Copper-mediated ortho-nitration of arene and heteroarene c-h bonds assisted by an 8-aminoquinoline directing group

Article abstract of DOI:10.1002/adsc.201400947

A copper-mediated, chelation-assisted ortho C-H bond nitration of benzoic acid derivatives using sodium nitrite as the source of the nitro group has been achieved with the aid of an 8-aminoquinoline directing group. Selective mono- or dinitration can be achieved by simply changing the reaction conditions. The method shows excellent functional group tolerance and provides a novel and straightforward route for the preparation of ortho-nitrated benzoic acids.

Full text of DOI:10.1002/adsc.201400947

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DOI: 10.1002/adsc.201400947
Copper-Mediated ortho-Nitration of Arene and Heteroarene
À
C H Bonds Assisted by an 8-Aminoquinoline Directing Group
Jidan Liu,a Shaobo Zhuang,a Qingwen Gui,a Xiang Chen,a Zhiyong Yang,a
and Ze Tana,*
a
State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan
University, Changsha 410082, Peopleꢀs Republic of China
Fax : (+86)-731-8882-2400; e-mail: ztanze@gmail.com
Received: September 29, 2014; Revised: November 11, 2014; Published online: && &&, 0000
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201400947.
Abstract: A copper-mediated, chelation-assisted
ortho C H bond nitration of benzoic acid deriva-
provide a powerful method for the construction of ni-
troarenes starting from aryl halides, pseudohalides
and arylboronic acids.[7] Since these methods all re-
quire the use of prefunctionalized arene starting ma-
terials, recent efforts are focused on the development
of new methods using the parent arenes as the start-
ing materials. Along this line, significant progress has
À
tives using sodium nitrite as the source of the nitro
group has been achieved with the aid of an 8-ami-
noquinoline directing group. Selective mono- or di-
nitration can be achieved by simply changing the
reaction conditions. The method shows excellent
functional group tolerance and provides a novel
and straightforward route for the preparation of
ortho-nitrated benzoic acids.
been made in the transition metal-catalyzed (or pro-
[8]
À
moted), chelation-assisted aromatic C H nitration.
However, the substrate scope of these recent develop-
ments is still limited. Thus there remains much room
for improvement in the field of selective nitration of
arenes.
À
Keywords: arenes; C H activation; copper; nitra-
tion; selectivity
In recent years, bidentate auxiliaries have attracted
considerable attention owing to their unique potential
[9]
À
for the activation of C H bonds. Since the pioneer-
ing work of Daugulis and co-workers on the introduc-
Aromatic nitro compounds are versatile building tion of picolinic acid and 8-aminoquinoline auxiliaries
blocks in the preparation of dyes, pharmaceuticals, as removable directing groups,[10] extensive research
plastics, perfumes and explosives.[1] Therefore, much efforts have been devoted to the development of
attention has been directed to the development of ef- methods for the palladium-catalyzed arylation, alkyla-
ficient and practical methods for the nitration of aro- tion, alkenylation, alkynylation, alkoxylation, boryla-
matic compounds. The mixed acid system (H2SO4/ tion, silylation and intramolecular amination of sp2
3
[10,11]
À
HNO3) and its derivatives are the benchmark method and sp C H bonds.
Additionally, investigations
À
in the classic electrophilic nitration of arenes. Howev- of these bidentate auxiliaries in C H bond functional-
er, in spite of the usefulness of these methods, they ization based on relatively cheaper metal catalysts
tend to suffer from regioselectivity and functional such as iron,[12] cobalt,[13] nickel,[14] and ruthenium[15]
group compatibility issues.[2] Most existing nitrating have also been carried out by several groups. As for
reagents are strong oxidants, which can limit their ap- the use of Cu salts, Daugulis and co-workers recently
plication scope for substrates such as phenols and ani- discovered the aminoquinoline- and picolinamide-di-
lines which can be easily oxidized. In order to over- rected, copper-catalyzed sulfenylation, amination, flu-
come these problems, several alternative strategies orination and etherification of arene and heteroarene
[16]
À
have been developed. For example, nitroarenes can C H bonds while Miura and co-workers discovered
be readily accessed via oxidation of aromatic primary the copper-mediated coupling of benzoic acid deriva-
amines[3] and azides.[4] Alternatively they can be syn- tives and 1,3-azoles with the aid of an 8-aminoquino-
thesized from arylmetals via nitrodemetallation of line-based double N,N-coordination strategy.[17] Stahl
[5]
À
aryl C M bonds (M=B, Li, Sn) or from aryl car- and co-workers reported the copper-mediated me-
boxylic acids[6] via nitrodecarboxylation. In addition, thoxylation of N-(8-quinolinyl)benzamide by employ-
transition metal-catalyzed (Pd or Cu) couplings also ing methanol as the solvent.[18] Later on, Niu inde-
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Table 1. Optimization of the reaction conditions.[a]
[a]
Reaction conditions: amide (0.3 mmol), NaNO2 (0.9 mmol), Cu salt (0.6 mmol),
base (0.6 mmol), solvent (1 mL).
Cu(OAc)2·H2O (1.5 equiv.).
Cu(OAc)2·H2O (1.0 equiv.).
At 808C.
[b]
[c]
[d]
pendently reported a copper-mediated direct aryloxy-
We commenced our studies with the aim to develop
lation of benzamides assisted by an N,O-bidentate di- a direct ortho nitration of benzoic acid derivatives
recting group.[19] Very recently, You and co-workers using the aminoquinoline moiety as the coordinating
À
reported a copper-mediated, tandem oxidative alkyn- group due to its wide applications in selective C H
ylation and annulation of arenes with terminal al- functionalizations. N-(Quinolin-8-yl)benzamide 1a
kynes by taking advantage of the bidentate-chelation was selected as a model substrate for optimizing the
assistance of an 8-aminoquinoline residue[20] while Yu reaction conditions, and the results are listed in
and co-workers discovered the copper-mediated ortho Table 1 (see the Supporting Information for more ex-
À
C H alkynylation and trifluoromethylation of arenes tensive screening results). When we treated N-(quino-
by using an amide-oxazoline directing group.[21] In ad- lin-8-yl)benzamide 1a (0.3 mmol) with NaNO2
3
À
dition, copper-catalyzed intramolecular C(sp ) H and (0.9 mmol) in the presence of Cu(OAc)2·H2O
2
À
C(sp ) H amidation with an 8-aminoquinoline or pi- (0.6 mmol) in MeOH (1 mL) under air, the desired
colinic acid group as the directing group was also de- mononitrated product 2a was isolated in 38% yield
veloped by several groups.[22] Inspired by these re- accompanied by the dinitrated product 3a in 2% yield
ports, we were tempted to test the use of bidentate (Table 1, entry 1). This showed that the first nitration
auxiliaries in the selective nitration of arenes. Herein step is faster than the second nitration step. The yield
we wish to disclose a copper-mediated, aminoquino- of 2a could be increased up to 42% by employing
line group-assisted nitration of benzoic acid deriva- 2 equiv. of NaOAc as the base (Table 1, entry 2). Ex-
tives. (During the preparation of this manuscript, tensive screening studies showed that the efficiency of
Gooßen reported a similar copper-mediated, ortho-ni- the reaction could be significantly affected by the
tration of benzamides using NMO as the oxidant, in choice of the base used and K2HPO4 was determined
which only the mononitrated product was ob- to be the best base for this reaction (Table 1, en-
served.[23]
)
tries 2–7). It is important to note that the selectivity
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Copper-Mediated ortho-Nitration of Arene and Heteroarene C H Bonds
towards mononitration did not change. Other copper
salts such as Cu(OAc)2, CuBr2, CuCl2 and CuI were
found to be less effective than Cu(OAc)2·H2O
(Table 1, entries 8–11). Decreasing the amount of
Cu(OAc)2·H2O to 1.5 or 1.0 equiv. led to lower yields
(Table 1, entries 12 and 13) and the reaction did not
work in the absence of copper salts (Table 1,
entry 14). Changing the solvent to toluene, THF, diox-
ane and CH3CN all gave no product (Table 1, en-
tries 15–18). When the reaction was conducted in
DMF, much to our surprise, the selectivity of mononi-
trated product 2a vs. dinitrated product 3a was re-
versed and they are isolated in a 1:2 ratio with a 46%
combined yield (Table 1, entry 19). To our delight,
highly selective dinitration can be achieved by elevat-
ing the reaction temperature to 808C and the dinitrat-
ed product 3a was isolated in 45% yield (Table 1,
entry 20). Further optimization of base showed the
yield of 3a could be raised to 65% if AgOAc was
used as the base (Table 1, entries 21–23).
We next examined the effect of directing groups. derivatives bearing fluoro, chloro, bromo, trifluoro-
No reaction occurred when a series of monodentate methyl and carboxylate groups on the para-position
directing groups with structures (A–D) similar to 1a of the benzene ring could also participate in the trans-
were tried in the reaction; which indicated that a bi- formation as well, but the yields were slightly lower
dentate coordinating group is essential for the reac- (2h–2l). In addition, substrates bearing methyl or
tion to proceed. In addition, other N,N- or N,O-biden- fluoro group at the ortho-position could be used as
tate directing groups (E–H) failed to promote this re- viable substrates to generate the desired products 2q
action, which showed the indispensable role of the 8- and 2r, showing that the reaction is not sensitive to
aminoquinoline moiety for this reaction.
steric hindrance. Finally, heteroaromatic amides in-
With the optimized conditions in hand, we next set cluding pyridine and thiophene derivatives can be
out to examine the scope of mononitration of benzoic also efficiently mononitrated (2s and 2t).
acid derivatives and the results are summarized in
Next, we turned our attention to the selective dini-
Table 2. Notably, better results were often achieved tration of various amides and the results are summar-
when electron-donating groups including methoxy, ized in Table 3. From this table, we can see that slight-
methyl, ethyl, isopropyl, tert-butyl, phenyl groups ly better results were obtained when electron-donat-
were placed on the para-position of the aromatic ring ing groups including methoxy, methyl, ethyl, isopro-
of the benzoic acid derivatives (2b–2g). Benzoic acid pyl, tert-butyl groups were placed on the para-position
Scheme 1. Control reactions.
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Table 2. Copper-mediated mononitration of carboxylic acid derivatives.[a]
[a]
Reaction conditions: amide
1
(0.3 mmol), NaNO2 (0.9 mmol), Cu(OAc)2·H2O
(0.6 mmol), K2HPO4 (0.6 mmol), MeOH (1 mL) under air for 12 h.
(3b–3f) whereas lower yields were observed when CH3OD, no deuterium was incorporated into the re-
electron-poor benzamides were used (3g and 3h). It is covered starting material or the product. This suggest-
À
worthwhile to point out that meta-substituted sub- ed that the C H activation step is irreversible
strates also reacted efficiently with NaNO2 to give the [Scheme 1, Eq. (1)].[18] The intermolecular KH/KD of
desired products 3i and 3j in yields above 50%. Inter- 1a to 1a-d5 was determined to be 2.0 [Scheme 1, Eq.
estingly, a heterocyclic amide such as isonicotinan- (2)] and a similar KIE was also obtained from the in-
mide can also be efficiently dinitrated in good yield tramolecular H/D competition experiment [KH/KD =
À
(3k).
2.4, Scheme 1, Eq. (3)], suggesting that the ortho C
To get some insights into the mechanism of this H bond cleavage of 1a was involved in the rate-deter-
new transformation, a series of control experiments mining step of the nitration. When the reaction was
was performed. When the reaction was conducted in carried out in the presence of the radical scavenger
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Copper-Mediated ortho-Nitration of Arene and Heteroarene C H Bonds
Table 3. Copper-mediated dinitration of carboxylic acid derivatives.[a]
[a]
Reaction conditions: amide
1
(0.3 mmol), NaNO2 (0.9 mmol), Cu(OAc)2·H2O
(0.6 mmol), AgOAc (0.6 mmol), DMF (1 mL) under air for 12 h.
2,2,6,6-tetramethylpiperidine
N-oxyl
(TEMPO,
1 equiv.), the yield of the desired product was only
slightly decreased, which ruled out the possibility of
a radical mechanism.
Although the exact mechanism is still not clear at
present, on the basis of the above results, a plausible
reaction mechanism is proposed and shown in
Scheme 2. As depicted in Scheme 2, coordination of
1a to a copper(II) species followed by ligand ex-
change generates the copper complex 5; 5 next under-
À
goes C H activation to form the aryl/Cu(II) species 6
by a cyclocupration process.[22] Subsequently, the
Cu(OAc)2-promoted oxidation of 6 affords a Cu(III)
In summary, we have developed a novel copper-
species 7.[24] Then 7 next reacts with sodium nitrite to mediated, chelation-assisted ortho C H bond nitra-
generate the copper complex 8. In the final step, 8 un- tion of benzoic acid derivatives using NaNO2 as the
dergoes reductive elimination to produce the desired source of the nitro group. The reaction was found to
À
À
nitration compound 2a. Alternatively, the C H activa- be critically dependent on the use of an 8-aminoqui-
tion step may take place after the center copper(II) noline directing group. Selective mono- or dinitration
ion has been oxidized to copper(III) as proposed by can be achieved by simply changing the reaction con-
Miura[17] and You.[20]
ditions. In addition, the auxiliary can be conveniently
In order to demonstrate the synthetic utility of our removed and recovered. Further studies on the mech-
method, 2a was hydrolyzed with HCl in water and 2- anistic details of this reaction and efforts to expand
nitrobenzoic acid was isolated in 78% yield. The di- the reaction scope are currently underway in our lab;
recting group 8-aminoquinoline could also be recov- the results will be reported in due course.
ered in 80% yield [Eq. (4)].
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Scheme 2. Plausible reaction mechanism.
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Experimental Section
À
General Procedure for Copper-Mediated C H
Mononitration of Benzoic Acid Derivatives
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Benzamide
1
(0.3 mmol), Cu(OAc)2·H2O (120 mg,
0.6 mmol), K2HPO4 (105 mg, 0.6 mmol), NaNO2 (62 mg,
0.9 mmol) and anhydrous MeOH (1 mL) were added to
a 25-mL Schlenk flask equipped with a high-vacuum PTFE
valve-to-glass seal. Then the flask was sealed under air and
the contents stirred at 608C for 12 h. After the completion
of the reaction, the solvent was evaporated under reduced
pressure and the residue was then quenched with aqueous
1M HCl solution (10 mL). The mixture was extracted with
ethyl acetate, and the combined organic layer was dried
over sodium sulfate. Concentration under vacuum followed
by silica gel column purification with petroleum ether/ethyl
acetate elutent gave the desired product 2.
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Acknowledgements
Support of this work by grants from the National Science
Foundation of China (No. 21072051), and the Fundamental
Research Funds for the Central Universities, Hunan Universi-
ty is gratefully acknowledged.
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8 Copper-Mediated ortho-Nitration of Arene and
À
Heteroarene C H Bonds Assisted by an 8-Aminoquinoline
Directing Group
Adv. Synth. Catal. 2015, 357, 1 – 8
Jidan Liu, Shaobo Zhuang, Qingwen Gui, Xiang Chen,
Zhiyong Yang, Ze Tan*
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