Copper-catalysed: Ortho -selective C-H bond functionalization of phenols and naphthols with α-aryl-α-diazoesters

Article abstract of DOI:10.1039/d0cc04495d

Herein, we reported the first copper-catalyzed highly efficient C(sp2)-H functionalization of unprotected naphthols and phenols with α-aryl-α-diazoesters. In this transformation, CuCl2 efficiently promoted the highly chemo- and site-selective C-H bond fun

Full text of DOI:10.1039/d0cc04495d

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Copper-catalysed ortho-selective C-H bond functionalization of
phenols and naphthols with α-aryl-α-diazoesters
Ben Ma,ab Zhiqiong Tang,a Junliang Zhang,*abc and Lu Liu*ab
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
Herein, we reported the first copper-catalyzed highly efficient operation to install and remove such directing groups limits the
C(sp2)–H functionaliztion of unprotected naphthols and phenols utilization of this approach in organic synthesis. Recently, Bedford
with α-aryl-α-dizaoesters. In this transformation, CuCl2 promoted and Ye et al. realized an alternative way for direct ortho–selective
efficiently the highly chemo- site-selective C−H bond C−H bond arylation of phenols and naphthols by using P-containing
functionalization under mild conditions, furnishing diverse phenols ligands R2PX as transient directing groups (Scheme 1b).5
derivatives in moderate to excellent yields from readily available Unfortunately, this strategy is still limited into few examples.
starting materials.
(a) Installing the direacting group (DG)
O
DG
H
Phenol and naphthol motifs are prevalent in natural products, dyes,
medicines, bioactive compounds, materials, as well as privileged
chiral ligands, and they also represent the most readily available
chemical feedstocks and versatile building blocks for diverse
transformations in the chemical science.1 Thus, the development of
straightforward strategies to synthesize phenol derivatives via
direct site-selective C-H bond functionalization of free phenols is
highly attractive to the synthetic community. However, chemo- and
site-selective C−H functionalization of unprotected phenols poses
considerable challenge, because there are four possible reacting
sites, including chemoselectivity of oxygen or carbon and the site-
selectivity of ortho-, meta- or para-position.2
In past decade, with the advance of transition-metal-catalysed
directed C−H bond functionalization,3 many strategies have been
developed to achieve ortho-selective functionalization of phenols.
In this regard, directing-group-assisted approach, which needs to
be installed the directing groups on oxygen atom to ensure ortho
selectivity, as well as to protect the hydroxyl group, have emerged
as one of the most efficient and popular solutions to address the
ortho-selectivity problem (Scheme 1a).4 However, this extra
O
DG
TM
O
DG
R
RX
TM
TM = Pd, Rh, Ir
(b) Transient DG (Bedford and Ye)
OH
R
P
Rh
OH
Ar
R
O
Rh
ArX
Ar
Ar
H
or
R1
OH
R1
R2PX
R2
(c) Carbene insertion
Copper-catalyzed ortho-C-H functionalization
Well Known O-H insertion
OH
+
OH R1
R
CuCl2
CO2R2
Cu
R
R
This work
O
R1
CO2R2
N2
 earth-abundant metal catalyst
excellent chemo- and site-selectivity
ambient conditions


R1
CO2R2
Scheme 1. Ortho-selective C-H functionalization of phenols.
Recently, the catalytic carbene transfer reaction, typically using
diazo compounds,6 has emerged as one of the most powerful
strategies for aromatic C(sp2)-H bond functionalizations.7
Nonetheless, most of the commonly used catalysts are based on
noble metals, including rhodium, gold, palladium and iridium,
which are becoming more and more expensive and scarce because
they are from dwindling resources.8 The development of effective
and abundant catalysts to replace the rare and toxic transition-
metals is a long-term desirable. Copper, which is earth abundant,
readily available, inexpensive, environmentally benign, and low-
toxic metal, which represents an ideal catalyst in organic synthesis.9
Although the use of Cu-catalysed carbene transfer reactions has
been over half a century, compared with the well-established O−H
bond insertion of phenols with copper-carbene,10 the analogous
a School of Chemistry and Molecular Engineering, East China Normal University,
500 Dongchuan Road Shanghai, 200241, P. R. China; E-mail:
lliu@chem.ecnu.edu.cn.
b Shanghai Engineering Research Center of Molecular Therapeutics and New Drug
Development, East China Normal University, Shanghai 200062, P. R. China
c Department of Chemistry, Fudan University, 2005 Songhu Road, Shanghai
200438, P. R. China; E-mail: junliangzhang@fudan.edu.cn.
† Footnotes relating to the title and/or authors should appear here.
Electronic Supplementary Information (ESI) available: [details of any
supplementary information available should be included here]. See
DOI: 10.1039/x0xx00000x
This journal is © The Royal Society of Chemistry 20xx
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C(sp2)−H bond functionalization is still unknown.11 Very recently, of ester group had no effect on this reaction (3ab-3ad). Various
View Article Online
Nemoto and we have reported ortho-C-H functionalization of commonly encountered functional groupsDsOuIc:h10a.1s03c9h/lDo0roC,Cb04ro4m95oD,
naphthols of phenols with diazoesters.12 However, these methods methyl, methoxyl, CF3 and so on at various positions of phenyl rings
need expensive catalysts, gold complexes or B(C6F5)3. In addition, of α-aryl-α-diazoacetates were well tolerated (3ae-3at). The strong
gold catalysts12b-c were suitable for naphthols, but were not electron-donating groups (OMe) could facilitate this reaction (3ah
compatible for phenols, and B(C6F5)312a was contrary. The general and 3ao), while the strong electron-withdrawing groups (CF3) would
approach to achieve ortho-alkylation of both phenols and slow down this reaction (3am). Furthermore, several substituted 1-
naphthols has not been developed so for. Herein, we reported the naphthols 1b-1e were tested in this transformation, delivering the
unprecedented CuCl2-catalysed highly chemo- and ortho-selective corresponding ortho-selective C-H functionalization products 3ba-
C-H bond functionalization of phenols and naphthols with 3ea in moderate to excellent yield (68% to 97%). It must note that all
diazoesters (Scheme 1c).
the reactions exhibited 100% ortho-selectivities.
OH
H
OH Ar
Table 1. Optimization of reaction conditions.a
CuCl2 (5 mol%)
N2
CO2R1
R'
Ar
CO2R1
CH2Cl2, r.t.
10 min-10 h
R'
N2
H
CO2Me
1
2
O
3
OH
Ph
CO2Me
Ph
H
1-naphthyl
CO2Me
OH Ph
2a
3ai
3aj
3ak
3al
3am
, R = 3-Br, 78%
, R = 3-CF3,81%
O
R
R
HO
CO2R1
cat. (5 mol%)
CH2Cl2, rt
Dimers
6aa
, R =2-Cl, 83%
, R = 2-Br, 89%
, R = 2-CF3, 53%
, R = 2-Me, 72%
, R = 2-OMe, 98%
OH
Ph
CO2Me
CO2Me
HO
3ae, R = Cl, 80%
3af
H
CO2Me
, R1 = Me, 82%
, R1 = Et, 80%
, R1 = iPr, 71%
Ph
4aa
3aa
3ab
3ac
3ad
1a
(1.5 equiv)
3an
3ao
5aa
, R = Br, 81%
3aa
3ag
, R = Me, 83%
, R = OMe, 92%
3ah
yield (%)a
,
R1 = tBu, 81%
X
OH Ph
CO2Me
entry
cat. (5 mol%)
R'
X
X
3/4/5/6
3ap
3aq
, X = 3,4,5-(OMe)3, 86%
1
Cu(ClO4)2ˑ6H2O
Cu(CH3CN)4PF6
CuOAc
CuOTf
60 (12)b/0/2/38
60 (18)b/0/2/38
68 (10)b/0/1/31
54 (24)b/0/0/46
72(4)b/0/0/22
85 (2)b/0/2/3
70(12)b/0/2/24
76 (2)b/0/5/5
53/0/3/35
, X = 3,5-(OMe)2, 82%
X
OH
OH
3ar
, X = 3,4-(-OCH2O-)2, 82%
3ba
, R' = 4-Br, 95%
, R' =4-Cl, 87%
, R' = 5-Br, 97%
, R' = 7-OMe, 68%
CO2Me
CO2Me
2
3as
, X = 2,4-Cl2, 79%
3ca
3at
, X = 2,3-Cl2, 87%
3da
3ea
3
3au
, 74%
4
Scheme 2. Ortho C-H bond functionalization of 1-naphthols.
5
CuCl
6
CuCl2
Subsequently, we turned to investigate the substrate scope of
CuCl2-catalyzed ortho-selective C-H bond functionalization of 2-
naphthols. All the reactions of 2-naphthols 7 with various
diazoacetates 2 proceeded smoothly under the standard conditions,
affording the corresponding ortho-selective products in 58% to 98%
yield with excellent chemo- and site-selectivity (Scheme 3).
7
CuF2
8c
9d
10e
CuCl2
CuCl2
CuCl2
25/0/5/31
Reaction Conditions: the solution of 2a (0.4 mmol) in 1 mL of
solvent was introduced into 1a (0.6 mmol) and catalyst (5 mol%) in
solvent (1 mL) at room temperature by a syringe in 15 min.a NMR
Ar
CO2R1
H
N2
OH
OH
CuCl2 (5 mol%)
CH2Cl2, rt
R'
R'
Ar
CO2R1
b
c
yield. Corresponding lactone 11 from 3aa was detected. DCE
2
instead of DCM. d toluene instead of DCM. e THF instead of DCM.
7
8
8ad
8ae
8af
, R = 2-OMe, 76%
, R = 2-Me, 58%
, R = 2-Cl, 98%
Initially, we performed the reaction of 1-naphthol 1a withα-
phenyl-α-diazoacetate 2a in the presence of 5 mol % Cu(ClO4)2ˑ6H2O
in DCM at room temperature. To our delight, the desired ortho-C-H
functionalization products, including 3aa and the corresponding
lactone 11 from 3aa, were obtained in 60% yield with 30 : 1 C-H/O-H
selectivity and regio-specific ortho-selectivity (Table 1, entry 1).
Encouraged by this result, various copper salts were then screened,
and CuCl2 was finally found out as the best catalyst, affording the
ortho-selective C-H bond alkylation product in 85% yield with
excellent chemo- and site-selectivity for 6h at room temperature
(Table 1, entries 2-7). Solvent screening showed that DCE, toluene
and THF could not improve the yield (Table 1, entries 10−12).
Ph
CO2R1
OH
R
Ph
CO2iPr
OH
8ag
8ah
8ai
8aj
, R = 2-Br, 84%
, R = 2-F, 78%
, R = 4-Me, 85%
, R = 4-F, 85%
CO2Me
OH
, R1 = Me, 78%
8aa
8ab
8ac
Br
8ak
8al
, R = 4-Cl, 95%
, R = 4-Br, 85%
, R1 = Et, 76%
8bc
, 68%
, R1 = iPr, 71%
X
Ph
CO2Me
OH
X
X
CO2Me
CO2Me
8am
OH
Br
, R = 3,4-Cl2, 86%
, R = 2,4-Cl2, 85%
, R = 3,4-(-OCH2O-), 71%
OH
8an
8ao
8ap,
8ba
, 81%
82%
Scheme 3. Ortho C-H bond functionalization of 2-naphthols.
Next, the scope of the copper-catalysed ortho-selective C-H
functionalization of 1-naphthol with various α-aryl-α-diazoacetates
was explored using CuCl2 (5 mol %) in DCM at room temperature. As
shown in Scheme 2, such reaction proved to be applicable to a wide
range of α-aryl-α-diazoacetates and the desired 2-alkylated 1-
naphthols were obtained in good to excellent yields and with
excellent levels of chemo- and site-selectivity. The steric hindrance
Furthermore, we wondered whether phenols were applicable to
this copper-catalysed ortho-C-H functionalization, which was more
challenging because the nucleophilicity of phenols was much lower
than that of naphthols. Indeed, all attempts to realize ortho-C-H
alkylation of unsubstituted phenol failed. To our delight, CuCl2 could
enable the ortho-C-H bond functionalization of alkoxyl-substituted
2 | J. Name., 2012, 00, 1-3
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phenols 9 with α-aryl-α-diazoacetates 2 to give the corresponding
products 10a-10d in good to excellent yield with excellent site-
selectivity (Scheme 4).
intermediate IA’, which would further coordinated O of phenol to
generate IB’. The following electrophilic addition of the copper-
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DOI: 10.1039/D0CC04495D
carbocation at ortho-position of phenols generated IC’, which
underwent the following aromatization, denitrogenation and
protonation to produce the target ortho-C-H bond functionalization
products and regenerate the copper catalyst. The further
mechanistic studies indicated that these two process were existed in
this reaction.15
Ar
CO2Me
H
N2
OH
OH
CuCl2 (5 mol%)
CH2Cl2, rt
R'
R'
Ar
CO2Me
Cl
2
9
10
Cl
N2
Path A : Carbene process
CO2Me
OH
CO2Me
OH
CO2Me
OH
CO2Me
OH
Ar
CO2Me
3, 8, 10
1
CuCl2
MeO
Diazo decomposition
aromatization
/protonation
O
OMe
O
OMe
OMe
10b
O
Ar
CuII
CO2Me
CuCl2
10d
, 76%
10c
, 91%
, 95%
10a
, 98%
H
+ HCl
R
Ar
CO2Me
IA
IC
Scheme 4. Ortho C-H bond functionalization of phenols.
C-H bond
functionalization
OH
Cl-
Cl
O
H
O
CuII
H
To demonstrate the practicality of this transformation, a gram-
scale reaction was carried out (Scheme 5). To our delight, the ortho-
selective alkylation was easy to scale-up to a gram-scale with even 1
mol% catalyst loading, affording the desired product 3aa (1.61 g,
92%). To showcase the utility of this method further, transformations
of the products were also performed. As shown in scheme 5, TFA-
catalyzed lactonization of 3aa and 10c could afford the
corresponding cyclized products 11 and 12 in 99% and 95% yields,
respectively. The structure of 12 was further confirmed by single-
crystal X-ray analysis.13
R
OMe
Ar
R
1, 7, 9
IB
Path B: Lewis acid process
3, 8, 10
1
CuCl2
aromatization
/denitrgenation
/protonation
Coordination
CuCl2
N
O
Ar
H
N
CuCl
N
N
CO2Me
R
Ar
CO2Me
IA'
+ HCl
Cl
IC'
Cl-
Cu
OH
C-H bond
functionalization
H
N
H
O
OH Ph
N
O
R
N2
1 mol%
)
CuCl2
(
CO2Me
1-naphthol
(1.5 eq.)
OMe
R
Ar
IB'
CH2Cl2 (0.1 M), r.t.
CO2R
Ph
1, 7, 9
2a
3a, 1.61 g 92%
,
CCDC 1834202
Scheme 6. Proposed catalytic cycle.
Ph
O
O
To conclude, we have described the first example of CuCl2-
catalyzed direct C−H functionalization of unprotected phenols
and naphthols with α-aryl-α-diazoacetates under mild
conditions, leading to diverse phenol derivatives with
convertible functional groups. This work would broaden the
application of copper catalysts in carbene transfer reactions.
The salient features of this reaction include inexpensive
catalyst, readily available starting materials, unprecedented
C−H functionalization rather than O−H insertion, good substrate
scope, mild conditions, and diverse convenient transformations
of the products. Further studies on the mechanism and the
application of this protocol in organic synthesis are currently
underway in our laboratory.
OMe
TFA
TFA
3aa 10c
O
12,
O
Ph
95%
11,
99%
Scheme 5. Gram-scale reactions and transformations of products
OMe
OMe Ph
N2
CuCl2 (5 mol%)
CH2Cl2, r.t.
CO2Me
(1)
Ph
CO2Me
2a
13
(3.0 eq.)
14 trace
,
To further gain the mechanistic insight of this copper-catalysed
ortho-C-H alkylation of phenols, the treatment of 1-
methoxynaphthalene 13 with the diazoester 2a in the presence of
CuCl2 only delivered a trace amount of ortho-selective C–H bond
functionalization products (eqn (1)). This result indicated that the
hydroxyl was vital not only for site-selectivity but also for reactivity,
and the interaction between the hydroxyl group and copper catalyst
could arise the ortho-selectivity.
We are grateful to the National Natural Science Foundation
of China (Nos. 21971066, 21772042) and the STCSM
(18JC1412300) for financial support.
Based on abovementioned results, two possible catalytic cycle
accounting for this transformation was depicted in Scheme 6. Path A
is Cu-carbene process. The Cu(II)-carbene intermediate IA was
formed from α-aryl-α-diazoesters 2 with CuCl2,14 which resulting the
intermediate IB via the coordination. The electrophilic addition of
the copper-carbene at ortho-position of phenols generated IC, which
underwent the following aromatization and protonation to produce
the target ortho-C-H bond functionalization products 3, 8 or 10 and
regenerate the copper catalyst. In path B, CuCl2 sever as a Lewis acid
to coordinate the N of α-aryl-α-diazoesters 2 to form the carbocation
Notes and references
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S. F. Lo, Z. Zhou and W.-Y. Yu, J. Am. Chem. Soc. 2012, 134, 15 According to the reviewer’s suggestion, we did several control
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experiments to understand the mechanism. Because of the
page limitation, all the details were in the Supplementary
information. We thank the reviewer for his/her helpful
suggestion.
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