Chelation-Assisted Palladium-Catalyzed γ-Arylation of Aliphatic Carboxylic Acid Derivatives

Article abstract of DOI:10.1002/adsc.201601121

A palladium(II)-catalyzed protocol for the highly regioselective remote γ-C–H arylation of aliphatic carboxylic acid has been disclosed. The 8-aminoquinoline moiety as an intramolecular bidentate chelator was found to be suitable for this γ-C–H arylation. Various aryl iodides successfully produced the regioselectively mono-arylated products with negligible diarylation. Functional group tolerance and easy-to-handle reaction conditions make this method attractive. (Figure presented.).

Full text of DOI:10.1002/adsc.201601121

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DOI: 10.1002/adsc.201601121
Chelation-Assisted Palladium-Catalyzed g-Arylation of Aliphatic
Carboxylic Acid Derivatives
Aniruddha Dey,+a Sandeep Pimparkar,+a Arghya Deb,a Srimanta Guin,a
and Debabrata Maitia,*
a
Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai – 400 076, India
Fax : (+91)-022–2576–7152; e-mail: dmaiti@chem.iitb.ac.in
+
Both of these authors have contributed equally to this work.
Received: October 11, 2016; Revised: January 11, 2017; Published online: && &&, 0000
Supporting information for this article can be found under http://dx.doi.org/10.1002/adsc.201601121.
Abstract: A palladium(II)-catalyzed protocol for
the highly regioselective remote g-C–H arylation of
aliphatic carboxylic acid has been disclosed. The 8-
aminoquinoline moiety as an intramolecular biden-
tate chelator was found to be suitable for this g-C–
H arylation. Various aryl iodides successfully pro-
duced the regioselectively mono-arylated products
with negligible diarylation. Functional group toler-
ance and easy-to-handle reaction conditions make
this method attractive.
One among these many strategies allowing the for-
mation of a carbon-carbon bond at an unactivated
alkyl C–H centre is by the use of a metal-catalyzed
chelation approach. Formation of a five-membered
metallacycle has led to a highly selective b-C–H func-
tionalization. The efficacy of Daugulisꢀ 8-aminoquino-
line directing group in this regard has been beneficial
which can be corroborated by recent literature re-
ports.[1g,2] Successful b-C–H arylation/alkylation via
the chelation approach in the presence of a variety of
metal salts has been demonstrated by Chatani, Ge
and others.[1d,3] A wish to further the scope of this pro-
tocol into taming more distal C–H bonds, viz. g-C–H
bonds, to undergo functionalization was foreseeable.
Progress on g-C–H functionalization was thus endea-
vored by various research groups.[4] g-C–H arylation
of amines by a 2-picolinic acid auxiliary was per-
Keywords: aliphatic g-C–H arylation; aminoquino-
lines; carboxylic acids; palladium
The inception of C–H activation in materializing re- formed by Daugulis. (Scheme 1).[2a,b] Pioneering re-
markable organic transformations in recent years has ports by Corey on the g-C–H functionalization of N-
revolutionized the modern trend of retrosynthetic dis- phthaloyl-a-amino amides as well as by Chen hold
connections. A series of success stories over the de-
cades serve as representative paradigms in this regard
which reflect the immense applicative potential of en-
visioning a C–H bond as an ideal functional core. This
has allowed a superior scope of selective functionali-
zation at sp2/sp3 carbon centres in the presence of an
organometallic catalyst in complex molecular environ-
ments.[1] With reference to the widely known genre of
C–H bonds, activation of an sp3 carbon centre is quite
problematic. Asserting the compliance of such
a bond, with the absence of a polarizable p-electron
cloud and a low-lying s* orbital, to undergo a metal-
catalyzed cleavage is seemingly tedious. A series of
strategies implemented over the years has thus helped
in the formidable task of making this inert class of C–
H bonds participate actively in chemical transforma-
tions.
Scheme 1. Auxiliary-assisted palladium-catalyzed g-C–H ary-
lation protocols.
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immense significance concerning their utility in drug catalyst would undergo an increase in its oxidation
research and development.[5] Seminal work by Carra- state by two while forming the metallacycle. This will
tero in performing remote C(sp3)–H arylation on di- require a donor group in the intermediate metallacy-
peptides by using an N-(2-pyridyl)sulfonamide-based cle which could stabilize the higher oxidation state of
chelating model is noteworthy.[6] In the last few years, the metal. Use of exogeneous ligands was shown to
Yu made significant advancements in this regard by be useful for this in earlier reports.[10] In this case, the
promoting the effective use of ligand controlled strat- bidentate 8-aminoquinoline was at first tethered to
egy towards highly site selective arylation at both sp2 a linear n-butyl carboxylic acid through an amide
and sp3 carbon centres.[7]
This was demonstrated in a one-pot sequential di- tance with palladium. Unfortunately, this yielded b-
arylation of alanine derivatives using a CONHArF arylated products exclusively. Later, we tethered tert-
[ArF =C6F4-(4-CF3)] auxiliary at the g-C–H bond.[8]
butylacetic acid with 8-aminoquinoline via an amide
linkage that would provide an active chelation assis-
ACHTUNGTRENNUNG
A
stepwise combination of a pyridine and quinolone- linkage for arylation with 4-nitroiodobenzene as ary-
based ligand derivatives was used for this reaction. g- lating source in presence of Pd(OAc)2 as catalyst and
C–H arylation using an amino acid as the directing AgOAc as oxidant. Interestingly, regioselective g-ary-
group had been also reported which was brought lation was observed (NMR yield: 50%) with a near
about by changes in the design of the ligands used.[9] exclusive formation of mono-arylated product
Very recently, while this work was under progress, Yu (mono:di>30:1). With these initial results at hand,
made a successful attempt towards the distal g-C–H detailed optimization of the reaction conditions was
arylation of carboxylic acid derivatives using CON- carried out. A sequential screening of the palladium
HArF as the directing group.[10] Arylation was per- salts and the oxidants resulted in Pd(PhCN)2Cl2 and
formed selectively at the g-position of valine, leucine AgOAc as the perfect catalyst-oxidant combination
and isoleucine derivatives. An intricate tuning of the for the reaction. Use of a bulky polar hydroxylic sol-
ligand helped to overcome the necessity of the steri- vent like t-BuOH was found to be beneficial for the
cally bulky phthalimido group, which was primarily reaction. The presence of a bulky anion like trifluoro-
required to attain the required metallated intermedi-
ate. During this time, activation of the remote aliphat-
ic g-C–H bond of carboxylic acid derivatives was
being investigated in our laboratory. Herein, we inde-
pendently report a facile protocol to perform a selec-
tive arylation at the remote g-position of aliphatic car-
boxylic acids using a palladium-catalyzed reaction
with 8-aminoquinoline as bidentate chelating auxiliary
in which both amine and quinoline nitrogens chelate
with the metal.
ACHTUNGTRENaNUGN cetate was useful for the reaction (Table 1). Inclusion
Table 1. Optimization of catalyst, oxidant and solvent for
the reaction condition starting with 0.3 mmol of amide and
0.1 mmol of aryl iodide.
While the g-C–H activation of amines requires
a five-membered metallacycle, the same in case of
carboxylic acids would proceed by a six-membered
cyclometallation pathway (Scheme 2). The metal pre-
En- Pd Catalyst
try
Oxidant Solvent
(2 mL)
Yield
[%][a]
1
2
3
4
5
6
7
8
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
PdCl2
AgOAc IPA
35[b]
40[b]
AgOAc HFIP
AgOAc CF3CH2OH 32[b]
AgOAc t-BuOH
AgI t-BuOH
Ag2CO3 t-BuOH
CuOAc t-BuOH
AgOAc t-BuOH
AgOAc t-BuOH
AgOAc t-BuOH
50[b]
20[b]
45[b]
32[b]
70[c,d]
50[c,d]
60[c,d]
75[c,d]
9
10
11
Pd(CH3CN)2Cl2
trans-Pd(PhCN)2Cl2 AgOAc t-BuOH
[a]
[b]
[c]
[d]
For mono-arylated product.
2 equiv. oxidant were used.
In the presence of CF3CO2Na.
3 equiv. of oxidant were used. See the Supporting Infor-
mation for more details.
Scheme 2. Formation of metallacycle for b- and g-C–H acti-
vation.
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of an exogeneous ligand failed to provide any addi- mode that helped in stabilizing the intermediary high
tional improvements on the reaction conditions. The oxidation states of palladium. Addition of an exoge-
importance of ligand design was emphasized by Yu in neous bulky ligand therefore did not help in improv-
his recent report on g-arylation. Moreover, g-arylation ing the yield as much since it might hinder the intra-
of carboxylic acids was confirmed to be unknown in molecular chelation by the 8-aminoquinoline group.[11]
absence of any ligands to date and therefore had re- This led to a facile activation of the remote g-C–H
mained as a challenge.[10] However, a prudent choice bond of the aliphatic carboxylic acid and the immi-
of the directing group has allowed this target to be nent g-arylation with impressive mono-selectivity.
achievable. The reaction conditions employed in our
With the optimized conditions in hand, we went on
case completely nullified the requirement of any exo- to contemplate the scope of the substrates
geneous ligands. This ensured an enhanced atom-eco- (Scheme 3). Both electron-donating and electron-
nomical catalytic conversion and easier reaction con- withdrawing aryl iodides were found to be effective
ditions without any compromise of the yield and for the regioselective g-arylation in moderate to good
mono-selectivity. Bidentate chelation by the tethered yields. Electron-rich arenes containing substituents
8-aminoquinoline ensured an apt placement of the like 3-methoxy (5b), 4-methoxy (5c), 4-methyl (5d) as
palladium catalyst in order to maintain the required well as 4-tert-butyl groups (5e) underwent successful
six-membered metallacycle (Scheme 2). The presence g-arylation with an excellent ratio in favour of mono-
of this directing group provided a strong coordination arylated products relative to di-arylation. Aryl iodides
Scheme 3. Arene scope for g-C–H arylation of carboxylic acid derivatives. Isolated yields are reported.
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containing electron-withdrawing groups such as tri-
fluoromethyl, carboxyl, formyl, esters and keto
groups were also found to be effective (5f–5n). Fluo-
rine-containing aryl groups have been found to be im-
portant in agrochemicals and pharmaceuticals. Nota-
bly, 4-fluorophenyl iodide gave mono-arylated prod-
uct (5o) with excellent selectivity and moderate yields
when subjected to the above reaction conditions. Par-
allel to this, other halogen like chloro and bromo sub-
stituted phenyl iodides also provided g-mono-arylated
products with enhanced selectivity (5p and 5q). How-
ever, iodo derivatives of heteroarenes, phenol and
benzyl alcohols failed to undergo the arylation reac-
tion as suitable coupling partners. Initial attempts for
arylation with n-butylamides had led to the exclusive
formation of b-arylated products with a variety of aryl
iodides (Scheme 4, 7a–7d). However, substrates with
a b-alkyl/aryl substituent (Scheme 5, 9a–9l) showed
high g-regioselectivity for arylation. Although the role
of the b-substituents is not clear at this stage, their
Scheme 4. b-Arylation with linear carboxylic acids.
role could be accredited towards rendering support in obtained (9j–9l). Interestingly, g-cyclization was ob-
formation of the six-membered metallacycle required tained for mesitoic acid amide which proceeded via
for g-C–H arylation of carboxylic acids (2 in intramolecular cyclization (9m).
Scheme 2). Mono-selective arylated products 9a–9e
Examination of the carboxylic acid scope was then
were obtained without any percentage of di-arylation carried out with N-protected amino acids such as l-
(Scheme 4). Substrates like isovaleric acid were also valine and l-isoleucine. Despite the presence of a b-
tested which yielded mono-g-arylated products (9f– hydrogen, both amino acids underwent successful g-
9i). Furthermore, using the initially obtained b-arylat- arylation in good to excellent yields (Scheme 6, 11a–
1
ed products, g-arylation was performed. Gratifyingly, 11h). Careful H NMR analysis revealed that products
exclusive formation of mono-g-arylated products was were formed in a good diastereomeric ratio (see the
Scheme 5. Scope of various b-unprotected carboxylic acids for g-C–H arylation.
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Scheme 6. Scope of N-protected amino acids for g-C–H arylation.
Supporting Information). Aryl iodides with electron- the protocol and the involved catalytic process is on-
donating or electron-withdrawing substituents under- going in our laboratory.
went the transformation with exceptional mono-selec-
tivity.
Control experiments were performed to understand
the role of AgOAc. In an independent set of reac-
tions, replacement of AgOAc either by air, oxygen or
N2 did not give corresponding product. Replacing
AgOAc with p-benzoquinone as an oxidant with 4-ni-
troiodobenzene (4a) as coupling partner did not yield
any product. Also replacing 4-nitroiodobenzene (4a)
with 4-nitrophenyl triflate (12) and using p-benzoqui-
none as the oxidant failed to produce 5a. Thus, the
aryl halide is a potent arylating source for this proto-
col. (Scheme 7). Moreover, AgOAc exhibits a dual
role by probably acting as halide scavenger as well as
reoxidant. These facts point towards a tentative
Pd(II)/Pd(IV) catalytic pathway.[12] Further applica-
tion of the protocol was demonstrated by the facile
removal of the 8-aminoquinoline directing group that
furnished the free ester (Scheme 7, 13) in 80% yield
along with recovery of the 8-aminoquinoline moiety
(14) in 75% yield. The latter could be reinstalled
again to achieve the g-arylation of other substrates.
In summary, a palladium-catalyzed protocol for se-
lective g-C–H arylation of carboxylic acids has been
developed. This strategy utilizes the chelating poten-
tial of the 8-aminoquinoline-based directing group for
the site selective C–H activation. Prudent application
of a suitable directing group has eliminated the neces-
sity of expensive exogeneous ligands for g-C–H aryla-
tion rendering the protocol cost effective and eco-
nomical. A detailed mechanistic investigation about removal and concomitant recovery of the directing group.
Scheme 7. Control experiments to study the role of AgOAc;
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General Procedure for g-Arylation of 8-Amino-
quinoline Amide
In a clean, oven-dried screw-cap reaction tube containing
magnetic stir-bar, 3,3-dimethyl-N-(quinolin-8-yl)butanamide
(3) (0.3 mmol), iodoarene (4) (0.1 mmol), Pd(PhCN)2Cl2
(10 mol%, 0.01 mmol), AgOAc (3 equiv., 0.3 mmol),
CF3CO2Na (2 equiv., 0.2 mmol) were added. Solid reagents
were weighed before the liquid reagents. Then t-BuOH
(2.0 mL) was added and the tube was tightly closed by
a screw cap fitted with a rubber septum. Finally, the reaction
tube was placed in a preheated oil bath at 1508C and the
mixture stirred vigorously (900 rpm) for 24 h. After comple-
tion, the reaction mixture was cooled to room temperature
and filtered through pad of Celite and ethyl acetate
(15 mL). This filtrate was concentrated under reduced pres-
sure and purified by column chromatography through silica
gel using petroleum ether/ethyl acetate as eluent.
Acknowledgements
This activity is supported by CSIR, India (funding to DM,
CSIR, 02(0242)/15/EMR-II). Financial support received from
CSIR, India (fellowship to AD) and DST-N.P.D.F (fellow-
ship to SG) is gratefully acknowledged.
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COMMUNICATIONS
8 Chelation-Assisted Palladium-Catalyzed g-Arylation of
Aliphatic Carboxylic Acid Derivatives
Adv. Synth. Catal. 2017, 359, 1 – 8
Aniruddha Dey, Sandeep Pimparkar, Arghya Deb,
Srimanta Guin, Debabrata Maiti*
Adv. Synth. Catal. 0000, 000, 0 – 0
8
ꢁ 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÞÞ
These are not the final page numbers!