Synthesis of 2,2′-biphenols through direct C(sp2)-H hydroxylation of [1,1′-biphenyl]-2-ols

Article abstract of DOI:10.1039/c6cc04756d

A novel synthesis of diversely substituted 2,2′-biphenols through Pd(ii)-catalyzed, ^tBuOOH-oxidized, and hydroxyl-directed C(sp²)-H hydroxylation of [1,1′-biphenyl]-2-ols has been developed. Notably, this finding is distinct from previous reports in which [1,1′-biphenyl]-2-ols underwent an intramolecular C-H activation and C-O bond formation to afford dibenzofurans under the promotion of Pd(ii) but in the absence of ^tBuOOH.

Full text of DOI:10.1039/c6cc04756d

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Synthesis of 2,2′-biphenols through direct C(sp2)–H hydroxylation
of [1,1'-biphenyl]-2-ols
Received 00th January 20xx,
Accepted 00th January 20xx
Shitao Duan, Yuanshuang Xu, Xinying Zhang* and Xuesen Fan*
DOI: 10.1039/x0xx00000x
www.rsc.org/
A novel synthesis of diversely substituted 2,2′-biphenols through a powerful tool for the formation of C–C and C–heteroatom
t
Pd(II)-catalyzed, BuOOH-oxidized, and hydroxyl-directed C(sp2)–H bonds.10 In particular, direct C(sp2)−H hydroxylaꢀon of arenes
hydroxylation of [1,1'-biphenyl]-2-ols have been developed. is emerging as a new tactics for the synthesis of phenol
Notably, this finding is distinct from previous reports in which derivatives.11 Compared with other methods, this strategy is
[1,1'-biphenyl]-2-ols underwent an intramolecular C−H acꢀvaꢀon arguably the most straightforward, sustainable and atom-
and C−O bond formaꢀon to afford dibenzofurans under the economy since it does not need pre-functionalization of
promotion of Pd(II) but in the absence of tBuOOH.
substrates, and thus holds advantages such as reduced
reaction steps, lower costs and less wastes. Generally, the
hydroxylation of arenes occurred under the assistance of a
directing group (DG), such as a ketone,12 aldehyde,13 ester,14
carboxyl acid,15 amide,16,17 oxime ether,18 anilide,19
carbamate,20 sulfide,21 2-pyridyl,22 or 2-benzoxazol-2-yl unit,23
and took place regio-selectively at the ortho-position(s) of the
DG to afford substituted phenols. Moreover, recent studies
demonstrated that the C(sp2)−H hydroxylaꢀon could also be
realized onto functionalized biphenyls such as [1,1'-biphenyl]-
2-carboxylic acid and [1,1'-biphenyl]-2-yl phosphonate to give
2'-hydroxy-[1,1'-biphenyl]-2-carboxylic acid,24 and 2'-hydroxy-
[1,1'-biphenyl]-2-yl phosphonate,25 respectively. Inspired by
those pioneering studies and as a continuation of our recent
interest in the synthesis and synthetic applications of 2-
arylphenols,26 we have studied the reaction of [1,1'-biphenyl]-
2-ol under the promotion of Pd(II) in the presence of tert-butyl
hydroperoxide (TBHP). We were pleased to find that under
these conditions, the hydroxyl group attached on one of the
two phenyl rings in [1,1'-biphenyl]-2-ol could act as a DG to
introduce a new hydroxyl group regio-selectively onto the 2'-
position of the other phenyl ring, thus resulting in a highly
convenient and efficient synthetic pathway toward 2,2′-
biphenol derivatives (Scheme 1, eq. 3). Notably, this finding is
distinct from previous reports in which 2-arylphenols
underwent an intramolecular C−H bond acꢀvaꢀon and C−O
bond formation to afford dibenzofuran derivatives under the
promotion of Pd(II) and the assistance of some specific
additives by using air (Scheme 1, eq. 1)27a or tert-butyl
peroxybenzoate (Scheme 1, eq. 2)27b as the oxidant.28 Herein
we wish to report our results on this regard.
The 2,2′-biphenol framework is a substructure frequently
found in natural products, pharmaceuticals and functional
materials.1,2 Moreover, 2,2′-biphenol and its derivatives are
also acting as efficient ligands in numerous metal-catalyzed
organic transformations and asymmetric synthesis.3
Due to their importance, tremendous efforts have been
made in developing efficient methods for the preparation of
2,2′-biphenols. So far, the most frequently used approach
toward 2,2′-biphenols is the oxidative homo- and cross-
coupling of phenols.4-6 Besides, other elegant strategies such
as radical cyclization,7 Ullmann-type coupling,8 and Suzuki-
Miyaura coupling9 have also been well established. While
these literature methods are generally efficient and reliable,
there are some challenging issues remained: (1) the couplings
of the electron-deficient substrates were much less efficient,
which restricted the scope of this synthetic strategy; (2) the
frequently required harsh reaction conditions could affect the
functional group compatibility; (3) in many cases, the poor
regio-selectivity led to the formation of side products, and the
expensive reagents and toxic heavy metal oxidants employed
therein compromised the sustainability. In view of the
increasing importance of 2,2′-biphenols and the need for
greener chemistry, more efficient, higher atom-economy and
more environmentally friendly synthetic approaches toward
2,2′-biphenols are still highly desirable.
In recent years, C–H bond activation has been developed as
School of Chemistry and Chemical Engineering, Collaborative Innovation Centre of
Henan Province for Green Manufacturing of Fine Chemicals, Key Laboratory of
Green Chemical Media and Reactions, Ministry of Education, Henan Normal
University, Xinxiang, Henan 453007, P. R. China.
E-mail: xinyingzhang@htu.cn; xuesen.fan@htu.cn
† Electronic Supplementary Informaꢀon (ESI) available: Experimental procedures,
mechanism studies, characterisation data and NMR spectra. See DOI: 10.1039/
x0xx00000x
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 1
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Table 1. Optimization studies on the formation of 2a a
Entry
Catalyst
Oxidant Ligand (eq.)
Base
Yield (%) b
1
2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
PdCl2
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
K2S2O8
oxone
m-CPBA
H2O2
-
-
-
-
-
K2CO3
Na2CO3
Cs2CO3
DABCO
-
25
22
3
34
Scheme 1. Transformations of [1,1'-biphenyl]-2-ol under
different conditions
4
33
5
-
6
PivOH (0.1) Cs2CO3
PivOH (0.5) Cs2CO3
45
Our study was initiated by treating 2-phenylphenol (1a) with
7
64
Pd(OAc)2, TBHP (70% aqueous solution) and K2CO3 in CH3CN at
80 oC for 18 h. From this reaction, [1,1'-biphenyl]-2,2'-diol (2a
8
PivOH (1)
Cs2CO3
76
)
9
PivOH (1.5) Cs2CO3
74
was obtained in 25% yield (Table 1, entry 1). Optimizations
were then carried out by varying the reaction parameters.
First, the effect of different bases including Na2CO3, Cs2CO3,
and DABCO was tested. Among them, Cs2CO3 was the most
effective (entries 1−4). In a control experiment, the formation
of 2a was not observed in the absence of a base (entry 5). To
our delight, using PivOH as a ligand could improve the reaction
significantly (entries 6-9). Next, replacing PivOH with AcOH
resulted in a decreased yield of 2a (entry 10). To check the
effect of different Pd catalysts, PdCl2, Pd2(dba)3, Pd(PPh3)4,
Pd(PPh3)2Cl2 and Pd(TFA)2 were tried. However, they were
found to be less effective than Pd(OAc)2 in promoting this
reaction (entries 11-15 vs 8). Other oxidants such as K2S2O8,
oxone, m-CPBA, H2O2 and air were ineffective for this reaction
(entries 16-20). Further study showed that changing the
reaction atmosphere from air to nitrogen did not affect the
yield of 2a obviously (entry 21 vs 8). Finally, when 70%
aqueous solution of TBHP was replaced by TBHP in decane (5.5
mol/L), 2a could be obtained in a yield of 75% (entry 22).
These results revealed that TBHP, rather than air or water, is
the oxygen source of the newly introduced hydroxyl group.
10
11
12
13
AcOH (1)
PivOH (1)
PivOH (1)
PivOH (1)
PivOH (1)
PivOH (1)
PivOH (1)
PivOH (1)
PivOH (1)
PivOH (1)
PivOH (1)
PivOH (1)
PivOH (1)
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
51
57
Pd2(dba)3
Pd(PPh3)4
55
50
14 Pd(PPh3)2Cl2
72
15
16
17
18
19
20
21c
22
Pd(TFA)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
50
trace
trace
trace
trace
-
-
TBHP
TBHP d
70
75
a Reaction conditions: 1a (0.5 mmol), catalyst (0.025 mmol), oxidant (4 eq.),
b
c
d
base (1.2 eq.), CH3CN (2 mL), 80 oC, air, 18 h. Isolated yields. Under N2.
5.5 mol/L in decane (dried over 4Å molecular sieve).
out that 2'-fluoro-, 2'-chloro-, and 2'-methyl-[1,1'-biphenyl]-2-
With the optimized reaction conditions in hands (Table 1, ols could also take part in this transformation to afford 2r
2s
entry 8), the scope and generality of this hydroxylation was and 2t, respectively, albeit in lower yields compared with their
,
,
explored. Initially, [1,1'-biphenyl]-2-ols bearing various 4'- or 3'-substituted counterparts.
functional groups (R2) on the phenyl unit onto which the new
Next, the reaction of [1,1'-biphenyl]-2-ols with different R1 were
hydroxyl group was going to be introduced were tried, and the tried. The results listed in Table 3 showed such substrates bearing a
results were included in Table 2. First, substrates bearing a fluoro, chloro, or methoxy group on the 4-position, or a chloro,
ha lid e, alky l , tr if lu o rom eth yl , ph en yl, al ko xy l, methyl, or methoxy group on the 3-position were all suitable for
trifluoromethoxy, phenoxy, or acetyl group on the 4'-position this hydroxylation process to give the corresponding products in
of the biphenyl-2-ols underwent this reaction smoothly to yields ranging from 75% to 85%. Interestingly, 3-(2-hydroxy
afford the corresponding products (2b−2n) in good yields. phenyl)naphthalene-2-ol (2v) was obtained in 58% yield from 2-
Notably, different kinds of functional groups were well (naphthalen-2-yl)phenol. Finally, 4-fluoro-4'-methoxy-[1,1'-bi
tolerated, and the electronic nature of the substituents did not phenyl]-2-ol, bearing substituents on both of the two phenyl
show obvious effect. Second, biphenyl-2-ols bearing a fluoro, units, took part in this reaction smoothly to give 2w in a yield
chloro, or methyl group on the 3'-position were found to be of 77%. Interestingly, as demonstrated by the synthesis of 2b
also able to participate in this reaction to give 2o−2q with good 2c
,
,
2j, 2p and 2q, this novel method could afford the same 2,2′-
efficiency. Meanwhile, for these 3'-substituted substrates, only biphenol from different [1,1'-biphenyl]-2-ol substrates (see Table
one of the two possible regio-isomers was obtained, indicating 2 and Table 3), thus resulting in a highly versatile method
that the hydroxylation proceeded regio-selectively at the less toward 2,2′-biphenol derivatives.
sterically hindered position. Third, [1,1'-biphenyl]-2-ols with a
[1,1'-Binaphthalen]-2-ol (1x) was also tried as a possible
substituent attached on the 2'-position were tested. It turned substrate for this oxidative hydroxylation with the aim to
2 | J. Name., 2012, 00, 1-3
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methylpiperidine oxide (TEMPO) were added as a radical
scavenger in the reaction of 1a. In this case, the yield of 2a
decreased to 35%. When the amount of TEMPO increased to 4
equiv, the formation of 2a was completely suppressed. The
obvious inhibitory effect shown by TEMPO indicated that this
hydroxylation reaction might involve a single electron transfer
process.
Table 2. Synthesis of 2,2′-biphenols (I) a,b
In a second control experiment, 2-methoxy-1,1'-biphenyl
(A) was found to be intact after being subjected to the
2d, 77%
2h, 80%
2l, 75%
2a, 76%
2e, 78%
2i, 77%
2m, 76%
2c, 77%
2g, 75%
2k, 75%
2b, 80%
2f, 75%
standard reaction conditions for 18 h. This result indicated that
removal of the proton in the hydroxyl group of [1,1'-biphenyl]-
2-ol should have been involved in the hydroxylation process.
Third, an intermolecular kinetic isotope effect was studied
by two side-by-side reactions of 1a and 1a-d5 under standard
reaction conditions. From these reactions, a kH/kD value of 1.8
was observed (Scheme 3).
2j, 75%
2n, 77%
Fourth, an intramolecular KIE experiment was conducted by
using 1a-d1 as the substrate to give a kH/kD value of 3.0
(Scheme 4). These results indicated that a C−H cleavage might
be involved in the rate-limiting step of this C(sp2)–H
hydroxylation process.
2o, 75%
2s, 55%
2p, 73%
Based on the above results and related reports,22
a
OH CH3
tentative mechanism for the formation of 2a from 1a is
illustrated in Scheme 5. Initially, 1a is transformed into an
anion (I) under the promotion of a base. Next, the phenoxide
HO
2q, 71%
2r, 58%
2t, 50%
a Reaction conditions: 1 (0.5 mmol), Pd(OAc)2 (0.025 mmol), TBHP (2 mmol),
ion-directed, ligand (
activation of affords intermediate III and releases LH via a
possible intermediate II. Meanwhile, homolysis of BuOOH
L)-assisted and Pd(II)-catalyzed C−H
PivOH (0.5 mmol), Cs2CO3 (0.6 mmol), CH3CN (2 mL), 80 oC, air, 18 h.
b
I
Isolated yields.
t
t
gives HO
radical from LH to release L
of HO and L to III affords a Pd(IV) intermediate IV. Then, a
reductive elimination occurs with IV to give a Pd(II)
•
and BuO•. The later then abstracts a hydrogen
Table 3. Synthesis of 2,2′-biphenols (II) a,b
•
. The following oxidative addition
•
•
2b, 85%
2q, 75%
2c, 80%
2u, 75%
2j, 76%
2v, 58%
2p, 76%
2w, 77%
Scheme 2. The reaction of [1,1'-binaphthalen]-2-ol (1x)
a Reaction conditions: 1 (0.5 mmol), Pd(OAc)2 (0.025 mmol), TBHP (2 mmol),
b
PivOH (0.5 mmol), Cs2CO3 (0.6 mmol), CH3CN (2 mL), 80 oC, air, 18 h.
Isolated yields.
develop an alternative synthetic approach toward [1,1'-bi
naphthalene]-2,2'-diol and its derivatives. However, treatment
of 1x under the optimized reaction conditions for 18 h
1-hydroxy-[1,1'-binaphthalen]-2(1H)-one29
(3,
Scheme 3. Intermolecular KIE experiment
afforded
Scheme 2), rather than the desired [1,1'-binaphthalene]-2,2'-
diol. This result might be attributed to the strong steric
hindrance between the two naphthyl units of the required
complex intermediate for the formation of [1,1'-binaphthalene]
-2,2'-diol.30
In order to clarify the reaction mechanism, some control
experiments were carried out. First, 2 equiv of 2,2,6,6-tetra-
Scheme 4. Intramolecular KIE experiment
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Scheme 5. Proposed reaction mechanism for the formation of 2a
intermediate V, which is then protonated to generate 2a and
release the Pd(II) species.
In conclusion, we have developed a novel synthesis of 2,2′-
biphenols via direct C(sp2)–H hydroxylation of [1,1'-biphenyl]-
2-ols. To our knowledge, this is the first example in which the
hydroxyl group is used as a DG to introduce another hydroxyl
group onto [1,1'-biphenyl]-2-ols. Generally, this new protocol
showed unique features such as broad substrate scope, good
functional group tolerance, sustainable oxidant, and excellent
regio-selectivity. Therefore, it is well complementary to the
existing methods for the synthesis of 2,2′-biphenols, and is
thus expected to find wide applications in related areas.
This work was financially supported by the National Natural
Science Foundation of China (NSFC) (grant numbers 21272058,
21572047), Program for Innovative Research Team in Science
and Technology in Universities of Henan Province (15IRTSTHN
003), and Program for Science and Technology Innovation
Talents in Universities of Henan Province (15HASTIT005).
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DOI: 10.1039/C6CC04756D
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A novel synthesis of diversely substituted 2,2′ꢀbiphenols through Pd(II)ꢀcatalyzed, BuOOH
ꢀoxidized, and hydroxylꢀdirected C(sp2)–H hydroxylation of [1,1'ꢀbiphenyl]ꢀ2ꢀols have been
developed.