Nitroarenes as the Nitrogen Source in Intermolecular Palladium-Catalyzed Aryl C–H Bond Aminocarbonylation Reactions

Article abstract of DOI:10.1002/anie.201612324

A three-component palladium-catalyzed aminocarbonylation of aryl and heteroaryl sp² C?H bonds using nitroarenes as the nitrogen source was achieved using Mo(CO)₆ as the reductant and origin of the CO. This intermolecular C?H bond functionalization does not requires any exogenous ligand to be added, and our mechanism experiments indicate that the palladacycle catalyst serves two roles in the aminocarbonylation reaction: reduce the nitroarene to a nitrosoarene and activate the sp² C?H bond.

Full text of DOI:10.1002/anie.201612324

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International Edition: DOI: 10.1002/anie.201612324
German Edition: DOI: 10.1002/ange.201612324
Aminocarbonylation
Nitroarenes as Nitrogen Source in Intermolecular Palladium-Catalyzed
Aryl C–H Bond Aminocarbonylation Reactions
Fei Zhou, Duo-Sheng Wang, Xinyu Guan, and Tom G. Driver*
Abstract: A three-component palladium-catalyzed aminocar-
bonylation of aryl and heteroaryl sp2 C H bonds using
À
nitroarenes as the nitrogen source was achieved using Mo-
(CO)6 as the reductant and origin of the CO. This intermo-
À
lecular C H bond functionalization does not requires any
exogenous ligand to be added, and our mechanism experiments
indicate that the palladacycle catalyst serves two roles in the
aminocarbonylation reaction: reduce the nitroarene to a nitro-
2
À
soarene and activate the sp C H bond.
À
Scheme 1. Intermolecular C H bond functionalization using nitroar-
enes.
À
I
ntermolecular C H bond functionalization of arenes and
heteroarenes continues to be pursued because of its potential
to selectively and efficiently increase the complexity of the
substrate.[1] Although significant progress has been ach-
ieved,[2] the development of transition metal-catalyzed pro-
these challenges and potential pit falls, we report herein that
the reactivity embedded in nitroarenes can be unlocked and
controlled using [Mo(CO)6] and a palladium catalyst to
À
À
cesses that transform C H bonds into amides has lagged and
often requires the use of isocyanates or other reactive
achieve intermolecular C H bond aminocarbonylation.
To determine if a nitroarene could be used as the nitrogen
reagents to effect bond construction.[3–5] Because of their
ready availability, the use of nitroarenes in these C H bond
aminocarbonylation reactions would be enabling. During the
course of our investigations into the reactivity of nitroarenes
towards [Mo(CO)6] and palladium,[6] we were curious if we
source in intermolecular C H bond functionalizations, 2-
À
À
para-tolylpyridine 1a was chosen because of its ubiquity in
these types of reactions (Table 1).[11] While only trace C H
À
bond functionalization was observed in the absence of
catalyst using [Mo(CO)6] as the reductant (entry 1),
20 mol% of palladium acetate produced amide 3a in 76%
À
could achieve intermolecular C H bond functionalization
reactions, a reactivity pattern of electrophilic metal N-aryl
catalytic intermediates, which had to date eluded our studies
into aryl azides (Scheme 1).[7] Such a reaction, however,
would require the unlocking the reactivity in both the
À
Table 1: Optimization of the C H bond aminocarbonylation reaction.
À
nitroarene and the C H bond to generate two reactive
species that could potentially participate in undesired side
À
reactions instead of reacting to produce the C H bond
functionalization product. Using [Mo(CO)6] also introduces
a potential complication: its presence in the reaction mixture
could enable insertion of a carbonyl fragment to achieve the
Entry Catalyst
x [mol%] CO
source
x equiv PivOH[a] 3a yield
[%][b]
À
1
2
3
4
…
…
20
20
20
20
20
20
20
20
10
5
[Mo(CO)6]
[Mo(CO)6]
[Mo(CO)6]
[Mo(CO)6]
CO
CO
DMF
CHCl3
[Mo(CO)6]
[Mo(CO)6]
[Mo(CO)6]
[Mo(CO)6]
2
2
2
2
1.5
1.5
1.5
1.5
trace
76
52
formation of three new bonds from a single C H bond
[Pd(OAc)2]
[Pd(TFA)2]
[Pd(dba)2]
[Pd(OAc)2]
[Pd(OAc)2]
[Pd(OAc)2]
[Pd(OAc)2]
[Pd(OAc)2]
[Pd(OAc)2]
[Pd(OAc)2]
À
(aminocarbonylation) in addition to C H bond amination.
While carbonylation reactions have a rich history in organic
42
synthesis,[8] adding an additional C1 unit using CO in C H
À
5
1.5 atm 1.5
1.5 atm 1.5
excess 1.5
6
2
2
2
2
n.r.
n.r.
dec.[f]
dec.[f]
82
78
74
80
bond functionalization processes remains rare.[9,10] Despite
6[c]
7[d]
8[e]
9
1.5
0.5
0.5
0.5
0.5
[*] F. Zhou, Dr. D.-S. Wang, X. Guan, Prof. T. G. Driver
Department of Chemistry, University of Illinois at Chicago
845 West Taylor Street, Chicago, IL 60607-7061 (USA)
E-mail: tgd@uic.edu
10
11
12[f] [Pd(OAc)2]
10
[a] equiv. [b] As determined using 1H NMR spectroscopy using CH2Br2 as
the internal standard. [c] 20 mol% [Mo(CO)6] added. [d] DMF, imida-
zole, KOt-Bu, 180–1908C; ref. [12b]. [d] CHCl3, CsOH·OH2; ref. [12c];
[e] Only urea observed. [f] Reaction performed under an air atmosphere.
py=pyridine; PivOH=pivalic acid; DCE=1,2-dichloroethane; Ac=a-
cetyl; TFA=trifluoroacetate; dba=dibenylideneacetone; DMF=dime-
thylformamide.
Prof. T. G. Driver
Institute of Next Generation Matter Transformation
College of Chemical Engineering, Huaqiao University
668 Jimei Boulevard, Xiamen, Fujian, 361021 (P.R. China)
Supporting information and the ORCID identification number(s) for
the author(s) of this article can be found under:
http://dx.doi.org/10.1002/anie.201612324.
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Table 3: Examination of N-heteroarenes to determine scope and site
selectivity.
yield (entry 2). Changing the identity of the palladium
counterion had a deleterious effect on the success of the
reaction (entries 3–4). The identity of the reductant was also
critical to the success of this reaction: no reaction was
observed using 20 mol% of [Mo(CO)6] and CO, or if
alternative sources of CO were used in place of [Mo(CO)6]
(entries 5–8).[12] The yield of the aminocarbonylation could be
improved if the amount of pivalic acid (PivOH) was reduced
to 0.5 equivalents (entry 9). While PivOH appears necessary
to promote a concerted metalation–deprotonation of the aryl
C H bond,[13] at too high of a concentration it has a negative
À
effect on our transformation by favoring protonation of the
À
pyridine to inhibit the desired C H bond activation. To our
delight, the transformation could be triggered successfully
using lower loadings of [Pd(OAc)2] (entries 10 and 11).
Finally, we were pleased to see that the reaction could be
performed in air without reducing the yield of amide 3a
(entry 12).
Using these optimal conditions, the effect of changing the
nitroarene and pyridine on the [Pd]-catalyzed amino-carbon-
ylation reaction was examined (Table 2). The electronic
Table 2: Investigation of the effect of changing the nitroarene and
pyridine directing group on the reaction outcome.
Entry R1
R2
R3
R4
R5
Compound Yield [%][a]
1
2
3
4
CO2Me
CF3
Br
Cl
F
H
Me
OMe
H
H
H
H
H
H
H
H
H
Me
H
H
H
H
H
H
H
H
H
H
H
H
Me
H
H
H
H
H
H
H
H
H
H
H
H
Me
H
H
H
H
H
H
H
H
H
H
H
H
3a
3b
3c
3d
3e
3 f
3g
3h
3i
80
70
68
81
72
63
66
30
n.r.
89
89
90
5
6[b]
7
8[b]
9
10
11
12
CO2Me
CO2Me
CO2Me
3j
3k
[a] Isolated after silica gel chromatography. [b] 1.0 equiv of PivOH added.
[c] Regioselectivity determined using 1H NMR spectroscopy; only prod-
uct obtained.
Me 3l
[a] Isolated after silica gel chromatography. [b] 1.0 equiv of PivOH added.
ethers, thioethers, and even hydroxy groups (entries 1–4).
À
nature of the nitroarene impacted the success of the reaction
(entries 1–8) with the highest yields observed when electron-
deficient R1-substituents were present on the nitroarene.
Increasing the steric environment around the nitro group,
however, had a detrimental effect on the reaction (entry 9).
The pyridine-directing group could also be modified without
adversely affecting the reaction: aminocarbonylation
smoothly occurred when substituents were added to the 3-,
4- or 5-positions on the pyridine (entries 10–12).[14]
Next, the scope of the reaction was surveyed by varying
the identity of the arene reaction site (Table 3). First,
variation of the para-substituent of the 2-aryl group on 4
revealed that the aminocarbonylation reaction tolerated
Next, the selectivity of the C H bond functionalization
reaction was probed (entries 5–7). Our reaction proved to be
site selective in that aminocarbonylation occurred only at the
À
sterically more accessible C H bond to produce amides 5e–
5g as single isomers. Changing the identity of the reaction site
to a heteroarene did not diminish the efficiency of the Pd-
catalyzed aminocarbonylation reaction: amides could be
formed from thiophene-, pyrrole- or indole substrates
(entries 8–14). In the latter two scaffolds, the N-pyridyl
substituent can be removed by treating the amide product
with MeOTf and PhSNa following the protocol reported by
Ackermann and co-workers.[4c,15] A series of methyl-substi-
tuted pyrroles were investigated to provide insight into the
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effect of increasing the steric environment around the
potential nitrogen source resulted in formation of only N,N’-
reaction center. A C2-methyl group was tolerated in 4j, and
pyrrole 4k demonstrated that aminocarbonylation could be
achieved at a sterically congested site without loss of
efficiency (entries 10 and 11). Despite the ability of the
diphenylurea.[11] In contrast, nitrosobenzene afforded the C
À
H bond functionalization product in 35% to suggest that it is
being formed and consumed in the catalytic cycle. In the
absence of [Pd(OAc)2], however, no aminocarbonylation was
observed using nitrosobenzene. Several experiments were
performed to ascertain the identity of the active palladium
species in the reaction (Scheme 2c). Towards this end,
dinuclear palladium(II) complex 6 was prepared from the
cyclopalladation of 2-phenylpyridine with [Pd(OAc)2],[18] and
was found to be a potent catalyst: exposure of 2-para-
tolylpyridine to 5 mol% of 6 produced amide 3a in 80% yield
and amide 5d in 88%. Increasing the stoichiometry of the
palladacycle to 1 equiv, however, did not produce any amide
product in the absence of the 2-arylpyridine.[19] The pyridy-
laryl ligand on 6 became labile once substrate was added:
exposure of 0.25 equiv of palladacycle 6 to 1 equiv of 2-
tolylpyridine and nitroarene produced a 2.23:1 mixture of
amides 3a and 5d.
À
reaction to occur at this position, our C H bond functional-
ization remained site selective: submission of C3-methyl-
substituted pyrrole 4l to reaction conditions produced amide
5l as a single isomer (entry 12). Indoles 4m and 4n also
proved to be competent substrates to produce C2-substituted
5m and 5n (entries 13 and 14). While the identity of the
directing-group could be altered to either a pyrimidine or an
indazole (entries 15 and 16), the yield of 5 was attenuated.
Several experiments were performed to provide more
insight into the mechanism of the transformation (Scheme 2).
The results from these experiments were used to construct
a potential catalytic cycle centered on the hypothesis that
palladium is required to reduce the nitroarene as well as
À
activate the ortho-C H bond (Scheme 3). Our mechanistic
Scheme 2. Mechanistic experiments.
First, a control experiment established that no H/D exchange
in substrate 4d occurred if PivOD was used in place of
PivOH.[16] Next, the reactivity of isotopologs [D1]4d and
[D5]4d were examined. A primary kinetic isotope effect
(KIE) of 3 was measured when 2-phenyl[D1]pyridine was
submitted to the reaction, and an intermolecular competition
experiment between 2-phenylpyridine and 2-phenyl-
[D5]pyridine exhibited a KIE of 2.3. Together, these experi-
Scheme 3. Possible catalytic cycle for Pd-catalyzed aminocarbonylation.
À
ments suggest that the C H bond activation step is both the
product-determining and the turnover-limiting step.
experiments suggest that the active catalyst is palladacycle
7.[18] This species is formed from the directed C H bond
À
Next, the reactivity of potential nitrogen and palladium
catalytic intermediates were tested. To gain insight into the
identity of the nitrogen reactive intermediate, several suspects
were investigated (Scheme 2b). Aminocarbonylation was not
observed using aniline, isocyanate, or N-hydroxyaniline as the
nitrogen-source. The lack of amide formation from isocyanate
was particularly surprising because it has been used as
a reagent in metal-catalyzed amidation reactions;[4] isocya-
nate is well-established as the product of Pd-catalyzed
reduction of nitroarenes with carbon monoxide;[17] and we
observed the formation of N,N’-diarylurea as a by-product of
our aminocarbonylation reaction. Instead, using stoichiomet-
ric- or substoichiometric amounts of isocyanate as the
activation of 2-para-tolylpyridine, which is in equilibrium with
the dimer 8.[20] Palladacycle 7 first reacts with CO liberated
from [Mo(CO)6] to produce palladium carbonyl complex 9,[21]
which reduces the nitroarene to produce nitrosoarene and
reform 7.[22] The second role of palladacycle 7 is to trigger the
À
C H bond activation of the substrate (1a) to produce
biscyclometallated 10.[23] The lack of H/D scrambling in the
recovered 2-arylpyridine substrate when PivOD is used
indicates that this step is irreversible. Insertion of CO into
À
the Pd aryl bond forms 11, which reacts with nitrosoarene to
form 13.[24] Reduction of the N O bond in 14 by molybdenum
À
or palladium then produces the product amide. This reduction
could occur before or after dissociation of the palladacycle
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catalyst. Alternatively, the amide could be formed from the
reaction of palladacycle 10 with arylisocyanate,[4,5] which
could be formed from the [Mo(CO)6]-mediated reduction of
the nitroarene,[17] or from the reaction of aniline or N-
hydroxy-aniline with acyl-Pd species 11. The lack of amide
formation when isocyanate, aniline, or N-hydroxyaniline are
used as the nitrogen source, however, strongly suggests that
bond formation does not occur through these two potential
pathways.
À
We have shown that Pd-catalyzed intermolecular C H
bond aminocarbonylation of 2-aryl- or 2-heteroarylpyridines
can be achieved using nitroarenes as the nitrogen source and
[Mo(CO)6] as the carbonyl source. Our mechanistic studies
revealed that the active catalyst is a palladacycle, which serves
to both reduce the nitroarene to a nitrosoarene as well as
À
activate the aryl C H bond. Our future studies will build on
these results by exploring the reactivity of palladacycles
À
towards nitroarenes to trigger intermolecular C N bond-
forming reactions to rapidly and efficiently build complexity
of simple heteroarenes.
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We are grateful to the National Science Foundation CHE-
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Chancellor for Research, Huaqiao University Xiamen, and
the Fujian Hundred Talents Plan for their generous financial
support. We thank Mr. Furong Sun (UIUC) for HRMS data.
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Conflict of interest
The authors declare no conflict of interest.
À
Keywords: aminocarbonylation · C H functionalization ·
homogeneous catalysis · nitroarenes · palladium
[11] Refer to the Supporting Information for more information.
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4
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van Leeuwen, Chem. Commun. 1996, 217; c) F. Ragaini, M.
Manuscript received: December 20, 2016
Revised: February 16, 2017
Final Article published: && &&, &&&&
Angew. Chem. Int. Ed. 2017, 56, 1 – 6
ꢀ 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
5
These are not the final page numbers!

Angewandte
Communications
Chemie
Communications
Aminocarbonylation
F. Zhou, D.-S. Wang, X. Guan,
T. G. Driver*
&&&& — &&&&
À
C H functionalization: A three-compo-
and origin of the CO. This intermolecular
À
Nitroarenes as Nitrogen Source in
Intermolecular Palladium-Catalyzed Aryl
C–H Bond Aminocarbonylation
Reactions
nent palladium-catalyzed aminocarbony-
C H bond functionalization does not
2
À
lation of sp C H bonds using nitro-
arenes as the nitrogen source was ach-
ieved using Mo(CO)6 as the reductant
require any exogenous ligand to be
added.
6
www.angewandte.org
ꢀ 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2017, 56, 1 – 6
These are not the final page numbers!