Utilization of Unsymmetric Diaryliodonium Salts in α-Arylation of α-Fluoroacetoacetamides

Article abstract of DOI:10.1002/asia.202001160

The use of unsymmetric diaryliodonium salts as a versatile class of arylating agents has been demonstrated by developing a novel strategy to quickly access α-arylated α-fluoroacetoacetamides. The protocol provides a convenient metal-free method for the α-arylation of a diverse class of fluorinated acetoacetamides, and the products are obtained in good yields. The strategy, upon use of electron-deficient diaryliodonium salts as an arylating agent, provides α-fluoroacetamides through a spontaneous arylation/deacylation cascade.

Full text of DOI:10.1002/asia.202001160

CHEMISTRY
AN ASIAN JOURNAL
www.chemasianj.org
Accepted Article
Title: Utilization of Diaryliodonium Salts in α-Arylation of α-
Fluoroacetoacetamides
Authors: Mohd Khalid Zaheer, Narendra Kumar Vaishanv, Ruchir Kant,
and Kishor Mohanan
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To be cited as: Chem. Asian J. 10.1002/asia.202001160
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Utilization of Unsymmetric Diaryliodonium Salts in α-Arylation of
α-Fluoroacetoacetamides
Mohd Khalid Zaheer,[a] Narendra Kumar Vaishanv,[a] Ruchir Kant[c] and Kishor Mohanan,* [a,b]
[a]
M. K. Zaheer, N. K. Vaishanv, Dr. K. Mohanan
Medicinal and Process Chemistry Division
CSIR-Central Drug Research Institute, Lucknow, 226031 (India)
E-mail: kishor.mohanan@cdri.res.in
[b]
[c]
Dr. K. Mohanan
Academy of Scientific and Innovative Research, Ghaziabad-201002, India
Dr. R. Kant
Molecular and Structural Biology
CSIR-Central Drug Research Institute, Lucknow, 226031 (India)
Supporting information for this article is given via a link at the end of the document.
Abstract: The use of unsymmetric diaryliodonium salts as a versatile
class of arylating agents has been demonstrated by developing a
novel strategy to quickly access α-arylated α-fluoroacetoacetamides.
The protocol provides a convenient metal-free method for the α-
arylation of a diverse class of fluorinated acetoacetamides, and the
products are obtained in good yields. The strategy, upon use of
electron-deficient diaryliodonium salts as an arylating agent, provides
α-fluoroacetamides through a spontaneous arylation/deacylation
cascade.
substrates under metal-free conditions (Scheme 1a).[12] Despite
the immense synthetic potential of this strategy, the applicability
in the arylation of fluorocarbon nucleophiles has been less studied.
With our interest in developing novel metal-free methods to
introduce fluoroalkyl groups into arenes,[13] we envisioned that
diaryliodonium salts could be used for the direct arylation of α-
fluoroacetoacetamides. Herein, we present an efficient protocol
for the direct α-arylation of α-fluoroacetoacetamides under mild
basic conditions to generate a quaternary benzylic fluoroalkyl
center. Interestingly, when electron-deficient arenes were
transferred to acetoacetamides, the products underwent
deacylation, constituting a new strategy to access α-aryl-α-
fluoroacetamides, a prominent structural subunit present in a wide
array of pharmaceuticals and agrochemicals (Scheme 1b).[14]
Nowadays, the introduction of fluoroalkyl groups into arenes has
become a common practice in medicinal chemistry to improve the
biological properties of drug candidates.[1] Obviously, this is
attributed to the unique electronic features possessed by fluorine,
which, unlike the other halogens, often refine the biological
properties, including metabolic stability, permeability, and protein
binding affinity.[2] These medicinal applications and the
widespread use in material science have fuelled the development
of practical methods for introducing fluorinated units into arenes.[3]
As such, the past two decades have witnessed remarkable
progress in devising strategies for the effective preparation of F-
and CF3-containing arenes.[4,5] However, this field has been
dominated by metal-catalyzed trifluoromethylation and
fluoroalkylations.[6] Aromatic
compounds
containing
α-
fluorocarbonyl groups are of particular interest as non-enolizable
analogues of the corresponding arylacetamides.[7] However, a
vast majority of the methods to synthesize them utilize Pd or Cu
catalyzed coupling reactions of aryl halides with fluoroenolates.[8]
Given the importance of this class of compounds in drug
discovery, a complementary method that obviates the need of
expensive catalysts, harsh conditions and directly uses simple
and readily available substrates would be highly important.
Scheme 1. Approaches to electrophilic α-arylation of C-nucleophiles using
diaryliodonium salts.
Recently, diaryliodonium salts have become broadly applied
arylating agents for metal-catalyzed and metal-free electrophilic
arylation reactions due to their wide scope and remarkable
functional group tolerance.[9,10] The efficiency of diaryliodonium
salts in transition metal-free arylation processes has been
illustrated with a broad range of heteroatom nucleophiles such as
O-, N-, S- and P-nucleophiles.[11] Furthermore, in recent years,
several elegant methodologies have been devised for the
Initially, 2-fluoro-3-oxo-N-phenylbutanamide 1a was chosen as an
appropriate enolizable substrate for the reaction with
phenyl(mesityl)iodonium salt 2a. The reaction conducted in the
presence of t-BuOK gave the α-arylated product 3a in 11% yield
in THF at 50°C (Table 1, entry 1). A brief survey of solvents was
then conducted to improve the reaction efficiency (entries 2-7),
straightforward α-arylation of
a wide range of enolizable
1
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and dioxane was found optimal, delivering the anticipated product
3a in 67 % yield in a reaction time of 30 min (entry 6). To improve
the yields further, we focused on other inorganic bases, and a
large set of frequently used inorganic bases including NaH, KOH,
Na2CO3, Cs2CO3 and CsF were screened. The use of Cs2CO3
increased the yield of the product to 78% (entry 11). Moreover,
the reactions attempted using organic bases such as DMAP and
DABCO were unsuccessful (entries 13,14). Further, the variation
of temperature was detrimental, and at a higher temperature, the
reaction produced a complex mixture (entry 16). The reaction was
subsequently checked for the influence of the counter anion using
triflate and tetrafluoroborate salts, and in these cases, there was
a decrease in the yield (entries 17,18).
electronically varied functional groups at meta-position of the aryl
ring, and the arylated products were obtained in moderate yields
(3i,3j). The reaction scope was successfully extended to α-
fluoroacetoacetamides derived from ortho-substituted anilines
(3k). The compatibility of this protocol was evaluated using
disubstituted α-fluoroacetoacetamides, and α-arylation occurred
to deliver the products in good yields (3l-3n).
Table 1. Optimization of the reaction conditions[a]
entry
1
anion X
OTs
OTs
OTs
OTs
OTs
OTs
OTs
OTs
OTs
OTs
OTs
OTs
OTs
OTs
OTs
OTs
BF4
base
solvent
THF
time (h)
yieldb (%)
11
t-BuOK
t-BuOK
t-BuOK
t-BuOK
t-BuOK
t-BuOK
t-BuOK
NaH
6
2
TBME
6
52
3
toluene
xylene
6
36
4
6
45
5
DME
6
55
6
dioxane
DMF
0.5
6
67
7
30
8
dioxane
dioxane
dioxane
dioxane
dioxane
dioxane
dioxane
dioxane
dioxane
dioxane
dioxane
6
57
9
KOH
6
46
10
11
12
13
14
15c
16d
17
18
Na2CO3
Cs2CO3
CsF
6
60
0.5
0.5
6
78
60
DMAP
DABCO
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
<5
6
<5
12
0.5
0.5
0.5
<5
55
68
OTf
73
Scheme 2. Substrate scope of α-fluoroacetoacetamides. General conditions: 1
(0.2 mmol), 2a (0.22 mmol), Cs2CO3 (0.22 mmol) in dioxane (2.0 mL) at 50 °C
for 30 min. Isolated yield after silica gel column chromatography. [a]The reaction
carried out using diphenyliodonium tosylate afforded 3a in 52% yield.
[a]General conditions: 1a (0.20 mmol), 2a (0.22 mmol) and base (0.22 mmol)
in solvent (2.0 mL) at 50 °C. [b]Isolated yield after silica gel column
chromatography. [c]Reaction carried out at 25 °C. [d]Reaction carried out at 80 °C.
Likewise, 1-naphthyl-substituted α-fluoroacetoacetamide was
converted to the product 3o in 60% yield. We were pleased to
note that, besides aryl substrates, the heteroaryl substrates, such
as those derived from 2-aminopyridine and 8-aminoquinoline,
were also competent as a nucleophile for this arylation process
(3p,3q). The scope of the reaction was further illustrated by using
N-benzyl and N-benzhydryl substrates under the standard
conditions, and the anticipated products were accomplished in
good yields (3r,3s). Of note, the viability of symmetric
diaryliodonium salts in this protocol was tested using
diphenyliodonium tosylate, and the product 3a was obtained in
52% yield. Disappointingly, the tertiary amide derivative was
found unreactive under the reaction conditions (3t).
With the reliable conditions identified for this α-arylation protocol,
we proceeded towards the evaluation of the substrate scope with
respect to the amide component using phenyl(mesityl)iodonium
salt 2a. Notably, the reactions of a diverse range of electronically
differentiated fluoroacetoacetamides delivered the α-arylated
products in moderate to good yields (Scheme 2). The
fluoroacetoacetamides bearing electron-donating substituents at
the para-position of the phenyl ring provided the desired products
in synthetically useful yields (3b,3c). Similarly, the reaction
furnished arylated products for substrates containing bromo,
chloro and fluoro moieties at the para-position of the phenyl ring
(3d-3f). The structure of 3d was ascertained by X-ray analysis.[15]
Moreover, amides bearing electron-withdrawing functional groups
such as trifluoromethyl, and acetyl at para-position of the aryl ring
were also transformed to the corresponding products in good
yields (3g,3h). The reaction also incorporated substrates having
Next, to explore the scope of the arylating agent, various
unsymmetric diaryliodonium salts retaining the mesityl group as
“dummy-group” were tested (Scheme 3).[16] Delightfully, the
iodonium salts bearing methoxy, t-butyl, i-propyl, ethyl, methyl,
2
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and phenyl substitutions at the para-position of the aryl group
fluoroacetoacetamides, a series of electronically differentiated
successfully
participated
to
deliver
the
arylated
amide
substrates
were
reacted
with
4-
fluoroacetoacetamides (3u-3z). The diaryliodonium salt having
meta-substituted aryl moiety took part in the reaction effectively
(3aa,3ab). Pleasingly, the reaction conducted using the 2-
naphthyliodonium salt furnished the arylated product in moderate
yield (3ac). Surprisingly, while expanding the scope of this
reaction employing electron-deficient diaryliodonium salts under
the optimized conditions, we observed a concomitant deacylation
process with arylation to provide access to arylfluoroacetamides
4 in good yield. This spontaneous deacylation may be attributed
to a further increase in electrophilicity of the α-carbon center
rendered by fluorine as well as the newly installed electron-
deficient aryl group.
carbomethoxyphenyl(mesityl)iodonium salt, and we were
delighted to find that the reaction proceeded smoothly to afford
the corresponding products in good yields (4h-4k). Besides
aromatic amides, the heteroaryl amide derived from 5-iodo-2-
aminopyridine was also viable for this deacylative transformation;
however, the reaction required longer time, and the product 4l
was obtained in moderate yield.
Scheme 4. Substrate scope for α-aryl-α-fluoroacetamide synthesis. General
conditions: 1 (0.2 mmol), 2 (0.22 mmol), Cs2CO3 (0.22 mmol), in dioxane (2.0
mL) at 50 °C for 30 min. Isolated yield after silica gel column chromatography.
[a]Reaction run for 3 h.
Finally, we were pleased to find that this new arylation reaction
can be used to access α-aryl-α-fluoroacetamides by K2CO3-
Scheme 3. Substrate scope of diaryliodonium salts. General conditions: 1a (0.2
mmol), 2 (0.22 mmol), Cs2CO3 (0.22 mmol), in dioxane (2.0 mL) at 50 °C for 30
min. Isolated yield after silica gel column chromatography. [a]Reaction carried
out with 0.30 mmol of Cs2CO3 for 2 h.
mediated
deacylation of the corresponding arylated
acetoacetamides. For instance, the methanolysis of compound 3a
provided fluoroacetamide 4m in 87% yield (Scheme 5).
It is worth noting that this deacylative arylation protocol constitutes
an efficient route for the synthesis of arylfluoroacetamides, which
are valuable synthetic building blocks in medicinal chemistry.
Encouraged by this finding, we sought to further explore the
substrate
aryl(mesityl)iodonium
scope
for
this
salts
methodology
bearing electron-withdrawing
by
varying
Scheme 5. Deacylative route to α-aryl-α-fluoroacetamides.
substituents. As shown in Scheme 4, a wide variety of
diaryliodonium salts bearing electron-deficient aryl moieties
smoothly underwent deacylative arylation to produce the
arylfluoroamides 4 as the sole product. The reaction tolerated
various electron-deficient functionalizable handles, such as triflate,
trifluoromethyl, cyanide, carbomethoxy, and carboethoxy groups
at the para-position of the aryl group, and the products were
obtained in moderate to good yields (4a-4e). In addition, the aryl
group having a cyano substitution at the meta-position was readily
transferred, and the desired product 4f was obtained in 64% yield.
In addition to monosubstituted salts, the reaction proceeded
smoothly with 3,4-disubstituted iodonium salt, and the anticipated
product was obtained in reasonable yield (4g). Finally, to check
whether the deacylative arylation strategy is applicable to other
It has been established that there are two possible pathways for
the metal-free arylation; 1) it proceeds through SET mechanism[17]
or 2) through the formation of a T-shaped intermediate.[18] To test
whether a radical pathway is involved in this case, a control
experiment was conducted for the arylation of α-
fluoroacetoacetamide 1a in the presence of radical-inhibitor
TEMPO, and the desired α-arylation product 3a was obtained in
64% yield. Thus, radical mechanism can be excluded. On the
basis of this transformation and literature reports, a reaction
pathway is posited in Scheme 6. The reaction likely operates
through one of the two possible tricoordinated iodine
intermediates I/II, formed by the coordination of the enolate
through the C-I or O-I bond. These intermediates are in fast
3
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equilibrium with each other, and subsequently undergo normal
[1,2] ligand coupling or [2,3]-rearrangement to furnish the arylated
product 3. Although not clear, we presume that the increased
electrophilicity of the resulting tetrasubstituted fluorocarbon
center upon installation of an electron-deficient aryl group
facilitates the base-mediated deacylation to afford the desired
arylfluoroamide 4.
thank Dr. Tejender S. Thakur, MSB division, CSIR-CDRI for
supervising the X-ray data collection and structure determination.
We thank SAIF division for analytical support.
Keywords: α-Fluoroacetoacetamides • Diaryliodonium salts • α-
Arylation • Metal-free • Deacylation
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deacylation protocol could be used to rapidly access
arylfluoroacetamides from arylated fluoroacetoacetamides.
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Financial support by the Science and Engineering Research
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5
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COMMUNICATION
Mohd Khalid Zaheer, Narendra Kumar
Vaishanv, Ruchir Kant and Kishor
Mohanan*
Page No. – Page No.
Utilization of Unsymmetric
Diaryliodonium Salts in α-Arylation of
α-Fluoroacetoacetamides
The use of diaryliodonium salts as a versatile class of arylating agents has been
demonstrated by developing a novel strategy to quickly access α-arylated α-
fluoroacetoacetamides.
6
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