic ethers and diarylmethanes under mild conditions.
Nuclear magnetic resonance (NMR) spectroscopy and density
functional theory (DFT) calculations are carried out to investigate
the mechanism. An unusual type of aromatic C-C ipso-
substitution reaction with a hydroxymethyl group as the C-based
leaving group is firstly described in detail.
2. Results and discussion
During the past two decades, a series of similar experiments
and theoretical model have been performed on the formation of
both cyclic and linear oligomers of benzyl alcohol derivatives
with bentonite or proton acid [19]. In this thesis, we present an
unusual transformation of 4-hydroxy and 4-methoxybenzylic
alcohol derivatives to form symmetrical benzylic ethers and
diarylmethanes using H-mont as media (Table 1). Under the H-
E mont-mediated reaction condition, benzylic alcohol derivatives
symmetrical diarylmethanes 2a-2c and benzylic ethers 3f-3h,
respectively (Table 1, entries 1-3 and 6-8). When using benzylic
derivatives 1d-1e and 1i-1j as substrates, the desired products are
rarely produced, together with some unidentified cyclic and
linear oligomers (Table 1, entries 4-5 and 9-10). A closer
inspection of the results reveals that para- and meta-substituents
on the aromatic ring of these benzylic alcohols plays an
important role on the reaction rate, product ratio and yield. With
a hydroxy group in the para-position and two symmetric
2 Tetrahedron Letters
hindering alkyl groups in the meta-positions, the reaction 5 3g i-Pr Me 14 76 (2g)
proceeds rapidly to give the corresponding diarylmethanes in 94-
96% yields, together with trace amounts of symmetrical benzylic 6c 3h Me Me 6 33 (2h)
ethers (Table 1, entries 1-3). In contrast, with a methoxy group in 7c 3j H Me 9.5 12 (2j)
the para-position and two symmetric hindering alkyl groups in a
the meta-positions, the benzylic ethers are the major products in Reaction conditions: each substrate (0.366 mmol), H-mont (260
mg), CH2Cl2 (3 mL), 25 oC.
32-83% yields, while the diarylmethanes are obtained in only 11- b Isolated yield.
19% yields after the consumption of starting materials (Table 1, c The linear and cyclic oligomers are the main byproduct.
entries 6-8). However, with hydrogen or methoxy groups in the
two meta-positions, the cyclic and linear oligomers are the main
products as similarly described in previous research [19] (Table 1, To investigate the reaction process, NMR technique was
entries 4-5 and 9-10). utilized to monitor the conversion of 1a to 2a and 3a. As shown
Table 1 H-mont-mediated transformation of 4-hydroxy and 4- in Fig. 1, the signal around 4.58 ppm is corresponding to the CH2
methoxybenzylic alcohol derivatives.a protons of 1a (Fig. 1a). After H-mont added to trigger this
R1 (m)
OH H-mont
R1 R1 R1
O
R1 reaction, the appearance of two new resonances in the 1H NMR
+
R 2O
(p)
o
CH2Cl2, 25 C R2O OR2 R 2O OR2 spectrum around 3.83 and 4.45 ppm (Fig. 1b and 1c), are
R1 R1 R1 R1 R1 corresponding to the CH2 protons of 2a and CH2OCH2 protons of
1 2 3
3a, respectively, which indicates the transformation of 1a into 2a
Time Yield of Yield of
Entry Comp. R1 R2 and 3a. As the reaction goes on, the signal of 4.45 ppm increases
(h) 2 (%)b 3 (%)b
to a peak then decreases until it disappeares completely.
1 1a t-Bu H 0.67 96 (2a) trace (3a)
Meanwhile, the signal of 3.83 ppm increases. It illustrates the
2 1b i-Pr H 0.83 96 (2b) trace (3b)
conversion of benzylic ethers 3a to diarylmethanes 2a under the
3 1c Me H 0.5 94 (2c) trace (3c)
H-mont-mediated reaction condition. Moreover, a significant
4c 1d OMe H 0.5 0 (2d) 0 (3d)
signal around 9.72 ppm is observed (Fig. 1d and 1e), which is
5c 1e H H 5 5 (2e) 0 (3e)
possible to indicate the formation of aldehyde compounds.
6 1f t-Bu Me 0.67 11 (2f) 83 (3f) In order to elucidate these observations described above, a
7 1g i-Pr Me 1.5 19 (2g) 65 (3g) plausible mechanism is proposed as shown in Scheme 2. With 4-
8c 1h Me Me 2 11 (2h) 32 (3h) hydroxybenzylic alcohol 1c as an example, it receives a proton
9c 1i OMe Me 8 0 (2i) 6 (3i) from H-mont to form p-quinone methide Ⅰ by losing a molecular
10c 1j H Me 0.25 12 (2j) 14 (3j) of H2O. Due to the p-hydroxy group as a secondary driving force
a Reaction conditions: each substrate (0.366 mmol), H-mont through electron delocalization, this process is easy and fast to
(260 mg), CH2Cl2 (3 mL), 25 oC. accomplish. The p-quinone methide Ⅰ is a strong electrophilic
b Isolated yield. species, which can be attacked by two different nucleophilic sites
c The linear and cyclic oligomers are the main byproducts. of another benzylic alcohol 1c as shown in Scheme 2. It's worth
noting that the symmetrical benzylic ether 3c generates more
easily than the diarylmethane 2c in the early stage of this process.
Interestingly, process monitoring of above reactions using thin To illustrate this phenomenon, density functional theory (DFT) at
layer chromatography (TLC) shows that benzylic ether 3 is B3LYP/6‒31G(d,p) level was employed to investigate and
unstable under the H-mont-mediated reaction condition, which compare the two possible reaction pathways in dichloromethane
can be converted into the corresponding diarylmethane 2 as the (DCM) solvation. Fig. 3 exhibits the free energy variation along
reaction going on. To further confirm this phenomenon, the the reaction pathway by using the energy sum of reactants
above reactions were terminated by filtering H-mont during the (benzylic alcohol 1c + p-quinone methide I) as a reference to
initial stage of reactions, and then a certain amount of benzylic make the next transformation steps share an energy scale. The
ethers 3a-3c, 3f-3h and 3j were prepared by flash theoretically calculated results are consistent with the
chromatograghy on silica gel. As shown in Table 2, benzylic experimental phenomenon. The electrophilic p-quinone methide I
ethers 3a-3c and 3f-3g can be readily converted into the is attacked more easily by the oxygen atom of hydroxy group
corresponding diarylmethanes 2a-2c and 2f-2g in moderate to (light blue) to give the symmetrical benzylic ether 3c (Scheme 2,
good yields (72%-92%) under the H-mont-mediated reaction path a), and the energy barrier is 18.98 kcal/mol. In comparison,
condition. However, due to the generation of linear and cyclic the electrophilic I attacked by the carbon atom of benzene ring
oligomers, benzylic ethers 3h and 3j can only give the desired (pink) is more slowly, to generate the cyclohexadienyl cation II
products 2h and 2j in low yields (12%-33%). with a new Ar-C bond formation (Scheme 2, path b), and the
energy barrier is 27.84 kcal/mol. The structures of transition-state
Table 2 H-mont-mediated transformation of symmetrical
TS-a and TS-b are shown in Fig. 2. Then, the electron
benzylic ethers 3 into diarylmethanes 2.a delocalization on the cyclohexadienyl cation Ⅱ promotes Ar-C
R1 R1 H-mont R1 R1
O
o
bond cleavage to give 2c with concomitant release of a
CH2Cl2, 25 C
R 2O OR2 R 2O OR2 formaldehyde molecule, which is successfully captured by NMR
R1 R1 R1 R1
spectroscopy. This is an unusual aromatic C-C ipso substitution
3 2
reaction with a hydroxymethyl group as the C-based leaving
group. On the other hand, the oxygen atom that joins both units
as a bridge in 3c is an electronegative center, which can capture a
Time Yield of 2 proton from H-mont. Then, the C-O ether bond cleaves assisting
Entry Comp. R1 R2 by p-hydroxy function as the secondary driving force through
(h) (%)b
electron delocalization in a mild condition. At last, nucleophilic
1 3a t-Bu H 0.67 87 (2a)
aromatic carbon (pink) of 1c interacts with electrophilic p-
2 3b i-Pr H 0.83 92 (2b) quinone methide Ⅰ to afford diarylmethane 2c through an unusual
aromatic C-C ipso substitution process. It’s interesting to
3 3c Me H 0.25 86 (2c) investigate the energetic variation with 4-methoxybenzylic
4 3f t-Bu Me 9 72 (2f) alcohol 1h as substrate. From Fig. S1, it can be seen that the
energy barrier from 1h + Ⅰ’ to 3h + H+ (path a’: 20.25 kcal/mol)
 3
is lower than that from 1h + Ⅰ’ to intermediate II’ (path b’: 26.60 formation is preferred, which is consistent with the
kcal/mol). These results indicate that in the case of 4- experimental phenomenon.
methoxybenzylic alcohol as substrate, the kinetic product

(a)

CH2 of 1a
0 min

(b)
CH2OCH2 of 3a
1 min

(c)

CH2 of 2a
5 min

(d)

20 min

(e)
O

60 min H H

Fig. 1 Real-time monitoring of the H-mont-mediated transformation of 1a to 2a and 3a by 1H NMR spectroscopy. Reaction conditions: 1a
(0.366 mmol), H-mont (260 mg), CDCl3 (6 mL), 25 oC. (a) 1H NMR spectrum of 1a in CDCl3 without the addition of H-mont. (b) 1H NMR
spectrum of reaction mixture at 1.0 min after the addition of H-mont. A molar ratio of 1a:2a:3a is approximately 40:1:9. (c) 1H NMR spectrum
of reaction mixture at 5.0 min after the addition of H-mont. A molar ratio of 1a:2a:3a is approximately 2:2:5. (d) 1H NMR spectrum of reaction
mixture at 20 min after the addition of H-mont. A molar ratio of 1a:2a:3a is approximately 2:11:2. (e) 1H NMR spectrum of reaction mixture at
60 min after the addition of H-mont.

H-mont

Me Me
H H H
H H-mont
O HO OH
Me Me Me
H 2O
H H H 2c
HO O
Me 1c H H

Path a
OH
Me
Me Me Me Me Me
O TS-a HO TS-b
H OH
HO OH HO HO OH
Me Me Me Path b Me Me Me
3c I 1c II
Scheme 2. Proposed mechanism for H-mont-mediated transformation of benzylic alcohol 1c.

TS-a TS-b
Fig. 2 The transition-state structures of TS-a and TS-b at the B3LYP/6-31+G(d,p) level of theory.
4 Tetrahedron
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Declaration of interests ☐The authors declare the following financial

interests/personal relationships which may be
☒ The authors declare that they have no known considered as potential competing interests:
competing financial interests or personal
relationships that could have appeared to influence
the work reported in this paper.
 5
Graphical Abstract

To create your abstract, type over the instructions in the

template box below.
Fonts or abstract dimensions should not be changed or altered.

Unusual transformation of 4- Leave this area blank for abstract info.

hydroxy/methoxybenzylic alcohols via C-C
ipso-substitution reaction using proton-
exchanged montmorillonite as media
Xuan Chen, Yangfang Yun, Zezhong Dong, Yu Zhou, Fei Li, Nan Jiang* and Dongyin Chen*
R1 R1
R 2O OR2
H-mont
at ion
R1 OR2 fic R1 R1
eri
Eth O
H H H Path b R1
O H
H 2O
R1 R1
OH HCHO R1 OR2
R 2O R 2O Path a
R1 R1 C R1
su -C ip
bs
R1 = H, Me, i-Pr, t-Bu titu so R1
tio
R2 = H, Me n
R 2O
R1