Ydroarylationof
Ydroarylationof
Ydroarylationof
Abstract: A mild and efficient Zn(II)-catalyzed regioselective other nucleophiles, such as aniline, indole and phenol
1,6-hydroarylation of para-quinone methides (p-QMs) with derivatives, offering the corresponding triarylmethanes with
electron-rich arenes protocol is reported. A variety of good yields under the standard conditions. The possible
electron-rich arenes and para-quinone methides are well mechanism for the formation of C(sp3) C(sp2) bonds in
tolerated under mild conditions, delivering a broad range of hydroarylation reactions has been explored by step-by-step
triarylmethanes in good to excellent yields. The present control experiments, and the reaction may follow a second-
method also works well for the hydroarylation of p-QMs with order manner in a chemical kinetic study.
Introduction
for the synthesis of asymmetric triarylmethanes through the ingly, it was found that the target product 3 a was generated in
enantioselective conjugate addition of 2-naphthols to p-QMs 91% yield in DCE solution through the synergetic catalysis of
under chiral phosphoric acid catalysis in 2019.[11] Meanwhile, ZnBr2 (5 mol%) and TMSCl (5 mol%) (Table 1, entry 1). For
Fan and partners studied the 1,6-conjugated reduction of p- further optimization, in addition to DCE as the solvent, we also
QMs for obtaining enantiomerically enriched triarylmethanes by investigated some other solvents, such as EtOAc, CH3CN,
copper catalysis, where Ph2SiH2 and Cu(OAc)2 are adopted to CH3OH, 1,4-dioxane, DMF, toluene, DMSO, THF and DCM
produce the active CuH in situ to promote the reaction.[12] (Table 1, entries 2–10), and 3 a could be constructed in DCM
Therefore, exploring a mild, low-cost and atom-efficient with the highest yield of 96%. For exploring the effect of
regioselective 1,6-hydroarylation of p-QMs is still challenging different catalysts in the reaction, different kinds of Lewis acids,
and demanding. such as ZnCl2, FeCl3, Et2O·BF3, B(C6F5)3, AgBF4, CuBr2 and Cu(OTf)2
In recent years, chemical reactions with mild conditions and were used in the reactions (Table 1, entries 11–17). It is obvious
high atomic economy, as well as the concept of green that ZnBr2 showed the best catalytic activity toward the
chemistry have attracted an increasing attention.[13] Our group’s reaction. The amount of catalyst used also has a great influence
enthusiasm in atom-efficient functionalization of p-QMs encour- on the reaction. When we operated the reaction in the absence
aged us to develop a scheme to build triarylmethanes by the of catalyst, the product 3 a could only be formed in 21% yield
regioselective 1,6-hydroarylation of p-QMs.[14] We focused our (Table 1, entry 18). Meanwhile, the amount of catalyst increased
attention on finding a Lewis acid system which could imple- from 1 mol% to 5 mol% resulted in the sharp increase of the
ment the hydroarylation at ambient temperature.[15] As a yield. However, with a further increase of the amount of catalyst
continuation of this study, we provide a Lewis acids synergetic from 5 mol% to 20 mol%, the yield of 3 a was not greatly
catalysis system for the regioselective 1,6-hydroarylation of p- affected (Table 1, entries 19–21). Based on the above results, we
QMs (Scheme 1e) at room temperature. As far as we know, the further optimized the dosage of TMSCl. When the amount of
direct hydroarylation of p-QMs with electron-rich arenes to form TMSCl was increased from 0 mol% to 20 mol% as the additive,
unsymmetrical triarylmethanes using such catalyst system has the highest yield was obtained with 5 mol% TMSCl (Table 1,
not been reported previously. entries 22–25). When the reaction temperature is increased
from 0 °C to 25 °C, the yield of 3 a could be greatly increased. A
further increase of the temperature lowers the yield of the
Results and Discussion desired product (Table 1, entries 26–29). Thus, after analyzing
the optimization results of a band of reaction conditions, the
Initially, the catalytic system of trimethylsilyl chloride (TMSCl) in optimal reaction condition is as follows: 5 mol% ZnBr2, 5 mol%
combination with various transition metals as catalyst for the TMSCl and DCM as solvent (Table 1, entry 10).
hydroarylation of anisole to p-QMs was explored. The reaction As shown in Table 2, the Zn(II)-catalyzed 1,6-hydroarylation
of 4-benzylidene-2,6-di-tert-butylcyclohexa-2,5-dienone (1 a) reactions of p-QMs with anisole 2 a are suitable for p-QMs with
with anisole (2 a) was selected as the model reaction. Surpris- various substituents, generating the target products in excellent
Table 3. Substrate scope of anisoles.[a] substrates which contain halogen atoms, alkene or alkyne
groups, can be further functionalized into more complex and
useful molecules.
As depicted in Table 4, in order to investigate the applic-
ability of this protocol, phenol (5 a), o-cresol (5 b), 2-bromophe-
nol (5 c) and naphthalen-2-ol (5 d) were allowed to react with
1 a, the intended products 6 a–6 d could be obtained in 76–90%
yields. The indole substrates 5 e–5 h also have excellent
reactivity at the C3 position, generating the target products
6 e–6 h in 86–92% yields. Meanwhile, the expected products 6 i–
6 k could be obtained in 76–83% yields through the reactions of
anilines (5 i, 5 j, 5 k,) with 1 a. Due to the strong nucleophilicity
of the amino group, the 1,6-conjugate addition of 1 a with
aniline (5 l) proceeded at the amino group, generating 6 l in
87% yield. When naphthyl compounds such as 1-meth-
oxynaphthalene (5 m) and 2-methoxynaphthalene (5 n) were
employed as the substrates for the reaction under the
optimized reaction conditions, the products 6 m and 6 n could
be synthesized in 76% and 80% yields, respectively. Interest-
ingly, the reaction of methyl(m-tolyl)sulfane (5 o) can also react
with 1 a to provide the corresponding product 6 o in 78% yield.
Besides these general substrates, we further adopted hetero-
cyclic thiophene ether (5 p) and thiophene thioether (5 q) as the
substrates to react with 1 a under the standard conditions, the
expected products 6 p and 6 q were produced as we expected
in 73% and 69% yields, respectively. However, when 4-meth-
oxypyridine (5 r), furan (5 s) and 2-methylfuran (5 t) are used as
raw materials, as monitored by GC-MS and NMR analysis, it is
oxyphenyl)(phenyl)methyl)-2,6-di-tert-butylphenol (4 l) and 4- Table 4. [a] Reaction conditions: 1 a (0.2 mmol), anisoles (2 b–ac,
0.2 mmol), ZnBr2 (0.01 mmol), TMSCl (0.01 mmol), DCM (1.0 mL), air, 25 °C,
((2-bromo-4,5-dimethoxyphenyl)(phenyl)methyl)-2,6-di-tert-bu- 3 h. Isolated yields.Table 4
tylphenol (4 m) were obtained in 73–87% yields through the Scope of other reactive substrates.[a]
reactions of 1 a with anisole derivatives 2 l–2 n under the
present reaction conditions. Additionally, the halogen function-
alized anisoles, such as 1-fluoro-2-methoxybenzene (2 o), 1-
chloro-2-methoxybenzene (2 p), 1-bromo-2-methoxybenzene
(2 q), 1-fluoro-3-methoxybenzene (2 r), 1-chloro-3-meth-
oxybenzene (2 s), 1-bromo-3-methoxybenzene (2 t) and 1-iodo-
3-methoxybenzene (2 u) also showed satisfactory results, pro-
ducing the 1,6-hydroarylation products 4 n–4 t with good to
excellent yields. For the products 4 q–4 t, since the methoxy
group has a stronger orienting effect than halogen on the aryl
ring, the above products become the only products in the
reaction. Meanwhile, 2-methoxy-1,1’-biphenyl (2 v), and 2-meth-
oxybenzaldehyde (2 w) also show good to excellent reactivity in
the reaction with the expected target products 4 u and 4 v
synthesized in 93% and 69% yield, respectively. Apart from
methoxybenzene, other analogues, such as ethoxybenzene
(2 x), propoxybenzene (2 y), (benzyloxy)benzene (2 z),
(allyloxy)benzene (2 aa), (prop-2-yn-1-yloxy)benzene (2 ab) and
oxydibenzene (2 ac) also works well in the reaction, generating
the corresponding products 4 w–4 ab in 74–92% yields. In other
common Lewis acid-catalyzed reactions involving anisole,
anisole is easy to be substituted in the ortho position, while in
the present zinc-catalyzed system, high para-position regiose-
lectivity is observed.[16] It is worth pointing out that the above
Z xA
Z t
dxA
¼ kCA0 dt
0 ð1 xA ÞðM xA Þ 0 71% yield (Scheme 3, eq. 5). Besides, we further explored the
competitive reaction which involves the hydroarylation of p-
QMs (1 a) with aniline and N,N-dimethylaniline in a one-pot
(3) The initial concentration ratio satisfies: CA0 ¼ CB0 , so, reaction under standard conditions, the products 6 i and 6 l
M¼1 could be synthesized in 87.1% and 7.9% yields as confirmed by
(4) The above formula can be transformed into: GC and 1H NMR analysis (Scheme 3, eq. 6). The result shows that
� � the compound 5 i has a higher nucleophilicity, which has a
1 1 0
CA CA0 ¼ k t
better reactivity than the compound 5 l in the competitive
Graphs of relation were depicted in the variable relationship reaction.
between (1/CA-1/CA0) at different time (Figure 2B). Since the Based on the above experimental results and previous
graphics of relationship of (1/CA-1/CA0) versus t fits well with a studies, a plausible mechanism is described as shown in
straight line, the experimental results show that reaction Scheme 4.[15a] First, ZnBr2 initially activates the C=O group of p-
process of 3 a, 6 a, 6 e, 6 i and 6 l probably follows the second- QMs (1 a) to form the intermediate (A). Then, the para C H
order reaction.[17] bond of anisole (2 a) reacts with the electron-deficient A,
In order to explore the reaction mechanism, a series of generating the arenium ion (B) via the 1,6-conjugated addition/
control experiments were implemented under standard con- aromatization processes. Subsequently, the possible intermedi-
ditions. When the free-radical scavenger 2,2,6,6-tetrameth- ate C was generated through the deprotonation reaction of B
ylpiperidine N-oxyl (TEMPO) was added to the reaction under with TMSCl, with the release of hydrogen chloride and zinc (II)
standard reaction conditions, to our surprise, 3 a could still be cation. Finally, the target product 3 a was obtained through the
formed in 82% yield (Scheme 3, eq. 1). Therefore, the reaction acidification of the hydrogen chloride. It is worth noting that
may be established not through a free radical mechanism. In the released zinc source and the regenerated TMSCl could be
addition, when 2,6-di-tert-butyl-4-methylphenol (BHT) was used reused to the next catalytic cycle.
as the radical inhibitor for the reaction under standard reaction
conditions, the hydroarylation product 3 a could be isolated in
91% yield (Scheme 3, eq. 2). On the other hand, when HCl was
used to replace TMSCl for the reaction, the expected product
3 a could be obtained in 92% yield (Scheme 3, eq. 3), indicating
that TMSCl presumably promotes the reaction by releasing HCl
to act as a Brønsted acid.[15a] Meanwhile, for proving the transfer
mechanism of hydrogen atom in the reaction process, CDCl3 as
the reaction solvent for the hydroarylation of phenol-d6 with p-
QMs (1 a) was performed (Scheme 3, eq. 4). However, because
the deuterated hydrogen atom of hydroxyl was very easy to be
replaced by hydrogen atoms from water and air, the retention
ratio of the deuterated atom of hydroxyl was only 30% after the
purification. The results show that the keto-enol tautomerism
may occur during the reaction. When one equivalent of H2O
was used to replace 2 a to react with 1 a under standard
conditions, 1 a first forms electron deficient intermediate by the
activation of catalytic system and then H2O attacked the
electron deficient intermediate to provide the product 3 a’ in Scheme 4. A plausible reaction mechanism.
Chem Asian J. 2023, 18, e202201156 (10 of 15) © 2022 Wiley-VCH GmbH
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(100 MHz, CDCl3, 25 °C, TMS): δ = 152.0 (s), 147.1 (s), 146.9 (s), 6.0 Hz), 129.1 (s), 128.1 (s), 126.1 (s), 125.9 (s), 124.9 (d, 1J(C,F) =
144.5 (s), 137.6 (s), 135.5 (s), 135.2 (s), 134.2 (s), 130.2 (s), 129.3 (s), 15.0 Hz), 109.4 (d, 1J(C,F) = 3.1 Hz), 101.5 (d, 1J(C,F) = 25.9 Hz),
128.1 (s), 126.0 (s), 125.9 (s), 115.4 (s), 113.7 (s), 113.1 (s), 55.9 (s), 55.5 (s), 48.7 (s), 34.4 (s), 30.3 (s). 19F NMR (376 MHz, CDCl3, 25 °C,
55.7 (s), 52.1 (s), 36.9 (s), 34.3 (s), 30.3 (s). HRMS (ESI) m/z: calcd. For TMS): δ = 114.4 (s). HRMS (ESI) m/z: calcd. For C28H34FO2 [M + H] + :
C32H41O3 [M + H] + : 473.3051, found: 473.3044. 421.2538, found: 421.2531.
4-((2-Bromo-4,5-dimethoxyphenyl)(phenyl)methyl)-2,6-di-tert-butyl 2,6-Di-tert-butyl-4-((2-chloro-4-methoxyphenyl)(phenyl) meth-
phenol (4 m). According to the general procedure, work-up and yl)phenol (4 r). According to the general procedure, work-up and
flash column chromatography (Rf = 0.4, Hexane/EtOAc: 20 : 1), flash column chromatography (Rf = 0.5, Hexane/EtOAc: 20 : 1),
product 4 m (74.7 mg, 0.146 mmol, 73%) was obtained as a yellow product 4 r (71.7 mg, 0.164 mmol, 82%) was obtained as a yellow
oil. 1H NMR (400 MHz, CDCl3, 25 °C, TMS): δ = 7.25–7.29 (m, 2 H), oil. 1H NMR (400 MHz, CDCl3, 25 °C, TMS): δ = 7.24–7.28 (m, 2 H),
7.17–7.21 (m, 1 H), 7.07–7.09 (m, 2 H), 7.03 (s, 1 H), 6.89 (s, 2 H), 6.49 7.16–7.20 (m, 1 H), 7.06–7.08 (m, 2 H), 6.92–6.93 (m, 1 H), 6.85–6.87
(s, 1 H), 5.75 (s, 1 H), 5.09 (s, 1 H), 3.85 (s, 3 H), 3.63 (s, 3 H), 1.36 (s, (m, 3 H), 6.71–6.73 (m, 1 H), 5.78 (s, 1 H), 5.07 (s, 1 H), 3.77 (s, 3 H),
18 H). 13C NMR (100 MHz, CDCl3, 25 °C, TMS): δ = 152.2 (s), 148.0 (s), 1.35 (s, 18 H). 13C NMR (100 MHz, CDCl3, 25 °C, TMS): δ = 158.4 (s),
147.9 (s), 143.6 (s), 136.1 (s), 135.6 (s), 133.3 (s), 129.3 (s), 128.2 (s), 152.1 (s), 143.7 (s), 135.5 (s), 134.8 (s), 134.7 (s), 133.3 (s), 131.5 (s),
126.2 (s), 126.1 (s), 115.5 (s), 115.3 (s), 114.0 (s), 56.1 (s), 55.8 (s), 129.4 (s), 128.1 (s), 126.2 (s), 126.1 (s), 114.7 (s), 112.6 (s), 55.5 (s),
55.4 (s), 34.4 (s), 30.4 (s). HRMS (ESI) m/z: calcd. For C29H36BrO3 [M + 52.6 (s), 34.4 (s), 30.4 (s). HRMS (ESI) m/z: calcd. For C28H34ClO2 [M +
H] + : 511.1843, found: 511.1835. H] + : 437.2242, found: 437.2237.
2,6-Di-tert-butyl-4-((3-fluoro-4-methoxyphenyl)(phenyl) meth- 4-((2-Bromo-4-methoxyphenyl)(phenyl)methyl)-2,6-di-tert-butylphe-
yl)phenol (4 n). According to the general procedure, work-up and nol (4 s). According to the general procedure, work-up and flash
flash column chromatography (Rf = 0.4, Hexane/EtOAc: 20 : 1), column chromatography (Rf = 0.5, Hexane/EtOAc: 20 : 1), product 4 s
product 4 n (63.9 mg, 0.152 mmol, 76%) was obtained as a yellow (80.9 mg, 0.168 mmol, 84%) was obtained as a yellow oil. 1H NMR
oil. 1H NMR (400 MHz, CDCl3, 25 °C, TMS): δ = 7.25–7.29 (m, 2 H), (400 MHz, CDCl3, 25 °C, TMS): δ = 7.24–7.28 (m, 2 H), 7.16–7.20 (m,
7.17–7.21 (m, 1 H), 7.09–7.10 (m, 2 H), 6.79–6.88 (m, 5 H), 5.36 (s, 1 H), 7.11–7.12 (m, 1 H), 7.06–7.07 (m, 2 H), 6.85–6.87 (m, 3 H), 6.75–
1 H), 5.09 (s, 1 H), 3.86 (s, 3 H), 1.36 (s, 18 H). 13C NMR (100 MHz, 6.78 (m, 1 H), 5.76 (s, 1 H), 5.07 (s, 1 H), 3.77 (s, 3 H), 1.35 (s, 18 H).
CDCl3, 25 °C, TMS): δ = 152.2 (d, 1J(C,F) = 243.6 Hz), 152.2 (s), 145.8 13
C NMR (100 MHz, CDCl3, 25 °C, TMS): δ = 158.3 (s), 152.1 (s),
(d, 1J(C,F) = 10.7 Hz), 144.4 (s), 138.2 (d, 1J(C,F) = 5.4 Hz), 135.6 (s), 143.7 (s), 136.3 (s), 135.5 (s), 133.4 (s), 131.5 (s), 129.5 (s), 128.1 (s),
133.9 (s), 129.3 (s), 128.2 (s), 126.2 (s), 125.9 (s), 124.9 (d, 1J(C,F) = 126.2 (s), 126.1 (s), 125.5 (s), 118.0 (s), 113.3 (s), 55.5 (s), 55.1 (s),
3.3 Hz), 117.1 (d, 1J(C,F) = 18.5 Hz), 113.0 (s), 56.3 (s), 55.9 (s), 34.4 (s), 34.4 (s), 30.4 (s). HRMS (ESI) m/z: calcd. For C28H34BrO2 [M + H] + :
30.3 (s). 19F NMR (376 MHz, CDCl3, 25 °C, TMS): δ = 135.6 (s). HRMS 481.1737, found: 481.1731.
(ESI) m/z: calcd. For C28H34FO2 [M + H] + : 421.2538, found: 421.2532.
2,6-Di-tert-butyl-4-((2-iodo-4-methoxyphenyl)(phenyl) meth-
2,6-Di-tert-butyl-4-((3-chloro-4-methoxyphenyl)(phenyl) meth- yl)phenol (4 t). According to the general procedure, work-up and
yl)phenol (4 o). According to the general procedure, work-up and flash column chromatography (Rf = 0.5, Hexane/EtOAc: 20 : 1),
flash column chromatography (Rf = 0.4, Hexane/EtOAc: 20 : 1), product 4 t (94.1 mg, 0.178 mmol, 89%) was obtained as a yellow
product 4 o (69.0 mg, 0.158 mmol, 79%) was obtained as a yellow oil. 1H NMR (400 MHz, CDCl3, 25 °C, TMS): δ = 7.39–7.40 (m, 1 H),
solid. 1H NMR (400 MHz, CDCl3, 25 °C, TMS): δ = 7.28–7.29 (m, 2 H), 7.24–7.28 (m, 2 H), 7.19–7.20 (m, 1 H), 7.05–7.07 (m, 2 H), 6.82–6.85
7.20–7.21 (m, 1 H), 7.14–7.15 (m, 1 H), 7.08–7.10 (m, 2 H), 6.93–6.95 (m, 4 H), 5.64 (m, 1 H), 5.07 (s, 1 H), 3.76 (s, 3 H), 1.35 (s, 18 H).
13
(m, 1 H), 6.88 (s, 2 H), 6.82–6.84 (m, 1 H), 5.35 (s, 1 H), 5.09 (s, 1 H), C NMR (100 MHz, CDCl3, 25 °C, TMS): δ = 158.1 (s), 152.1 (s),
3.87 (s, 3 H), 1.36 (s, 18 H). 13C NMR (100 MHz, CDCl3, 25 °C, TMS): 143.7 (s), 139.5 (s), 135.5 (s), 133.6 (s), 130.7 (s), 129.7 (s), 128.1 (s),
δ = 153.2 (s), 152.2 (s), 144.4 (s), 138.2 (s), 135.6 (s), 133.8 (s), 126.3 (s), 126.1 (s), 124.6 (s), 114.1 (s), 102.3 (s), 59.7 (s), 55.5 (s),
131.1 (s), 129.3 (s), 128.5 (s), 128.2 (s), 126.2 (s), 125.9 (s), 122.0 (s), 34.4 (s), 30.4 (s). HRMS (ESI) m/z: calcd. For C28H34IO2 [M + H] + :
111.7 (s), 56.2 (s), 55.8 (s), 34.4 (s), 30.3 (s). HRMS (ESI) m/z: calcd. For 529.1598, found: 529.1593.
C28H34ClO2 [M + H] + : 437.2242, found: 437.2238.
2,6-Di-tert-butyl-4-((6-methoxy-[1,1’-biphenyl]-3-yl)(phenyl) meth-
4-((3-Bromo-4-methoxyphenyl)(phenyl)methyl)-2,6-di-tert-butylphe- yl)phenol (4 u). According to the general procedure, work-up and
nol (4 p). According to the general procedure, work-up and flash flash column chromatography (Rf = 0.5, Hexane/EtOAc: 20 : 1),
column chromatography (Rf = 0.4, Hexane/EtOAc: 20 : 1), product 4 p product 4 u (89.0 mg, 0.186 mmol, 93%) was obtained as a yellow
(69.3 mg, 0.144 mmol, 72%) was obtained as a yellow oil. 1H NMR oil. 1H NMR (400 MHz, CDCl3, 25 °C, TMS): δ = 7.46–7.48 (m, 2 H),
(400 MHz, CDCl3, 25 °C, TMS): δ = 7.32–7.33 (m, 1 H), 7.25–7.29 (m, 7.34–7.38 (m, 2 H), 7.24–7.29 (m, 3 H), 7.11–7.19 (m, 4 H), 7.01–7.04
2 H), 7.17–7.21 (m, 1 H), 7.08–7.10 (m, 2 H), 6.97–6.99 (m, 1 H), 6.88 (m, 1 H), 6.94 (s, 2 H), 6.87–6.89 (m, 1 H), 5.42 (s, 1 H), 5.07 (s, 1 H),
(s, 2 H), 6.79–6.81 (m, 1 H), 5.35 (s, 1 H), 5.09 (s, 1 H), 3.86 (s, 3 H), 3.78 (s, 3 H), 1.36 (s, 18 H). 13C NMR (100 MHz, CDCl3, 25 °C, TMS):
1.36 (s, 18 H). 13C NMR (100 MHz, CDCl3, 25 °C, TMS): δ = 154.1 (s), δ = 154.8 (s), 152.1 (s), 145.1 (s), 138.7 (s), 137.2 (s), 135.4 (s),
152.2 (s), 144.4 (s), 138.7 (s), 135.6 (s), 134.1 (s), 133.8 (s), 132.0 (s), 134.4 (s), 132.0 (s), 130.2 (s), 129.6 (s), 129.3 (s), 129.3 (s), 128.1 (s),
129.3 (s), 128.3 (s), 126.2 (s), 125.9 (s), 111.6 (s), 111.4 (s), 56.2 (s), 127.9 (s), 126.8 (s), 126.0 (s), 125.9 (s), 110.9 (s), 56.1 (s), 55.6 (s),
55.7 (s), 34.4 (s), 30.3 (s). HRMS (ESI) m/z: calcd. For C28H34BrO2 [M + 34.4 (s), 30.4 (s). HRMS (ESI) m/z: calcd. For C34H39O2 [M + H] + :
H] + : 481.1737, found: 481.1732. 479.2945, found: 479.2937.
2,6-Di-tert-butyl-4-((2-fluoro-4-methoxyphenyl)(phenyl) meth- 5-((3,5-Di-tert-butyl-4-hydroxyphenyl)(phenyl)methyl)-2-methoxy
yl)phenol (4 q). According to the general procedure, work-up and benzaldehyde (4 v). According to the general procedure, work-up
flash column chromatography (Rf = 0.5, Hexane/EtOAc: 20 : 1), and flash column chromatography (Rf = 0.5, Hexane/EtOAc: 20 : 1),
product 4 q (68.1 mg, 0.162 mmol, 81%) was obtained as a yellow product 4 v (59.4 mg, 0.138 mmol, 69%) was obtained as a yellow
oil. 1H NMR (400 MHz, CDCl3, 25 °C, TMS): δ = 7.16–7.28 (m, 3 H), oil. 1H NMR (400 MHz, CDCl3, 25 °C, TMS): δ = 10.42 (s, 1 H), 7.64–
7.05–7.10 (m, 2 H), 6.78–6.89 (m, 3 H), 6.51–6.61 (m, 2 H), 5.65 (s, 7.65 (m, 1 H), 7.26–7.31 (m, 3 H), 7.17–7.21 (m, 1 H), 7.08–7.09 (m,
1 H), 5.07 (s, 1 H), 3.77 (s, 3 H), 1.36 (s, 18 H). 13C NMR (100 MHz, 2 H), 6.87–6.92 (m, 3 H), 5.41 (s, 1 H), 5.09 (s, 1 H), 3.91 (s, 3 H), 1.35
CDCl3, 25 °C, TMS): δ = 161.1 (d, 1J(C,F) = 244.7 Hz), 159.3 (d, 1J(C,F) = (s, 18 H). 13C NMR (100 MHz, CDCl3, 25 °C, TMS): δ = 190.0 (s),
10.8 Hz), 152.2 (s), 143.9 (s), 135.5 (s), 133.1 (s), 131.1 (d, 1J(C,F) = 160.3 (s), 152.2 (s), 144.2 (s), 137.4 (s), 136.7 (s), 135.6 (s), 133.7 (s),
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Research Article
129.3 (s), 129.2 (s), 128.3 (s), 126.2 (s), 125.9 (s), 124.4 (s), 111.5 (s), 56.1 (s), 55.9 (s), 34.4 (s), 30.4 (s). HRMS (ESI) m/z: calcd. For C30H35O2
55.9 (s), 55.7 (s), 34.4 (s), 30.3 (s). HRMS (ESI) m/z: calcd. For C29H35O3 [M + H] + : 427.2632, found: 427.2627.
[M + H] + : 431.2581, found: 431.2575.
2,6-Di-tert-butyl-4-((4-phenoxyphenyl)(phenyl)methyl) phenol
2,6-Di-tert-butyl-4-((4-ethoxyphenyl)(phenyl)methyl)phenol (4 w). (4 ab). According to the general procedure, work-up and flash
According to the general procedure, work-up and flash column column chromatography (Rf = 0.4, Hexane/EtOAc: 20 : 1), product
chromatography (Rf = 0.4, Hexane/EtOAc: 20 : 1), product 4 w 4 ab (79.9 mg, 0.172 mmol, 86%) was obtained as a yellow oil.
(76.7 mg, 0.184 mmol, 92%) was obtained as a yellow oil. 1H NMR 1
H NMR (400 MHz, CDCl3, 25 °C, TMS): δ = 7.29–7.33 (m, 3 H), 7.26–
(400 MHz, CDCl3, 25 °C, TMS): δ = 7.24–7.27 (m, 2 H), 7.15–7.19 (m, 7.27 (m, 1 H), 7.18–7.22 (m, 1 H), 7.12–7.14 (m, 2 H), 7.05–7.08 (m,
1 H), 7.10–7.12 (m, 2 H), 7.00–7.02 (m, 2 H), 6.90 (s, 2 H), 6.79–6.81 3 H), 6.98–7.00 (m, 2 H), 6.90–6.93 (m, 4 H), 5.43 (s, 1 H), 5.09 (s, 1 H),
(m, 2 H), 5.39 (s, 1 H), 5.07 (s, 1 H), 3.97-4.02 (m, 2 H), 1.35–1.41 (m, 1.36 (s, 18 H). 13C NMR (100 MHz, CDCl3, 25 °C, TMS): δ = 157.5 (s),
3 H), 1.35 (s, 18 H). 13C NMR (100 MHz, CDCl3, 25 °C, TMS): δ = 155.2 (s), 152.1 (s), 144.8 (s), 139.9 (s), 135.5 (s), 134.2 (s), 130.6 (s),
157.2 (s), 152.0 (s), 145.2 (s), 137.0 (s), 135.4 (s), 134.5 (s), 130.3 (s), 129.7 (s), 129.4 (s), 128.2 (s), 126.1 (s), 126.0 (s), 123.0 (s), 118.8 (s),
129.4 (s), 128.1 (s), 126.0 (s), 126.0 (s), 114.1 (s), 63.4 (s), 56.0 (s), 118.6 (s), 56.1 (s), 34.4 (s), 30.3 (s). HRMS (ESI) m/z: calcd. For
34.4 (s), 30.4 (s), 15.0 (s). HRMS (ESI) m/z: calcd. For C29H37O2 [M + C33H37O2 [M + H] + : 465.2789, found: 465.2782.
H] + : 417.2789, found: 417.2785.
2,6-Di-tert-butyl-4-((4-hydroxyphenyl)(phenyl)methyl) phenol (6 a).
2,6-Di-tert-butyl-4-(phenyl(4-propoxyphenyl)methyl)phenol (4 x). According to the general procedure, work-up and flash column
According to the general procedure, work-up and flash column chromatography (Rf = 0.4, Hexane/EtOAc: 10 : 1), product 6 a (4 h,
chromatography (Rf = 0.5, Hexane/EtOAc: 20 : 1), product 4 x 69.9 mg, 0.180 mmol, 90%) was obtained as a colorless oil.[14c]
(80.9 mg, 0.188 mmol, 94%) was obtained as a yellow oil. 1H NMR 1
H NMR (400 MHz, CDCl3, 25 °C, TMS): δ = 7.24–7.28 (m, 2 H), 7.16–
(400 MHz, CDCl3, 25 °C, TMS): δ = 7.23–7.27 (m, 2 H), 7.15–7.19 (m, 7.19 (m, 1 H), 7.09–7.11 (m, 2 H), 6.96–6.98 (m, 2 H), 6.89 (s, 2 H),
1 H), 7.10–7.12 (m, 2 H), 7.00–7.02 (m, 2 H), 6.90 (s, 2 H), 6.79–6.81 6.72–6.74 (m, 2 H), 5.37 (s, 1 H), 5.06 (s, 1 H), 4.70 (s, 1 H), 1.35 (s,
(m, 2 H), 5.38 (s, 1 H), 5.07 (s, 1 H), 3.89 (t, J = 6.6 Hz, 2 H), 1.74–1.83 18 H). 13C NMR (100 MHz, CDCl3, 25 °C, TMS): δ = 153.7 (s), 152.0 (s),
(m, 2 H), 1.36 (s, 18 H), 1.02 (t, J = 7.4 Hz, 3 H). 13C NMR (100 MHz, 145.1 (s), 137.3 (s), 135.4 (s), 134.4 (s), 130.6 (s), 130.5 (s), 129.3 (s),
CDCl3, 25 °C, TMS): δ = 157.4 (s), 152.0 (s), 145.3 (s), 136.9 (s), 128.1 (s), 126.0 (s), 114.9 (s), 56.0 (s), 34.3 (s), 30.3 (s).
135.4 (s), 134.5 (s), 130.3 (s), 129.4 (s), 128.1 (s), 126.0 (s), 125.9 (s),
114.1 (s), 69.5 (s), 56.0 (s), 34.4 (s), 30.4 (s), 22.7 (s), 10.6 (s). HRMS 2,6-Di-tert-butyl-4-((4-hydroxy-3-methylphenyl)(phenyl) meth-
(ESI) m/z: calcd. For C30H39O2 [M + H] + : 431.2945, found: 431.2940. yl)phenol (6 b). According to the general procedure, work-up and
flash column chromatography (Rf = 0.4, Hexane/EtOAc: 10 : 1),
4-((4-(Benzyloxy)phenyl)(phenyl)methyl)-2,6-di-tert-butyl phenol product 6 b (4 h, 71.7 mg, 0.178 mmol, 89%) was obtained as a
(4 y). According to the general procedure, work-up and flash colorless oil.[14c] 1H NMR (400 MHz, CDCl3, 25 °C, TMS): δ = 7.24–7.27
column chromatography (Rf = 0.4, Hexane/EtOAc: 20 : 1), product 4 y (m, 2 H), 7.15–7.19 (m, 1 H), 7.09–7.11 (m, 2 H), 6.90 (s, 3 H), 6.76–
(82.3 mg, 0.172 mmol, 86%) was obtained as a yellow oil. 1H NMR 6.79 (m, 1 H), 6.65–6.67 (m, 1 H), 5.34 (s, 1 H), 5.06 (s, 1 H), 4.60 (s,
(400 MHz, CDCl3, 25 °C, TMS): δ = 7.40–7.42 (m, 2 H), 7.34–7.37 (m, 1 H), 2.18 (s, 3 H), 1.36 (s, 18 H). 13C NMR (100 MHz, CDCl3, 25 °C,
2 H), 7.23–7.31 (m, 3 H), 7.17–7.18 (m, 1 H), 7.10–7.12 (m, 2 H), 7.01– TMS): δ = 152.0 (s), 152.0 (s), 145.3 (s), 137.1 (s), 135.4 (s), 134.5 (s),
7.03 (m, 2 H), 6.87–6.89 (m, 4 H), 5.39 (s, 1 H), 5.06 (s, 1 H), 5.02 (s, 132.1 (s), 129.3 (s), 128.1 (s), 127.9 (s), 126.0 (s), 125.9 (s), 123.3 (s),
2 H), 1.35 (s, 18 H). 13C NMR (100 MHz, CDCl3, 25 °C, TMS): δ = 114.6 (s), 56.1 (s), 34.4 (s), 30.4 (s), 15.9 (s).
157.1 (s), 152.1 (s), 145.2 (s), 137.4 (s), 137.2 (s), 135.5 (s), 134.5 (s),
130.4 (s), 129.4 (s), 128.6 (s), 128.2 (s), 127.9 (s), 127.6 (s), 126.0 (s), 4-((3-Bromo-4-hydroxyphenyl)(phenyl)methyl)-2,6-di-tert-butyl
126.0 (s), 114.5 (s), 70.1 (s), 56.1 (s), 34.4 (s), 30.4 (s). HRMS (ESI) m/z: phenol (6 c). According to the general procedure, work-up and flash
calcd. For C34H39O2 [M + H] + : 479.2945, found: 479.2939. column chromatography (Rf = 0.4, Hexane/EtOAc: 20 : 1), product 6 c
(4 h, 74.8 mg, 0.160 mmol, 80%) was obtained as a colorless oil.
1
4-((4-(Allyloxy)phenyl)(phenyl)methyl)-2,6-di-tert-butyl phenol (4 z). H NMR (400 MHz, CDCl3, 25 °C, TMS): δ = 7.24–7.29 (m, 2 H), 7.18–
According to the general procedure, work-up and flash column 7.22 (m, 2 H), 7.08–7.10 (m, 2 H), 6.91–6.96 (m, 2 H), 6.87 (s, 2 H),
chromatography (Rf = 0.4, Hexane/EtOAc: 20 : 1), product 4 z 5.41 (s, 1 H), 5.35 (s, 1 H), 5.09 (s, 1 H), 1.36 (s, 18 H). 13C NMR
(66.9 mg, 0.156 mmol, 78%) was obtained as a yellow oil. 1H NMR (100 MHz, CDCl3, 25 °C, TMS): δ = 152.3 (s), 150.4 (s), 144.4 (s),
(400 MHz, CDCl3, 25 °C, TMS): δ = 7.24–7.28 (m, 2 H), 7.15–7.19 (m, 138.8 (s), 135.6 (s), 133.7 (s), 132.6 (s), 130.2 (s), 129.3 (s), 128.3 (s),
1 H), 7.09–7.11 (m, 2 H), 7.00–7.02 (m, 2 H), 6.89 (s, 2 H), 6.81–6.83 126.3 (s), 125.9 (s), 115.6 (s), 110.0 (s), 55.7 (s), 34.4 (s), 30.3 (s). HRMS
(m, 2 H), 6.00–6.10 (m, 1 H), 5.40 (d, J = 6.8 Hz, 2 H), 5.26 (d, J = (ESI) m/z: calcd. For C27H32BrO2 [M + H] + : 467.1581, found: 467.1574.
5.2 Hz, 1 H), 5.06 (s, 1 H), 4.50 (d, J = 2.6 Hz, 2 H), 1.35 (s, 18 H).
13
C NMR (100 MHz, CDCl3, 25 °C, TMS): δ = 156.9 (s), 152.0 (s), 1-((3,5-Di-tert-butyl-4-hydroxyphenyl)(phenyl)methyl) naphthalen-
145.2 (s), 137.3 (s), 135.4 (s), 134.5 (s), 133.5 (s), 130.3 (s), 129.4 (s), 2-ol (6 d). According to the general procedure, work-up and flash
128.1 (s), 126.0 (s), 125.9 (s), 117.6 (s), 114.3 (s), 68.9 (s), 56.0 (s), column chromatography (Rf = 0.4, Hexane/EtOAc: 10 : 1), product 6 d
34.4 (s), 30.4 (s). HRMS (ESI) m/z: calcd. For C30H37O2 [M + H] + : (4 h, 66.7 mg, 0.152 mmol, 76%) was obtained as a yellow solid.[14b]
1
429.2789, found: 429.2781. H NMR (400 MHz, CDCl3, 25 °C, TMS): δ = 8.01–8.03 (m, 1 H), 7.71–
7.79 (m, 2 H), 7.40–7.44 (m, 1 H), 7.23–7.33 (m, 6 H), 7.06–7.08 (m,
2,6-Di-tert-butyl-4-(phenyl(4-(prop-2-yn-1-yloxy)phenyl) meth- 1 H), 7.01 (s, 2 H), 6.29 (s, 1 H), 5.39 (s, 1 H), 5.20 (s, 1 H), 1.32 (s,
yl)phenol (4 aa). According to the general procedure, work-up and 18 H). 13C NMR (100 MHz, CDCl3, 25 °C, TMS): δ = 153.1 (s), 153.0 (s),
flash column chromatography (Rf = 0.4, Hexane/EtOAc: 20 : 1), 142.1 (s), 136.8 (s), 133.5 (s), 131.8 (s), 129.6 (s), 129.5 (s), 129.0 (s),
product 4 aa (63.1 mg, 0.148 mmol, 74%) was obtained as a yellow 128.9 (s), 128.7 (s), 126.9 (s), 126.7 (s), 125.7 (s), 123.0 (s), 122.9 (s),
oil. 1H NMR (400 MHz, CDCl3, 25 °C, TMS): δ = 7.24–7.28 (m, 2 H), 120.3 (s), 120.0 (s), 48.6 (s), 34.4 (s), 30.2 (s).
7.15–7.19 (m, 1 H), 7.09–7.11 (m, 2 H), 7.03–7.05 (m, 2 H), 6.87–6.89
(m, 4 H), 5.39 (s, 1 H), 5.06 (s, 1 H), 4.65 (d, J = 1.2 Hz, 2 H), 2.49 (s, 4-((1H-indol-3-yl)(phenyl)methyl)-2,6-di-tert-butylphenol (6 e). Ac-
1 H), 1.35 (s, 18 H). 13C NMR (100 MHz, CDCl3, 25 °C, TMS): δ = cording to the general procedure, work-up and flash column
155.9 (s), 152.1 (s), 145.0 (s), 138.1 (s), 135.5 (s), 134.4 (s), 130.4 (s), chromatography (Rf = 0.5, Hexane/EtOAc: 10 : 1), product 6 e
129.4 (s), 128.2 (s), 126.0 (s), 126.0 (s), 114.6 (s), 78.8 (s), 75.4 (s), (74.9 mg, 0.182 mmol, 91%) was obtained as a white solid.[14a]
1
H NMR (400 MHz, CDCl3, 25 °C, TMS): δ = 7.86 (s, 1 H), 7.29–7.31 (m,
1 H), 7.11–7.25 (m, 7 H), 7.04 (s, 2 H), 6.94–6.98 (m, 1 H), 6.57–6.58
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Research Article
(m, 1 H), 5.56 (s, 1 H), 5.04 (s, 1 H), 1.36 (s, 18 H). 13C NMR (100 MHz, 2,6-Di-tert-butyl-4-((4-(diethylamino)-2-methylphenyl)
CDCl3, 25 °C, TMS): δ = 152.1 (s), 144.7 (s), 136.7 (s), 135.4 (s), (phenyl)methyl)phenol (6 k). According to the general procedure,
134.5 (s), 129.0 (s), 128.2 (s), 127.2 (s), 126.0 (s), 125.6 (s), 123.9 (s), work-up and flash column chromatography (Rf = 0.5, Hexane/EtOAc:
122.0 (s), 120.8 (s), 120.1 (s), 119.3 (s), 111.0 (s), 48.9 (s), 34.4 (s), 10 : 1), product 6 k (10 h,76.0 mg, 0.166 mmol, 83%) was obtained as
30.4 (s). a colorless oil. 1H NMR (400 MHz, CDCl3, 25 °C, TMS): δ = 7.21–7.25
(m, 2 H), 7.13–7.16 (m, 1 H), 7.07–7.09 (m, 2 H), 6.86 (s, 2 H), 6.62–
2,6-Di-tert-butyl-4-((5-methoxy-1H-indol-3-yl)(phenyl) meth- 6.64 (m, 1 H), 6.43–6.49 (m, 2 H), 5.44 (s, 1 H), 5.02 (s, 1 H), 3.28–3.33
yl)phenol (6 f). According to the general procedure, work-up and (m, 4 H), 2.16 (s, 3 H), 1.35 (s, 18 H), 1.13 (t, J = 7.0 Hz, 6 H). 13C NMR
flash column chromatography (Rf = 0.4, Hexane/EtOAc: 10 : 1), (100 MHz, CDCl3, 25 °C, TMS): δ = 151.8 (s), 146.2 (s), 145.2 (s),
product 6 f (79.5 mg, 0.180 mmol, 90%) was obtained as a white 137.2 (s), 135.2 (s), 134.6 (s), 130.6 (s), 130.1 (s), 129.4 (s), 128.0 (s),
solid.[14a] 1H NMR (400 MHz, CDCl3, 25 °C, TMS): δ = 7.80 (s, 1 H), 126.3 (s), 125.6 (s), 114.1 (s), 109.4 (s), 52.8 (s), 44.3 (s), 34.3 (s),
7.25–7.26 (m, 4 H), 7.16–7.20 (m, 2 H), 7.05 (s, 2 H), 6.77–6.80 (m, 30.4 (s), 20.7 (s), 12.7 (s). HRMS (ESI) m/z: calcd. For C32H44NO [M +
1 H), 6.57–6.58 (m, 2 H), 5.50 (s, 1 H), 5.05 (s, 1 H), 3.64 (s, 3 H), 1.35 H] + : 458.3418, found: 458.3411.
(s, 18 H). 13C NMR (100 MHz, CDCl3, 25 °C, TMS): δ = 153.6 (s),
152.0 (s), 144.6 (s), 135.4 (s), 134.5 (s), 131.9 (s), 129.0 (s), 128.2 (s), 2,6-Di-tert-butyl-4-(phenyl(phenylamino)methyl)phenol (6 l). Ac-
127.6 (s), 126.0 (s), 125.6 (s), 124.6 (s), 120.6 (s), 112.0 (s), 111.6 (s), cording to the general procedure, work-up and flash column
102.1 (s), 55.7 (s), 49.0 (s), 34.4 (s), 30.4 (s). chromatography (Rf = 0.4, Hexane/EtOAc: 10 : 1), product 6 l (8 h,
67.4 mg, 0.174 mmol, 87%) was obtained as a colorless oil. 1H NMR
2,6-Di-tert-butyl-4-((4-methoxy-1H-indol-3-yl)(phenyl) meth- (400 MHz, CDCl3, 25 °C, TMS): δ = 7.39–7.41 (m, 2 H), 7.30–7.34 (m,
yl)phenol (6 g). According to the general procedure, work-up and 2 H), 7.19–7.25 (m, 1 H), 7.07–7.12 (m, 4 H), 6.65–6.68 (m, 1 H), 6.53–
flash column chromatography (Rf = 0.5, Hexane/EtOAc: 10 : 1), 6.55 (m, 2 H), 5.40 (s, 1 H), 5.16 (s, 1 H), 4.24 (s, 1 H), 1.38 (s, 18 H).
product 6 g (81.3 mg, 0.184 mmol, 92%) was obtained as a white 13
C NMR (100 MHz, CDCl3, 25 °C, TMS): δ = 153.0 (s), 147.7 (s),
solid.[14a] 1H NMR (400 MHz, CDCl3, 25 °C, TMS): δ = 7.87 (s, 1 H), 143.1 (s), 136.0 (s), 134.1 (s), 129.1 (s), 128.6 (s), 127.1 (s), 126.9 (s),
7.18–7.24 (m, 4 H), 7.10–7.14 (m, 1 H), 7.01–7.06 (m, 3 H), 6.92–6.94 124.6 (s), 117.3 (s), 113.4 (s), 63.2 (s), 34.4 (s), 30.3 (s). HRMS (ESI)
(m, 1 H), 6.38–6.44 (m, 2 H), 5.97 (s, 1 H), 5.00 (s, 1 H), 3.58 (s, 3 H), m/z: calcd. For C27H34NO [M + H] + : 388.2635, found: 388.2631.
1.36 (s, 18 H). 13C NMR (100 MHz, CDCl3, 25 °C, TMS): δ = 155.0 (s),
151.7 (s), 146.0 (s), 138.2 (s), 135.6 (s), 135.1 (s), 129.0 (s), 127.7 (s), 2,6-Di-tert-butyl-4-((1-methoxynaphthalen-2-yl)(phenyl) meth-
125.7 (s), 125.3 (s), 122.8 (s), 122.5 (s), 121.7 (s), 117.6 (s), 104.2 (s), yl)phenol (6 m). According to the general procedure, work-up and
100.1 (s), 55.1 (s), 49.3 (s), 34.3 (s), 30.4 (s). flash column chromatography (Rf = 0.5, Hexane/EtOAc: 10 : 1),
product 6 m (68.8 mg, 0.152 mmol, 76%) was obtained as a yellow
2,6-Di-tert-butyl-4-((5-nitro-1H-indol-3-yl)(phenyl)methyl) phenol oil. 1H NMR (400 MHz, CDCl3, 25 °C, TMS): δ = 8.28–8.30 (m, 1 H),
(6 h). According to the general procedure, work-up and flash 7.95–7.97 (m, 1 H), 7.39–7.44 (m, 2 H), 7.22–7.25 (m, 2 H), 7.10–7.18
column chromatography (Rf = 0.5, Hexane/EtOAc: 10 : 1), product 6 h (m, 3 H), 6.89–6.93 (m, 2 H), 6.82–6.84 (m, 1 H), 6.70–6.72 (m, 1 H),
(78.5 mg, 0.172 mmol, 86%) was obtained as a white solid.[14a] 6.07 (s, 1 H), 5.07 (s, 1 H), 3.97 (s, 3 H), 1.34 (s, 18 H). 13C NMR
1
H NMR (400 MHz, CDCl3, 25 °C, TMS): δ = 8.51 (s, 1 H), 8.16–7.17 (m, (100 MHz, CDCl3, 25 °C, TMS): δ = 154.2 (s), 152.0 (s), 144.8 (s),
1 H), 8.03–8.05 (m, 1 H), 7.20–7.35 (m, 6 H), 7.03 (s, 2 H), 6.79–6.80 135.4 (s), 134.3 (s), 132.8 (s), 132.8 (s), 129.4 (s), 128.2 (s), 127.4 (s),
(m, 1 H), 5.59 (s, 1 H), 5.11 (s, 1 H), 1.36 (s, 18 H). 13C NMR (100 MHz,
126.4 (s), 126.0 (s), 126.0 (s), 125.9 (s), 124.7 (s), 124.3 (s), 122.4 (s),
CDCl3, 25 °C, TMS): δ = 13C{1H} NMR (100 MHz, CDCl3, 25 °C, TMS): δ =
103.0 (s), 55.4 (s), 52.7 (s), 34.3 (s), 30.4 (s). HRMS (ESI) m/z: calcd. For
152.4 (s), 143.8 (s), 141.4 (s), 139.8 (s), 135.8 (s), 133.6 (s), 128.8 (s), C32H37O2 [M + H] + : 453.2789, found: 453.2783.
128.4 (s), 126.9 (s), 126.6 (s), 126.5 (s), 125.5 (s), 123.4 (s), 117.7 (s),
117.5 (s), 111.1 (s), 48.5 (s), 34.4 (s), 30.4 (s). 2,6-Di-tert-butyl-4-((2-methoxynaphthalen-1-yl)(phenyl) meth-
yl)phenol (6 n). According to the general procedure, work-up and
2,6-Di-tert-butyl-4-((4-(dimethylamino)phenyl)(phenyl) meth- flash column chromatography (Rf = 0.4, Hexane/EtOAc: 10 : 1),
yl)phenol (6 i). According to the general procedure, work-up and product 6 n (74.2 mg, 0.160 mmol, 80%) was obtained as a yellow
flash column chromatography (Rf = 0.4, Hexane/EtOAc: 10 : 1), oil. 1H NMR (400 MHz, CDCl3, 25 °C, TMS): δ = 7.60–7.65 (m, 2 H),
product 6 i (10 h, 67.3 mg, 0.162 mmol, 81%) was obtained as a 7.42 (s, 1 H), 7.25–7.29 (m, 3 H), 7.14–7.21 (m, 3 H), 7.08–7.10 (m,
colorless oil.[14c] 1H NMR (400 MHz, CDCl3, 25 °C, TMS): δ = 7.23–7.26
2 H), 6.96 (s, 2 H), 5.56 (s, 1 H), 5.09 (s, 1 H), 3.90 (s, 3 H), 1.35 (s,
(m, 2 H), 7.11–7.17 (m, 3 H), 6.96–6.98 (m, 2 H), 6.92 (s, 2 H), 6.66–
18 H). 13C NMR (100 MHz, CDCl3, 25 °C, TMS): δ = 157.4 (s), 152.1 (s),
6.68 (m, 2 H), 5.34 (s, 1 H), 5.04 (s, 1 H), 2.91 (s, 6 H), 1.36 (s, 18 H). 144.8 (s), 140.2 (s), 135.5 (s), 134.2 (s), 133.1 (s), 129.5 (s), 129.4 (s),
13
C NMR (100 MHz, CDCl3, 25 °C, TMS): δ = 151.9 (s), 148.9 (s), 128.9 (s), 128.7 (s), 128.2 (s), 127.5 (s), 126.6 (s), 126.1 (s), 126.0 (s),
145.7 (s), 135.3 (s), 134.8 (s), 133.1 (s), 129.9 (s), 129.4 (s), 128.0 (s), 118.5 (s), 105.6 (s), 56.8 (s), 55.3 (s), 34.4 (s), 30.4 (s). HRMS (ESI) m/z:
126.0 (s), 125.7 (s), 112.6 (s), 56.0 (s), 40.8 (s), 34.3 (s), 30.4 (s). calcd. For C32H37O2 [M + H] + : 453.2789, found: 453.2782.
2,6-Di-tert-butyl-4-((4-(dimethylamino)-2-fluorophenyl) 2,6-Di-tert-butyl-4-((2-methyl-4-(methylthio)phenyl)(phenyl) meth-
(phenyl)methyl)phenol (6 j). According to the general procedure, yl)phenol (6 o). According to the general procedure, work-up and
work-up and flash column chromatography (Rf = 0.4, Hexane/EtOAc: flash column chromatography (Rf = 0.4, Hexane/EtOAc: 10 : 1),
10 : 1), product 6 j (10 h, 65.9 mg, 0.152 mmol, 76%) was obtained as
product 6 o (67.5 mg, 0.156 mmol, 78%) was obtained as a yellow
a colorless oil. 1H NMR (400 MHz, CDCl3, 25 °C, TMS): δ = 7.23–7.27
oil. 1H NMR (400 MHz, CDCl3, 25 °C, TMS): δ = 7.23–7.25 (m, 2 H),
(m, 2 H), 7.15–7.18 (m, 1 H), 7.10–7.12 (m, 2 H), 6.91 (s, 2 H), 6.75– 7.15–7.19 (m, 1 H), 7.04–7.05 (m, 3 H), 6.98–7.01 (m, 1 H), 6.82 (s,
6.79 (m, 1 H), 6.36–6.41 (m, 2 H), 5.61 (s, 1 H), 5.05 (s, 1 H), 2.91 (s, 2 H), 6.73–6.76 (m, 1 H), 5.50 (s, 1 H), 5.07 (s, 1 H), 2.45 (s, 3 H), 2.19
6 H), 1.36 (s, 18 H). 13C NMR (100 MHz, CDCl3, 25 °C, TMS): δ = 161.5 (s, 3 H), 1.34 (s, 18 H). 13C NMR (100 MHz, CDCl3, 25 °C, TMS): δ =
(d, 1J(C,F) = 241.6 Hz), 152.0 (s), 150.6 (d, 1J(C,F) = 10.7 Hz), 144.5 (s), 152.1 (s), 144.0 (s), 140.6 (s), 137.3 (s), 135.5 (s), 135.4 (s), 133.6 (s),
135.4 (s), 133.6 (s), 131.0 (d, 1J(C,F) = 6.3 Hz), 129.1 (s), 128.0 (s), 129.9 (s), 129.5 (s), 128.6 (s), 128.2 (s), 126.2 (s), 126.0 (s), 123.9 (s),
125.9 (s), 125.9 (s), 119.3 (d, 1J(C,F) = 15.4 Hz), 107.8 (s), 99.5 (d, 53.1 (s), 34.4 (s), 30.4 (s), 20.0 (s), 16.0 (s). HRMS (ESI) m/z: calcd. For
1
J(C,F) = 26.9 Hz), 48.7 (s), 40.5 (s), 34.3 (s), 30.4 (s). 19F NMR C29H37OS [M + H] + : 433.2560, found: 433.2552.
(376 MHz, CDCl3, 25 °C, TMS): δ = 116.0 (s). HRMS (ESI) m/z: calcd.
For C29H37FNO [M + H] + : 434.2854, found: 434.2848. 2,6-Di-tert-butyl-4-((5-(methylthio)thiophen-2-yl)(phenyl) meth-
yl)phenol (6 p). According to the general procedure, work-up and
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Research Article
flash column chromatography (Rf = 0.4, Hexane/EtOAc: 40 : 1), 2-(4-((3,5-Di-tert-butyl-4-hydroxyphenyl)(4-methoxyphenyl) meth-
product 6 p (62.0 mg, 0.146 mmol, 73%) was obtained as a yellow yl)benzylidene)malononitrile (7 d). According to the general proce-
oil. 1H NMR (400 MHz, CDCl3, 25 °C, TMS): δ = 7.27–7.31 (m, 2 H), dure, work-up and flash column chromatography (Rf = 0.4, Hexane/
7.21–7.24 (m, 3 H), 7.01 (s, 2 H), 6.89–6.90 (m, 1 H), 6.51–6.52 (m, EtOAc: 10 : 1) gave product 7 d (71.8 mg, 0.150 mmol, 75%) as a
1 H), 5.48 (s, 1 H), 5.11 (s, 1 H), 2.43 (s, 3 H), 1.38 (s, 18 H). 13C NMR yellow oil. 1H NMR (400 MHz, CDCl3, 25 °C, TMS): δ = 7.81–7.83 (m,
(100 MHz, CDCl3, 25 °C, TMS): δ = 152.5 (s), 152.1 (s), 144.2 (s), 2 H), 7.72 (s, 1 H), 7.27–7.29 (m, 2 H), 6.99–7.01 (m, 2 H), 6.83–6.86
135.6 (s), 135.5 (s), 133.7 (s), 131.0 (s), 128.8 (s), 128.3 (s), 126.6 (s), (m, 4 H), 5.44 (s, 1 H), 5.13 (s, 1 H), 3.79 (s, 3 H), 1.36 (s, 18 H).
13
126.4 (s), 125.4 (s), 52.7 (s), 34.4 (s), 30.3 (s), 22.4 (s). HRMS (ESI) m/z: C NMR (100 MHz, CDCl3, 25 °C, TMS): δ = 159.7 (s), 158.3 (s),
calcd. For C26H32OS2 [M + H] + : 425.1967, found: 425.1961 153.5 (s), 152.5 (s), 135.9 (s), 135.3 (s), 132.9 (s), 130.9 (s), 130.6 (s),
130.3 (s), 128.9 (s), 125.8 (s), 114.0 (s), 113.9 (s), 112.9 (s), 81.5 (s),
2,6-Di-tert-butyl-4-((5-methoxythiophen-2-yl)(phenyl) meth- 56.2 (s), 55.3 (s), 34.4 (s), 30.3 (s). HRMS (ESI) m/z: calcd. For
yl)phenol (6 q). According to the general procedure, work-up and C32H35N2O2 [M + H] + : 479.2694, found: 479.2686.
flash column chromatography (Rf = 0.4, Hexane/EtOAc: 40 : 1),
product 6 q (56.4 mg, 0.138 mmol, 69%) was obtained as a yellow 4-((4-(1H-benzo[d]imidazol-2-yl)phenyl)(4-methoxyphenyl) methyl)-
oil. 1H NMR (400 MHz, CDCl3, 25 °C, TMS): δ = 7.20–7.30 (m, 5 H), 2,6-di-tert-butylphenol (7 e). According to the general procedure,
7.01 (s, 2 H), 6.22–6.23 (m, 1 H), 5.97–5.98 (m, 1 H), 5.37 (s, 1 H), 5.09 work-up and flash column chromatography (Rf = 0.3, Hexane/EtOAc:
(s, 1 H), 3.82 (s, 3 H), 1.38 (s, 18 H). 13C NMR (100 MHz, CDCl3, 25 °C, 10 : 1) gave product 7 e (96.5 mg, 0.186 mmol, 93%) as a yellow oil.
1
TMS): δ = 165.4 (s), 152.4 (s), 144.4 (s), 135.5 (s), 135.0 (s), 133.8 (s), H NMR (400 MHz, CDCl3, 25 °C, TMS): δ = 8.06–8.10 (m, 2 H), 7.51 (s,
128.8 (s), 128.2 (s), 126.4 (s), 125.5 (s), 123.2 (s), 102.6 (s), 60.1 (s), 2 H), 7.15–7.19 (m, 4 H), 6.99–7.01 (m, 2 H), 6.88 (s, 2 H), 6.79–6.81
52.6 (s), 34.4 (s), 30.3 (s). HRMS (ESI) m/z: calcd. For C26H32O2S [M + (m, 2 H), 5.39 (s, 1 H), 5.09 (s, 1 H), 3.76 (s, 3 H), 1.33 (s, 18 H).
13
H] + : 409.2196, found: 409.2191. C NMR (100 MHz, CDCl3, 25 °C, TMS): δ = 158.0 (s), 152.2 (s),
152.2 (s), 152.1 (s), 147.8 (s), 136.4 (s), 135.6 (s), 133.9 (s), 130.3 (s),
4-((3,5-Di-tert-butyl-4-hydroxyphenyl)(4-methoxyphenyl) meth- 130.2 (s), 127.6 (s), 127.6 (s), 126.6 (s), 125.9 (s), 122.8 (s), 113.7 (s),
yl)benzyl diphenylphosphinate (7 a). According to the general 55.9 (s), 55.3 (s), 34.4 (s), 30.4 (s). HRMS (ESI) m/z: calcd. For
procedure, work-up and flash column chromatography (Rf = 0.3, C35H39N2O2 [M + H] + : 519.3007, found: 519.3002.
Hexane/EtOAc: 3 : 1) gave product 7 a (98.7 mg, 0.156 mmol, 78%)
as a yellow oil. 1H NMR (400 MHz, CDCl3, 25 °C, TMS): δ = 7.79–7.84 2,6-Di-tert-butyl-4-((4-(di(1H-indol-3-yl)methyl)phenyl)(4-methoxy
(m, 4 H), 7.49–7.52 (m, 2 H), 7.41–7.44 (m, 4 H), 7.25–7.26 (m, 2 H), phenyl)methyl)phenol (7 f). According to the general procedure,
7.08–7.10 (m, 2 H), 7.00–7.02 (m, 2 H), 6.89 (s, 2 H), 6.80–6.82 (m, work-up and flash column chromatography (Rf = 0.3, Hexane/EtOAc:
2 H), 5.37 (s, 1 H), 5.09 (s, 1 H), 5.04 (d, J = 6.4 Hz, 2 H), 3.78 (s, 3 H), 10 : 1) gave product 7 f (94.4 mg, 0.146 mmol, 73%) as a yellow oil.
1.36 (s, 18 H). 13C NMR (100 MHz, CDCl3, 25 °C, TMS): δ = 157.9 (s), 1
H NMR (400 MHz, CDCl3, 25 °C, TMS): δ = 7.81 (s, 2 H), 7.36–7.38 (m,
152.1 (s), 145.4 (s), 136.8 (s), 135.5 (s), 134.2 (s), 134.0 (d, J(C,P) = 2 H), 7.30–7.32 (m, 2 H), 7.21–7.23 (m, 2 H), 7.12–7.16 (m, 2 H), 6.96–
7.5 Hz), 132.2 (d, J(C,P) = 2.7 Hz), 131.7 (d, J(C,P) = 10.1 Hz), 131.4 (d, 7.03 (m, 6 H), 6.87 (s, 2 H), 6.78–6.80 (m, 2 H), 6.60 (s, 2 H), 5.83 (s,
J(C,P) = 135.8 Hz), 130.3 (s), 129.5 (s), 128.5 (d, J(C,P) = 13.1 Hz), 1 H), 5.36 (s, 2 H), 5.03 (s, 1 H), 3.76 (s, 3 H), 1.34 (s, 18 H). 13C NMR
127.7 (s), 125.9 (s), 113.5 (s), 66.2 (d, J(C,P) = 5.5 Hz), 55.8 (s), 55.2 (s), (100 MHz, CDCl3, 25 °C, TMS): δ = 157.8 (s), 151.9 (s), 142.7 (s),
34.4 (s), 30.3 (s). 31P NMR (160 MHz, CDCl3, 25 °C, TMS): δ = 32.2. 141.6 (s), 137.3 (s), 136.7 (s), 135.3 (s), 134.9 (s), 130.4 (s), 129.2 (s),
HRMS (ESI) m/z: calcd. For C41H46O4P [M + H] + : 633.3129, found: 128.5 (s), 127.1 (s), 126.0 (s), 123.6 (s), 121.9 (s), 120.0 (s), 119.9 (s),
633.3124. 119.2 (s), 113.5 (s), 111.0 (s), 55.7 (s), 55.2 (s), 39.8 (s), 34.4 (s),
30.4 (s). HRMS (ESI) m/z: calcd. For C45H47N2O2 [M + H] + : 647.3633,
2,6-Di-tert-butyl-4-((4-(1-hydroxy-2-methylbuta-2,3-dien-1- found: 647.3629.
yl)phenyl)(4-methoxyphenyl)methyl)phenol (7 b). According to the
general procedure, work-up and flash column chromatography 2,6-Di-tert-butyl-4-(hydroxy(phenyl)methyl)phenol (3 a’). According
(Rf = 0.3, Hexane/EtOAc: 10 : 1) gave product 7 b (88.2 mg, to the general procedure, work-up and flash column chromatog-
0.182 mmol, 91%) as a yellow oil. 1H NMR (400 MHz, CDCl3, 25 °C, raphy (Rf = 0.5, Hexane/EtOAc: 20 : 1) gave product 3 a’ (44.4 mg,
TMS): δ = 7.26–7.28 (m, 2 H), 7.08–7.10 (m, 2 H), 7.00–7.02 (m, 2 H), 0.142 mmol, 71%) as a yellow oil. 1H NMR (400 MHz, CDCl3, 25 °C,
6.88 (s, 2 H), 6.79–6.82 (m, 2 H), 5.38 (s, 1 H), 5.06 (s, 2 H), 4.88 (s, TMS): δ = 7.76–7.78 (m, 2 H), 7.73 (s, 2 H), 7.54–7.57 (m, 1 H), 7.45–
2 H), 3.77 (s, 3 H), 2.21 (s, 1 H), 1.56 (t, J = 3.0 Hz, 3 H), 1.35 (s, 18 H). 7.49 (m, 2 H), 5.73 (s, 1 H), 1.45 (s, 18 H). HRMS (ESI) m/z: calcd. For
13
C NMR (100 MHz, CDCl3, 25 °C, TMS): δ = 204.7 (s), 157.9 (s), C21H29O2 [M + H] + : 313.2163, found: 313.2158.
152.1 (s), 144.8 (s), 139.4 (s), 137.0 (s), 135.5 (s), 134.5 (s), 130.3 (s),
129.3 (s), 126.4 (s), 126.0 (s), 113.54 (s), 102.8 (s), 77.8 (s), 74.5 (s), 4-((3,5-Di-tert-butyl-4-hydroxyphenyl)(phenyl)methyl)phen-2,3,5,6-
55.8 (s), 55.2 (s), 34.4 (s), 30.4 (s), 14.7 (s). HRMS (ESI) m/z: calcd. For d4-ol (6 a’). According to the general procedure, work-up and flash
C33H41O3 [M + H] + : 485.3051, found: 485.3045. column chromatography (Rf = 0.5, Hexane/EtOAc: 10 : 1) gave prod-
uct 6 a’ (67.8 mg, 0.172 mmol, 86%) as a yellow oil. 1H NMR
2,6-Di-tert-butyl-4-((4-(1-hydroxy-3-phenylprop-2-yn-1-yl) (400 MHz, CDCl3, 25 °C, TMS): δ = 7.24–7.28 (m, 2 H), 7.16–7.19 (m,
phenyl)(4-methoxyphenyl)methyl)phenol (7 c). According to the 1 H), 7.09–7.11 (m, 2 H), 6.89 (s, 2 H), 5.38 (s, 1 H), 5.07 (s, 1 H), 4.77
general procedure, work-up and flash column chromatography (s, 0.7 H), 1.35 (s, 18 H). 13C NMR (100 MHz, CDCl3, 25 °C, TMS): δ =
(Rf = 0.4, Hexane/EtOAc: 10 : 1) gave product 7 c (87.4 mg, 153.6 (s), 153.6 (s), 152.0 (s), 145.1 (s), 137.1 (s), 135.4 (s), 134.4 h (s),
0.164 mmol, 82%) as a yellow oil. 1H NMR (400 MHz, CDCl3, 25 °C, 129.3 (s), 128.1 (s), 126.0 (s), 114.9 (s), 114.8 (s), 55.9 (s), 34.4 (s),
TMS): δ = 7.54–7.56 (m, 2 H), 7.48–7.51 (m, 2 H), 7.34–7.35 (m, 2 H), 30.3 (s).
7.29 (s, 1 H), 7.18–7.20 (m, 2 H), 7.05–7.07 (m, 2 H), 6.95 (s, 2 H),
6.84–6.86 (m, 2 H), 5.70 (s, 1 H), 5.44 (s, 1 H), 5.12 (s, 1 H), 3.81 (s,
3 H), 2.34 (s, 1 H), 1.40 (s, 18 H). 13C NMR (100 MHz, CDCl3, 25 °C,
TMS): δ = 157.9 (s), 152.1 (s), 145.7 (s), 138.2 (s), 136.8 (s), 135.5 (s), Acknowledgements
134.2 (s), 131.8 (s), 130.3 (s), 129.6 (s), 128.6 (s), 128.3 (s), 126.7 (s),
125.9 (s), 122.5 (s), 113.5 (s), 88.8 (s), 86.6 (s), 65.0 (s), 55.8 (s), This work was supported by the National Natural Science
55.3 (s), 34.4 (s), 30.4 (s). HRMS (ESI) m/z: calcd. For C37H41O3 [M + Foundation of China (21606080, 21908050), Natural Science
H] + : 533.3051, found: 533.3044. Foundation of Hunan Province (2019JJ50203), Scientific Research
Fund of the Hunan Provincial Education Department (19 A197),
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Research Article
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