O-iodoxybenzoic acid mediated N-arylation of aromatic amines by using arylhydrazines as the arylating counterpart

Article abstract of DOI:10.1002/ejoc.201300917

Through free-radical trapping experiments we have established, for the first time, the combination of arylhydrazines with o-iodoxybenzoic acid (IBX) for the generation of aryl free radicals. On the basis of this finding, a method was developed for the N-arylation of aromatic amines under mild conditions (base-free, -5 °C) by using arylhydrazines as the arylating counterpart and arylamines. The scope of this method was demonstrated by using a number of arylhydrazines and arylamines, which gave the N-arylated amines in good yields. Through free-radical trapping experiments, the present work describes the combination of arylhydrazines with o-iodoxybenzoic acid (IBX) for the generation aryl free radicals. This finding is exploited in the development of a mild method for the N-arylation of arylamines by using arylhydrazines as the arylating agents. The scope of this method is demonstrated through a number of examples. Copyright

Full text of DOI:10.1002/ejoc.201300917

SHORT COMMUNICATION
DOI: 10.1002/ejoc.201300917
o-Iodoxybenzoic Acid Mediated N-Arylation of Aromatic Amines by Using
Arylhydrazines as the Arylating Counterpart
Ravindra R. Jadhav,[a] Sameerana N. Huddar,[a] and Krishnacharya G. Akamanchi*[a]
Keywords: Amines / Arylation / Arylhydrazines / Copper / Hypervalent compounds
Through free-radical trapping experiments we have estab-
lished, for the first time, the combination of arylhydrazines
with o-iodoxybenzoic acid (IBX) for the generation of aryl
free radicals. On the basis of this finding, a method was de-
veloped for the N-arylation of aromatic amines under mild
conditions (base-free, –5 °C) by using arylhydrazines as the
arylating counterpart and arylamines. The scope of this
method was demonstrated by using a number of arylhydraz-
ines and arylamines, which gave the N-arylated amines in
good yields.
aldehydes, and alcohols leading to the formation of disub-
stituted alkenes with vicinal stereocenters. In light of all
these points and the requirement for N-arylated amines,
there is a scope for new methods. Our research group, at-
tracted by the mild and chemoselective nature of hyperva-
lent iodine(V) reagents,[8] is extensively exploring new appli-
cations of these reagents, and the present work, which offers
a new method for the N-arylation of amines, is an outcome
of one such exploration.
Aryldiazonium salts produce aryl free radicals, very reac-
tive unstabilized σ radicals, upon heating or upon reaction
with metals such as Al, Cu, Pd, Ag, Pt, Au, and so on.[9]
Similarly, aryl free radicals can also be produced by using
arylhydrazines in the presence of oxidizing agents.[10]
Hypervalent iodine(V) reagents, mainly o-iodoxybenzoic
acid (IBX) and Dess–Martin periodinane (DMP), have be-
come alternative oxidizing agents for various metal oxi-
dants.[11] The versatility of these reagents has been firmly
established by various transformations they bring about,
such as oxidative C–C coupling, oxidative cyclization, oxi-
dative rearrangements, oxidative deoximation, oxidative
ring expansion and contraction, C–N bond formation, oxi-
dation of alcohols, and others.[12] Because of their mild na-
ture and their ability to be chemoselective, these reagents
are preferred in the total synthesis of complex molecules,
including natural products.[13]
Introduction
The N-arylation of amines is an active area of research
in organic synthesis, because N-arylated compounds are
used in the synthesis of numerous substances including nat-
ural products, agrochemicals, dyes, and pharmaceuticals.[1]
In the literature, many methods for the N-arylation of
amines are reported. For instance, the coupling of electro-
philic aryl halides and nucleophilic primary or secondary
amines by using Pd and Cu catalysts, pioneered by Buch-
wald, Hartwig, and others, is a hallmark reaction in this
field.[2] Another method, independently developed by
Chan, Evans, and Lam, based on the Cu-mediated oxidat-
ive amination of arylboronic acids with amines and other
nucleophiles, provides a valuable alternative in the construc-
tion of carbon–heteroatom bonds.[3] The drawbacks of Pd-
and Cu-catalyzed N-arylation reactions include the require-
ment of high temperatures, long reaction times, the need for
ligands and bases, and the generation of corrosive halide
ions in many cases. By utilizing diaryliodonium salts, Be-
ringer[4] established yet another method for N-arylation;
however, owing to difficulties in the synthesis of these salts,
the applicability of this method is limited. In the presence of
copper salts, phenyllead triacetate[5] and triphenylbismuth[6]
have found use in the synthesis of arylamines, but these rea-
gents suffer from nonreactivity towards substrates contain-
ing electron-withdrawing substituents, and they are not eco-
friendly, and, therefore, they are less popular. Recently, Lutz
and Thomson[7] reported a hypervalent iodine initiated
fragment-coupling cascade reaction of N-allylhydrazones,
Results and Discussion
It has been shown that IBX reactions proceed through
a single-electron transfer (SET) mechanism.[14] IBX reacts
violently with hydrazine and is reduced to o-iodobenzoic
acid. We hypothesized that, on the same lines, IBX would
oxidatively decompose phenylhydrazine to produce the
phenyl radical by expelling the oxidized hydrazine group as
nitrogen gas. To prove this hypothesis, we undertook two
[a] Department of Pharmaceutical Sciences and Technology,
Institute of Chemical Technology,
Matunga, Mumbai 400019, India
E-mail: kgap@rediffmail.com
kg.akamanchi@ictmumbai.edu.in
http://www.ictmumbai.edu.in
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejoc.201300917.
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R. R. Jadhav, S. N. Huddar, K. G. Akamanchi
SHORT COMMUNICATION
free-radical trapping experiments and were successful. In
To establish the reaction conditions, preliminary experi-
the first experiment, phenylhydrazine was treated carefully ments were carried out by using aniline and phenylhydraz-
at room temperature with IBX in acetonitrile in the pres- ine as model substrates. Treatment of phenylhydrazine (2a,
ence of CCl4 as a radical trap. After workup, chlorobenzene 1.5 equiv.) with IBX (3 equiv.) in the presence of aniline (1a,
was isolated in 25% yield (Scheme 1a). In the second ex- 1.0 equiv.) and Cu(OAc)2 (0.1 equiv.) as the catalyst in ace-
periment, performed under the same reaction conditions as
those used in the first experiment, (2,2,6,6-tetramethylpip-
Table 2. N-Arylation of amines by using phenylhydrazine (2a) as
the arylating counterpart.
eridin-1-yl)oxyl (TEMPO), a compound already in the free-
radical state, was used as the radical trapping agent in the
presence of a catalytic amount of Cu(OAc)2; the expected
product,
1-[(2,2,6,6-tetramethylpiperidinyl)oxy]benzene,
was formed in 30% yield (Scheme 1b).
Scheme 1. Trapping of the phenyl free radical.
At that point, having established the generation of the
free radical, experiments were carried out by adding phenyl-
hydrazine to a mixture of IBX and an arylamine in the pres-
ence of a catalytic amount of Cu(OAc)2. It was anticipated
that the generated phenyl free radical would be trapped by
the amine to form an N-arylamine, and this would offer a
new method for the N-arylation of amines. This, in fact,
happened, and the details are discussed below.
Table 1. Optimization of reagents and reaction conditions.[a]
Entry Oxidant Cu(OAc)2 Solvent Temp.
Yield[b] [%]
(equiv.)
[equiv.]
[°C]
3a
4a
1
2
3
4
5
6
7
8
9
IBX (1.5)
IBX (3)
IBX (3)
IBX (3)
IBX (3)
IBX (4)
IBX (3)
IBX (0)
IBX (3)
DMP (3)
DIB (3)
0.1
0.1
0.1
0.1
0.1
0.1
0
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
DMF
–5
–5
r.t.
–20
–5
–5
–5
–5
–5
–5
–5
30
78
50
–
05
10
20
25
10[c]
10
15
10
15
05
20
78[c]
78
10
20
60
–
3
0.1
0.1
0.1
10
11
CH3CN
CH3CN
–
[a] All reactions were carried out on a 5 mmol scale with aniline
(1 equiv.) and phenylhydrazine (1.5 equiv.). [b] Yield of isolated
product after chromatography (silica gel #60-120; ethyl acetate/hex-
ane, 2:98); reaction time 3 h. [c] Reaction time 7 h.
[a] All reactions were carried out on a 5 mmol scale with the amine
(1 equiv.), phenylhydrazine (1.5 equiv.), IBX (3 equiv.), and
Cu(OAc)2 (0.1 equiv.). [b] Yield of isolated product after
chromatography (silica gel #60-120; ethyl acetate/hexane, 2:98).
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o-Iodoxybenzoic Acid Mediated N-Arylation of Aromatic Amines
tonitrile as the solvent at –5 °C led to the formation of di- 30% for 3a (Table 1, Entry 1). To ascertain the role of
phenylamine (3a) and azobenzene (4a) in 78 and 10% yield, Cu(OAc)2, a reaction was carried out in the absence
respectively (Table 1, Entry 2). To study the effect of tem- Cu(OAc)2, and 3a was formed in a very low yield of 10%
perature, the reactions were repeated separately at room (Table 1, Entry 7). Copper salts are known to oxidize phen-
temperature and at –20 °C. In both cases, the yields of the ylhydrazine,[15] and therefore, a reaction was performed by
products were affected: a decrease in the yield of 3a to 50% using Cu(OAc)2 (3.0 equiv.) as the sole oxidizing agent.
and an increase in the yield of 4a to 20% was observed at Product 3a was formed but only in a very low yield of 20%
room temperature (Table 1, Entry 3), whereas at the lower (Table 1, Entry 8). These results indicated that either IBX
temperature of –20 °C, 3a was not formed, but 4a was ob- or Cu(OAc)2 alone was not efficient for the reaction. DMF,
tained in 25% yield (Table 1, Entry 4). There was no im- screened as an alternative solvent, was found to be viable,
provement in the yield with a prolonged reaction time but it delivered 3a in an inferior yield of 60% (Table 1, En-
(Table 1, Entry 5) or an increase in the amount of IBX to try 9). Other hypervalent iodine reagents such as DMP and
4 equiv. (Table 1, Entry 6); however, a decrease in the (diacetoxyiodo)benzene (DIB) were also studied under the
amount of IBX to 1.5 equiv. resulted in a lower yield of optimized reaction conditions. In both cases, the formation
of 3a was not observed; instead, these reactions resulted in
the formation of a complex mixture in which small amounts
Table 3. N-Arylation of amines by using (2-ethylphenyl)hydrazine
of 4a were present (Table 1, Entries 10 and 11).
To explore the generality of the reaction, various substi-
tuted anilines and different arylhydrazines were trans-
formed into N-arylamines under the optimized reaction
conditions, and the results are recorded in Tables 2, 3, and
4.
(2b) as the arylating counterpart.
Reactions were carried out with phenylhydrazine (2a) as
the arylating counterpart with various substituted anilines
(Table 2). In all cases, the expected N-arylanilines were ob-
tained. Substrates containing electron-donating groups gave
Table 4. N-Arylation of amines by using (4-fluorophenyl)hydrazine
(2c) as the arylating counterpart.
[a] All reactions were carried out on a 5 mmol scale with the amine
(1 equiv.), (2-ethylphenyl)hydrazine (1.5 equiv.), IBX (3 equiv.), and
Cu(OAc)2 (0.1 equiv.). [b] Yield of isolated product after
chromatography (silica gel #60-120; ethyl acetate/hexane, 5:95).
[a] All reactions were carried out on a 5 mmol scale with the aniline
(1 equiv.), (4-fluorophenyl)hydrazine (1.5 equiv.), IBX (3 equiv.),
and Cu(OAc)2 (0.1 equiv.). [b] Yield of isolated product after
chromatography (silica gel #60-120; ethyl acetate/hexane, 5:95).
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R. R. Jadhav, S. N. Huddar, K. G. Akamanchi
SHORT COMMUNICATION
the products in good yields of 78–71% (Table 2, Entries 1– phenyl)hydrazine (2f) in addition to 2a–c were evaluated in
9), whereas substrates containing electron-withdrawing the reaction with aniline (Table 5). In all cases, the reactions
groups gave the products in lower yields of 67–63% were smooth, and the N-arylated products were obtained in
(Table 2, Entries 10–12).
78–66% yield (Table 5, Entries 1–6).
Reactions with (2-ethylphenyl)hydrazine (2b) as the aryl-
An attempt was made to formulate a tentative mecha-
ating agent also gave good yields of the N-arylated products nism for this reaction. Given that iodine is an electrophilic
(Table 3). Here again, substrates containing electron-donat- center in IBX, initial formation of IBX–phenylhydrazine
ing groups gave the products in good yields of 72–67% adduct intermediate A is considered, which upon oxidative
(Table 3, Entries 1–6), whereas substrates containing elec- decomposition would form phenyldiazine B and o-iodoso-
tron-withdrawing groups gave the products in lower yields benzoic acid (IBA). Phenyldiazine B, thus formed, reacts
of 63–60% (Table 3, Entries 7 and 8).
with a second molecule of IBX and undergoes oxidative
Similarly, all the reactions attempted with (4-fluoro- cleavage through single-electron transfer to form phenyl
phenyl)hydrazine (2c) as the arylating counterpart with a free radical D, which is subsequently trapped by aniline in
variety anilines were successful, and the same trend in the the presence of Cu(OAc)2, and this leads to the formation
yield of the N-arylated products was observed with respect of N-phenylaniline (3a, Scheme 2). The role of Cu2+ could
to the nature of the substituents. Substrates containing elec- be to stabilize the phenyl free radical and to bring together
tron-donating groups gave good yields of the products in this radical and aniline through complexation;[16] this would
the range of 68–66% (Table 4, Entries 1–4), whereas lower lead to efficient trapping and consequently to a higher yield
yields of 60% were observed with substrates containing of the product.
electron-withdrawing groups (Table 4, Entries 5 and 6).
To study the scope of the arylhydrazine counterpart,
other arylhydrazines such as (2-chlorophenyl)hydrazine
(2d), (3,5-dichlorophenyl)hydrazine (2e), and (2-bromo-
Table 5. N-Arylation of aniline by using arylhydrazines 2 as the
arylating counterpart.
Scheme 2. Tentative mechanism depicted for N-phenylation of anil-
ine by using 2a as the arylating counterpart.
Conclusions
Through free-radical trapping experiments we have es-
tablished, for the first time, the combination of arylhydraz-
ines with IBX for the generation of aryl free radicals. On
the basis of this observation, a method was developed for
the N-arylation of aromatic amines under mild conditions
(base-free, –5 °C) by using arylhydrazines as the arylating
[a] All reactions were carried out on a 5 mmol scale with aniline
counterpart. The scope of the reaction was demonstrated
(1 equiv.), arylhydrazine (1.5 equiv.), IBX (3 equiv.), and
with a number of arylhydrazines and arylamines. This work
may attract attention for further developments.
Cu(OAc)2 (0.1 equiv.). [b] Yield of isolated product after
chromatography (silica gel #60-120; ethyl acetate/hexane, 2:98).
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o-Iodoxybenzoic Acid Mediated N-Arylation of Aromatic Amines
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General Procedure for the N-Arylation of Arylamines: Copper(II)
acetate (0.5 mmol) was added to a stirred solution of acetonitrile
(20 mL) and the arylamine (5 mmol), and the mixture was cooled
to –5 °C in an ice/salt bath and stirred for 15 min. IBX (15 mmol)
was added to this cold solution. The mixture was stirred for 5 min
followed by the dropwise addition of arylhydrazine (7.5 mmol) in
acetonitrile (5 mL) over a period of 20 min and then stirred until
the reaction was complete. Upon completion of the reaction (3 h,
by TLC), the reaction mixture was filtered, and the filtrate was
concentrated under reduced pressure to remove acetonitrile. The
residue was slurried by adding water (20 mL), neutralized with 10%
NaHCO3 solution, and extracted with chloroform (2ϫ 20 mL).
The organic layer was dried with anhydrous sodium sulfate, con-
centrated, and chromatographed (silica gel #60-120; ethyl acetate/
hexane) to afford the pure product.
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NMR spectra.
Acknowledgments
We sincerely thank the University Grants Commission (UGC) of
India for financial support under UGC-SRF (NET). We are grate-
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Received: June 22, 2013
Published Online: September 23, 2013
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