Copper-Catalyzed C-4 Carboxylation of 1-Naphthylamide Derivatives with CBr4/MeOH

Article abstract of DOI:10.1002/adsc.201900482

A simple and practical copper catalyzed C-4 carboxylation reaction of 1-naphthylamide derivatives using carbon tetra bromide and methanol is reported here. Picolinamide and its derivatives are used as a bidentate directing group for the distal C4-H functi

Full text of DOI:10.1002/adsc.201900482

Title: Copper-Catalyzed C-4 Carboxylation of 1-Naphthylamide
Derivatives with CBr4/MeOH
Authors: Subhash Ghosh, Tapan Sahoo, Chiranjit Sen, Harshvardhan
Singh, and Suresh E
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To be cited as: Adv. Synth. Catal. 10.1002/adsc.201900482
Link to VoR: http://dx.doi.org/10.1002/adsc.201900482

Advanced Synthesis & Catalysis
10.1002/adsc.201900482
COMMUNICATION
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
Copper-Catalyzed C-4 Carboxylation of 1-Naphthylamide
Derivatives with CBr /MeOH
4
Tapan Sahoo, Chiranjit Sen, a, b Harshvardhan Singh, a, b E. Suresh b, c and Subhash
a, b
a, b
Chandra Ghosh*
a
b
Natural Products and Green Chemistry Division; Analytical and Environmental Science Division and Centralized
c
Instrument Facility; Academy of Scientific and Innovative Research
Central Salt and Marine Chemicals Research Institute (CSIR), G.B. Marg, Bhavnagar-364002, Gujarat, India. Phone (+91)
2
78- 2567760; Fax- (+91) 278- 0278-2567562;
E-mail: scghosh@csmcri.res.in; schandra1976@gmail.com
Received: ((will be filled in by the editorial staff))
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201######.((Please
delete if not appropriate))
Abstract. A simple and practical Copper catalyzed C-4
carboxylation reaction of 1-naphthylamide derivatives
using carbon tetra bromide and methanol is reported here.
Picolinamide and its derivatives are used as a bidentate
directing group for the distal C4-H functionalization.
Various substituted naphthylamide derivatives, and
anilides are employed for the carboxylation and proceeds
in good yields under mild condition. From the outcome
of experimental results, it is proposed that C4-H
carboxylation reaction of 1-naphthylamides might
proceed through a single electron transfer (SET) pathway
Keywords: Carboxylation; Copper-catalyzed;
regioselective; 1-naphthaylamide; SET
Transition
metal
catalyzed
direct
C-H
Scheme 1. para-selective C-H functionalization of
naphthalene
functionalization strategy is rapidly growing for the
[1]
synthesis of valuable organic molecules. In this
active research area, the regioselective carboxylation
of arenes and heteroarenes is one of the important
group. Later, Weng and Lu et al. reported the copper
organic transformation to install a C1 unit in the
[9]
aromatic moiety.[
2]
catalyzed sulfonylation of 1-naphthylamide. Ru/ Cu
Naphthalenes are privileged
[10]
or Cu/Ag catalyzed C4-H sulfonylation and silver
catalyzed amination were reported by Wu and co-
aromatic compounds that widely presents in numerous
pharmaceuticals, agrochemicals and functional
[11]
workers. Recently, Yu et al. reported Cu catalyzed
materials
electroluminescent materials.
like
organic
semiconductor,
or
[12]
[3]
C-4 phosphorylation and trifluromethylation. Most
of the reports are on C-hetero atom bond forming
reactions. Key steps for the remote functionalization is
bidentate chelation controlled SET to the naphthalene
ring to generate the reactive radical cation species,
followed by the addition of nucleophile or radical. The
regioselective carboxylation of naphthalene is a vital
transformation and as it could be elaborated to
important functional group like acid, ester and amides.
Therefore, the development of a simple and practical
method for carboxylation (C-C bond formation) at C4-
position of naphthylamide is still remain a challenge
and strongly desired.
In this context,
considerable efforts have been made for the synthesis
of substituted naphthalene compounds via direct C-H
functionalization.[
4]
Among them, regioselective
functionalization of 1-nathylamine scaffolds using a
bidentate chelation controlled strategy achieved
[5]
significant progress in recent years. Directing group
assisted adjacent ortho (C-2) and peri (C-8) selective
C-H functionalization is very common, as it is
[6]
controlled by the cyclometalation strategy. However,
over the couple of years’ a little progress has been
achieved
on
para-(C-4)
selective
C-H
functionalization which proceeds through bidentate
chelation assisted single electron transfer pathway. In
In this direction, CBr
4
was recognized as a masked
st
[7]
carboxylating agent, was
1
reported by
2
017, Manolikakes and co-workers first reported the
Khusnutdinovand co-workers for C2-carboxylation of
benzofuran using an iron catalyst at 140 C.
Ruthenium catalyzed meta-carboxylation of 2-phenyl
copper catalyzed remote para C-H sulfonylation of 1-
[8]
naphthylamide
developed bidentate picolinamide (PA) as a directing
framework
using
Daugulis
1
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Advanced Synthesis & Catalysis
10.1002/adsc.201900482
Table 1: Optimization of reaction condition a
Table 2: Substrate scope of 1-naphthylamides
Yield
%)
Entry Catalyst (mol%)
Base
Additive
(
1
2
Cu(OTf)
Cu(OTf)
Cu(OTf)
2
2
2
(10%)
(20%)
(30%)
K
K
2
CO
CO
3
3
-
-
36
63
2
3
4
5
6
K
2
CO
3
-
-
-
63
32
56
71
[
b]
CuBr
Cu(OAc)
2
K
K
K
2
CO
2
CO
2
CO
3
3
3
2
Cu(OTf)
Cu(OTf)
Cu(OTf)
Cu(OTf)
Cu(OTf)
Cu(OTf)
2
(20%)
(20%)
(20%)
(20%)
(20%)
(20%)
(20%)
(20%)
(20%)
DMAP
7
8
9
1
1
2
2
2
2
2
2
2
2
Na
2
CO
3
DMAP
DMAP
64
33
35
27
34
3 4
K PO
NaOAc DMAP
iPr NH DMAP
DABCO DMAP
0
1
2
1
1
1
1
1
1
2
3
4
5
6
7
Cu(OTf)
Cu(OTf)
Cu(OTf)
-
Et
-
3
N
DMAP
DMAP
-
DMAP
DMAP
DMAP
41
36
19
nr
20
27d
1
4 2 3
(0.2 mmol), CBr (3 equiv.), K CO (2 equiv.), DMAP (20
mol%) and MeOH (1ml) at 85C, for 18h, in a sealed tube
under inert atmosphere.
-
K
K
2
CO
CO
3
3
c
Cu(OTf)
2
2
(20%)
(20%)
2
2
Cu(OTf)
K
CO
3
increases the yield to 71% (entry 6).
a1a (0.2 mmol), CBr
(3 equiv.), base (2 equiv.), additive (20
Next, we replaced K
2
CO with other inorganic and
3
4
organic bases, but inferior results were obtained
entries 7-12). Control experiments revealed that base
mol%) and MeOH (1ml) at 85C, for 18h, otherwise
(
mentioned in a sealed tube under inert atmosphere, isolated
b
c
is essential for this reaction (entries 13-14). The
reaction does not proceed in absence of the catalyst
yields. bromination product obtained ~20%; air
d
atmosphere; at 65 C;
(
entry 15). When reaction was carried under air
atmosphere resulted lower yield (entry 16), indicates
the interference of oxygen in the reaction. In addition,
performing the reaction at lower temperature,
decreased the yield (entry 17).
pyridine and C2-carboxylations of indoles are
[13]
[14]
independently reported by Greaney and Bandini
group respectively. carboxylation of styrene using
cooperative Eosin-Y as photocatalyst and cobalt
Under the optimized reaction conditions (entry 6), we
then explored the substrate scope of the various
naphthaylamide derivatives, as shown in Table 2. The
carboxylation with various substituents at the C2, C6
and C8 position of the naphthalene ring was first
explored, C2-methyl substituent provided the desired
carboxylated product in good yield (Table 2, 2b, 73%),
the structure of the compound was confirmed by single
iodide as catalyst with CBr[
4
and DMSO was reported
15]
by Tang and co-workers.
In continuation of our
[16]
work on regioselective C-H bond functionalization,
herein, we report a simple and practical strategy for the
regioselective carboxylation of 1-naphthalene amide
derivatives at C-4 position by exploring bidentate
chelation controlled SET strategy using carbon tetra
bromide as C1-source. We began our studies using N-
[17]
crystallography. Various electron -donating and –
withdrawing substituent at C8 position of 1-
naphthylamine had showed excellent compatibility
and almost similar yields were obtained. Electron
donating groups like methyl, piperidin-1-yl, -SPh, -Ph
afforded good yields of desired carboxaylated product
(
naphthalene-1-yl) picolinamide (1a) as a model
substrate for the carboxylation of 1-naphthalne amide
framework with CBr and MeOH (2 mL). The results
are summarized in Table 1. Initially Cu(OTf) (10
mol%) was chosen as a catalyst, K CO was used as a
4
2
2
3
(
entries 2c-2f). In the presence of bromo as electron
withdrawing group, similar yield was observed (2g,
0%,). C6-methoxy substituted naphthylamide
base, a modest yield (36%, Table 1, entry 1) of our
desired para-selective carboxylated product was
obtained. We realized that, increase of catalyst loading
might be effective for this reaction, to our delight with
7
derivatives afforded the corresponding carboxylated
product in high yields (2i, 81%). When the C4-
position is blocked, no carboxylation was observed, as
expected (2i).
Next, the role of the directing group in the
carboxylation reaction was examined. Several
2
0 mol% catalyst loading 63% of desired product was
obtained, further increase of catalyst loading to 30
mol% does not have any affect (62%, entry 3), Also,
other copper salts were found less reactive (entries 4-
5). Notably, addition of DMAP (20 mol%) as additive
2
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Advanced Synthesis & Catalysis
10.1002/adsc.201900482
Table 3: Substrate scope for carboxylation reaction a
Scheme 2: Sequential C-H functionalization of 1-
naphthaylamide moiety.
carried out the carboxylation with ethanol and 2,2,2-
trifluoroethanol with the model substrate (1a) and
afforded ethyl carboxylate (2v-2w) and fluorinated
carboxylate (2x, 51%) in moderate yields, for the latter
case (2x) elongated reaction time (36h) is required to
complete the reaction. In this case after 18h, we have
isolated the intermediate (orthoester, 3x) as a major
product. To showcase the synthetic utilty of our
developed methodology, we have regioselectivity
a1 (0.2 mmol), CBr
DMAP (20 mol%) and MeOH (1ml) at 85
in a sealed tube under inert atmosphere; 36h.
(3 equiv.), K
CO
(2 equiv.),
C, for 18h,
4
2
3

b
carboxylated
TSQ
(6-Methoxy-8-p-
common
Further, we
substituted and analogous amides of picolinamide
were tested and the results are summarized in table 3.
Under the optimal reaction condition, C3-methyl and
C5-bromo substituted pyridine are well tolerated and
desired carboxylated products were obtained in similar
yield (Table 3, entries 2j-2k, 70 and 66 %). The
structure of the carboxylated products were well
Toluenesulfonamido-Quinoline, 1y),
a
[18]
fluorescent sensor for cellular zinc.
have carried out the sequential C-H functionalization
of 1-naphthayl amide moiety to synthesize various
substituted naphthalene in a regioselective manner
(Scheme 2). In path A, Pd catalyzed peri-selective
[6d]
st
amination
was carried out in the 1 step, to get
[17]
characterized
by
single
crystallography.
intermediate 1c, which was carboxylated by our newly
developed methodology at C4 position. In path B, C-
H functionalization sequence was reversed, initially
carboxylation at C-4 position and next, amination was
carried out, little higher overall yield was obtained in
path B. The reaction can be easily scaled-up without
affecting the yield, also selective deprotection of
picolinamide with HCl afforded high yield, further
showcased the synthetic utility of our methodology
(scheme 3).
Interestingly, additional N atom in the pyridine ring,
pyrazine also furnished good yield (entry 2l, 70%).
Instead of pyridine when isoquinoline (1m) and
quinoline carboxamide (1n) were tested, similar
effectivity was observed (entries 2m and 2n). Next, we
turned our attention for the carboxylation of other
aromatic and heteroaromatic compounds (table 3).
First, reaction with aniline derivatives were
investigated,
interestingly
our
developed
carboxylation is sensitive to the benzene ring, with
simple aniline moiety no carboxylated product was
obtained (2o), whereas substrates bearing electron
donating group (-OMe), carboxylation proceeds,
furnished in low yields (2p, 29%), Furthermore, the
carboxylation occurs smoothly with quinoline moiety,
under the standard condition N-(quinolin-5-
yl)picolinamide afforded the C8-carboxylated product
in good yield (entry 2q, 52%). Interestingly, where 8-
amino quinoline moiety act as a directing group, with
various substituted benzamide moiety, reaction
proceeds well, and the desired carboxylated products
were obtained in good yields (entries 2r-2u). To further
demonstrate the potential application of our developed
methodology, we have
Scheme 3: a) Gram Scale Synthesis b) deprotection of DG
To better understand the reaction profile we have monitored
the reaction progress with time by HPLC (Figure 1-a).
Interestingly, we have found the
3
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Advanced Synthesis & Catalysis
10.1002/adsc.201900482
100
Strating Material
Intermediate
Product
(
a)
(b)
80
60
40
20
0
0
2
4
6
8
10
12
14
16
18
Time (h)
Scheme 4: Radical Inhibitor and Kinetic Isotope study
Figure 1: (a) Reaction kinetics; (b) EPR spectra
reaction condition to get some insight on the co-
ordination of substrate with copper, but no
caboxylated products were obtained. These results
suggest that the presence of both pyridine nitrogen and
amide nitrogen played key roles and N, N bidentate
ligand might be crucial for carboxylation reaction.
Also, it confirmed that reaction does not proceed
through the classical aromatic electrophilic
substitution pathway, otherwise, more electron rich
substrate 4a might afford better result compare to 1a.
formation of an intermediate along with the desired
product. However, in TLC monitoring we have not
found any intermediate spot, may be it has the same Rf
with the product. We have identified the intermediate
(
3a), tri-methoxy compound by HRMS analysis (see
SI for details), which indiactes that the reaction
proceed via complete methanolysis pathway with the
formation
of
an
ortho
ester,
(
trimethoxymethyl)naphthalene (3a). From the
reaction kinetics, it was observed that initial few hours
6h) reaction produces intermediate 3a along with
On the basis of above experimental outcome and in
(
[9,10, 13]
combination with previous reports,
a plausible
carboxylated product 2a. The maximum formation of
orthoester 3a was observed around 6h with ~70%
conversion of starting material and, after that it
essentially converted to the desired ester product 2a
mechanism is presented as shown in Scheme 5.
(II)
Initially, the coordination of 1a with copper triflate
took place and led to a chelated intermediate A. Next,
an intermolecular SET from Cu(II) complex to CBr
4
(
figure 1a) within 18h. To investigate the reaction
mechanism, we have carried out kinetic isotope effect
KIE) experiment. KIE was determined by the
afforded CBr radical and Cu(III) complex B. Then,
3
the intermediate B, proceeds through an
intramolecular SET oxidation pathway, generated aryl
radical cation species C. Then the intermediate D was
(
intermolecular competitive reaction of two
isotopomeric substrates (1a and 1a-D, Scheme 4-A),
and k
H
/k =1.04 was obtained. Which indicates that C-
D
H bond cleavage was not involved in the rate
determining step.
Next, we carried out the radical inhibition and capture
experiment (Scheme 4-B) upon addition of the radical
scavenger, TEMPO or BHT the reaction was
completely inhibited, we have also identified the BHT
trapped CBr compound as well as BHT trapped 1a in
3
HRMS (see ESI for details). Which suggest that the
reaction might undergo through a single electron
transfer (SET) pathway. To get more information, EPR
(
electro paramagnetic resonance) experiments were
carried out, showed in Figure 1b, (a) Cu(OTf) in
methanol solvent showed a EPR signal at g = 2.2016.
b) After addition of the substrate 1a with catalyst in
2
(
methanol, complex formation takes place, which
clearly showed in EPR with a signal at g = 2.0607, and
also (c) similar EPR signals with all the reagents (g =
2
.0586) and (d) in absence of CBr (g = 2.0622).
4
moreover presence of Cu(II) species was clearly
observed in all conditions. Several designed substrates
(
4a-4d) were synthesized and tested under the standard
Scheme 5: Plausible Reaction mechanism
4
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Advanced Synthesis & Catalysis
10.1002/adsc.201900482
generated by the radical combination between CBr
3
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radical and intermediate C. The proton transfer
process afforded intermediate E, and ligand exchange
of which leads the regeneration of intermediate A to
continue the catalytic cycle along with intermediate F,
which upon methanolysis gave the desired product 2a.
In summary, we have developed a simple copper
catalyzed regioselective C4 carboxylation of 1-
naphthylamine and other aromatic and heteroaromatic
substrates, with CBr and alcohol using picolinamide
4
and analogous amide as directing group. The
carboxylation showed wide substrate scope, good
functional group tolerance and easy to scale up.
Deprotection of directing group and functionalization
of TSQ, fluorescent probe for Zn(II), and sequential C-
H functionalization of 1-naphthayl amide moiety to
poly substituted naphthalene showcased the
applicability of our developed methodology. Control
experiments, with trapping of radicals intermediates
revealed that reaction proceeds through a single
electron transfer (SET) pathway.
[
4] For selected examples naphthalene derivatives C−H
Experimental section
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A mixture of Amide (1a) (49.6 mg, 0.2 mmol), CBr
199 mg, 0.6 mmol, 3 eqv], Cu(OTf) (14.5 mg, 20
mole%), K CO (55.3 mg, 0.4 mmol) and DMAP (4.9
4
(
2
2
3
mg, 20 mole%) were taken in a carousel screw cap
reaction tube equipped with a cross shape stirring bar.
The reaction tube was evacuated and refill with
nitrogen, 1 mL dry methanol was added over it and
stirred at 85 C for 12-18 h. Reaction was monitored
by TLC. After completion the reaction, mixture was
cooled to room temperature and filtered through a plug
of celite, the filtrate was concentrated, and evaporated
to dryness in rotary evaporator. The crude residue was
purified by Flash column chromatography (Ethyl
acetate: Hexane 5:95) to isolate methyl 4-
[5] For selected examples on the functionalization of 1-
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6
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Acknowledgment
2
017, 6, 1693–1698. f) S. Roy, S. Pradhan, T.
We are thankful to the SERB, DST, India
Punniyamurthy, Chem. Commun. 2018, 3–6. g) G. You, K.
Wang, X. Wang, G. Wang, J. Sun, G. Duan, C. Xia, Org.
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Sun, Appl. Organomet. Chem. 2016, 30, 680–683.
(
EMR/2016/002427), for financial support for this
work. The authors also acknowledge AESD&CIF of
CSIR-CSMCRI for constant analytical support. TS,
CS, and HS thanks to DST, CSIR, and UGC for their
fellow-ship
respectively.
CSIR-CSMCRI
Communication No. 051/2019
[
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Advanced Synthesis & Catalysis
10.1002/adsc.201900482
[
2
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Advanced Synthesis & Catalysis
10.1002/adsc.201900482
COMMUNICATION
Copper-Catalyzed C-4 Carboxylation of 1-
Naphthylamide Derivatives with CBr /MeOH
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Adv. Synth. Catal. Year, Volume, Page – Page
Tapan Sahoo, Chiranjit Sen, Harshvardhan Singh,
E. Suresh, and Subhash Chandra Ghosh*
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