Direct: N -formylation of nitroarenes with CO2

Article abstract of DOI:10.1039/d0cc03098h

Herein we describe a straightforward N-formylation of nitroarenes with CO2 to access N-aryl formamides exclusively in the presence of iron and hydrosilane as additives. This protocol showcases a good tolerance of a wide range of nitroarenes and nitroheteroarenes.

Full text of DOI:10.1039/d0cc03098h

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Direct N-formylation of Nitroarenes with CO2
Ni Shen, a Shi-Jing Zhai,a Chi Wai Cheung,*ab and Jun-An Ma*ab
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
Herein we describe a straightforward N-formylation of nitroarenes nitroarenes and CO or its surrogates. To our knowledge, the merger
with CO2 to access N-aryl formamides exclusively in the presence of of CO2 and nitroarenes for straightforward amide synthesis remains
iron and hydrosilane as additives. This protocol showcases a good unexplored. We envisioned that the use of suitable and compatible
tolerance of a wide range of nitroarenes and nitroheteroarenes.
reductants and activating agents could induce the integration of both
CO2 and nitroarenes for amide formation. Herein, we unveil the
direct N-formylation of nitroarenes with CO2 in the presence of iron
powder and hydrosilane additives (Scheme 1c). This alternative and
complementary method would open a conceptually novel avenue for
more step-economic and expedient access to formamides without
the need of conventional anilines.
Carbon dioxide (CO2) constitutes an ideal C1 source in organic
synthesis owing to its abundance and stability.1 In particular, CO2
serves as the best-suited substitute of more reactive C1 building
blocks, such as carbon monoxide (CO), methyl iodides, and
phosgene.2 Despite its high activation barrier and thermodynamic
stability,2 CO2 has been widely exploited for decades to access a
diverse array of functionalized compounds via carboxylation,3
carbonylation,4 or C-H bond construction.5 In this context, the
incorporation of amines and CO2 towards synthesis of value-added
nitrogen-containing compounds,6 especially N-formylation of amines
with CO2,7-13 is among the most important chemical transformations
due to the versatility of nitrogen-based compounds in academia and
industry. Taking the advantage of commercially available
hydrosilanes as activating and hydrogenating agents along with
various catalysts, such as organic superbases,7 carbenes,8 ionic
liquids and organic salts,9 inorganic salts,10 polar aprotic solvents,11
diazophospholene,12 and B(C6F5)3,13 a variety of formamides can be
accessed based on amines and CO2 (Scheme 1a). Additionally, the
Ding14 and Bernskoetter15 groups described the seminal Ru- and Fe-
catalyzed N-formylation of alkylamines based on the CO2/H2 system,
respectively (Scheme 1b). On the other hand, nitroarenes prove to
be reliable aminating agents for direct synthesis of amines16 and
amides17 without preforming the more reactive anilines via
hydrogenation. Recently, Beller,17a Driver,17b Hu,17c Mankad,17f
Wu,17d,e as well as our group17g disclosed the aminocarbonylation
reactions to access aryl amides, a class of important compounds in
chemical, pharmaceutical, and agrochemical industries, based on
Scheme 1. Developments of N-formylation based on CO2.
(a) Organocatalytic/salt-catalyzed N-formylation of amines with CO2
R
N
R
N
catalysts
CO2
H
+
H
R'
hydrosilanes
or boranes
R'
R = aryl, alkyl, H
O
organic superbases, carbenes, ionic liquids,
organic salts, inorganic salts, polar aprotic
solvents, diazophospholene, B(C6F5)3
catalysts =
(b) Ru/Fe-catalyzed N-formylation of alkyl amines with CO2
alkyl
alkyl
Ru, Fe catalysts
N
H
CO2
N
H
+
R
H2
R
O
R = alkyl, H
(c) This work: N-formylation of nitroarenes with CO2
FG
H
FG
NO2
N
H
Fe
CO2
+
O
hydrosilane
stable and readily accessible nitroarenes
commerically available additives
broad scope of N-aryl formamides
We commenced the study on N-formylation of CO2 using 4-
nitroanisole (1a) as the model substrate (Table 1). In the presence of
3 equivalents of Zn powder as reductant and 3 equivalents of
phenylsilane as additive, 1a reacted with CO2 under balloon pressure
in dimethylformamide (DMF) solvent at 110 oC to give N-4-
methoxyphenyl formamide 2a exclusively in 49% yield (Entry 1). In
the absence of Zn or hydrosilane, no formylation took place,
indicating that both metal reductant and hydrosilane are essential
for reaction (Entries 2 and 3). When triethoxysilane was used in place
a Department of Chemistry, Tianjin Key Laboratory of Molecular Optoelectronic
Sciences, and Tianjin Collaborative Innovation Center of Chemical Science &
Engineering, Tianjin University, Tianjin 300072, People’s Republic of China
b
Joint School of National University of Singapore and Tianjin University,
International Campus of Tianjin University, Binhai New City, Fuzhou 350207, P. R.
of China
E-mail: zhiwei.zhang@tju.edu.cn
E-mail: majun_an68@tju.edu.cn
† Electronic Supplementary Information (ESI) available: [Experimental and Spectral
Data]. See DOI: 10.1039/x0xx00000x
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of phenylsilane, formylation underwent at 135 oC to offer 2a in 56% benzothiophene (1v), and benzoxazole (1w), delivering the
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DOI: 10.1039/D0CC03098H
yield (Entry 4). Further, when Fe powder was employed instead of corresponding N-heteroaryl formamides 2p-2w in 43-85% yields.
Zn, 2a was also obtained in 51% yield (Entry 5). Noteworthily, the Noteworthily, the employment of 3 equivalents of Fe metal (Table 1,
yield could be enhanced to 63% yield when 10 mol% of KI was added entry 10) could improve remarkably the formylation of electron-rich
as additive in the Fe-mediated reaction (Entry 6). Subsequently, nitro(hetero)arenes 1c, 1o and 1s, affording the corresponding
1,1,3,3-tetramethyldisiloxane (TMDSO) was found to be the superior formamides 2c, 2o and 2s in 80%, 60% and 63% yields, respectively.
additive, giving 2a in 75% yield (Entries 7-9). Intriguingly, the use of On the contrary, the reactions of electron-deficient nitroarenes with
Fe nano powder allowed the reduction of loadings of both Fe and the additional equivalent of Fe led to substantial diminishment of
TMDSO to 2 equivalents in association with the yield enhancement yields. Gratifyingly, by adding FeCl2 (2 equiv) and slightly increasing
to 83% yield (Entries 10-12). Such promoting effect would be the loading of TMDSO and KI, electron-deficient nitroarenes such as
attributed to the more efficient reduction process provided by the 1j-1m could react more efficiently to afford the formamides in higher
more soluble and finely powdered Fe. In the presence of other polar yields (48-68%). This protocol was also amenable to multigram
aprotic solvents such as dimethylacetamide (DMA) and N- synthesis of 2a in synthetically useful yield.
methylpyrrolidine (NMP), 2a was formed in similar yields without
other side products (Entries 13 and 14). Furthermore, no formamide
Scheme 2. Substrate scope of nitroarenes in N-formylation.a
was formed when CO2 was omitted (Entry 15). These control
experiments suggested that the carbonyl group of 2a originates from
H
N
FG
FG
Fe nano powder (2 equiv)
TMDSO (2 equiv)
KI (10 mol %)
NO2
H
CO2
+
O
DMF, 135 oC, 28 h
CO2 rather than solvent.
1a-1w
2a-2w
H
H
H
H
N
Table 1. Optimization of N-formylation of nitroarenes with CO2.a
Me
N
H
N
H
N
H
H
H
O
O
O
O
O
O
PhO
2c
Me
MeO
H
2a
, 83%
30 mmol 1a
NO2
b
metal
(equiv)
hydrosilane
2b
2d
2h
, 61%
, 40% (80%)
H
, 75%
N
H
: 44%
(equiv)
H
H
N
H
N
CO2
+
N
H
H
additive
solvent, 135 oC, 28 h
O
N
H
MeO
MeO
1a
2a
O
O
O
PhS
Cl
MeS
F
2e
2f
2g
, 79%
, 56%
, 48%
, 82%
Entry Metal
(equiv)
Solvent Yield (%)b
Hydrosilane Additive
H
H
N
H
N
H
N
(equiv)
PhSiH3 (3)
PhSiH3 (3)
none
(mol %)
none
none
none
none
N
H
Br
H
MeO2C
H
H
1c
2c
3c
4
Zn (3)
none
Zn (3)
Zn (3) (EtO)3SiH (3)
Fe (3) (EtO)3SiH (3)
Fe (3) (EtO)3SiH (3)
Fe (3) Me(EtO)2SiH
(3)
DMF
DMF
DMF
DMF
DMF
DMF
DMF
49
0
0
56
51
63
25
O
O
O
O
MeO
2j
Me
Cl
c
c
c
2k
, 49% (62%)
2i
, 46% (48%)
2l
, 37% (49%)
, 58%
Me
H
H
N
H
N
H
N
MeO
Me
H
NC
Me
H
H
H
N
H
O
O
O
5
6
7
none
KI (10)
KI (10)
O
O
O
Me
b
c
2p
, 85%
2o
, 48% (60%)
2n
2m
, 73%
, 44% (68%)
H
N
H
N
H
N
H
H
H
N
H
O
O
O
O
8
9
Fe (3)
Fe (3)
Fe (3)
Fe (2)
Fe (1)
Fe (2)
Fe (2)
Fe (2)
PMHS (3)
TMDSO (3)
TMDSO (3)
TMDSO (2)
TMDSO (2)
TMDSO (2)
TMDSO (2)
TMDSO (2)
KI (10)
KI (10)
KI (10)
KI (10)
KI (10)
KI (10)
KI (10)
KI (10)
DMF
DMF
DMF
DMF
DMF
DMA
NMP
DMF
32
75
83
83
35
83
75
0
N
N
N
MeO
H
N
Bn
Me
b
2q
2r
2t
, 43%
, 63%
, 75%
2s
, 48% (63%)
H
10d
11d
12d
13 d
14 d
15d,e
H
N
H
H
H
N
O
N
N
Ph
nBu
O
O
O
S
O
2u
, 75%
2v
, 78%
2w
, 78%
aReaction conditions: nitroarene (0.5 mmol), CO2 (balloon), nano Fe (1 mmol),
o
TMDSO (1 mmol), KI (0.05 mmol), DMF (1.5 ml), 135 C, 28 h. Isolated yield
aGeneral procedure: 1a (0.5 mmol), CO2 (balloon), metal powder (1-1.5
mmol), hydrosilane (1-1.5 mmol), additive (10 mol %), solvent (1.5 mL), 135
oC, 28 h. bIsolated yield. cReaction conducted at 110 oC. dFe nano powder used.
eArgon atmosphere without CO2.
were shown. b 3 equiv of Fe. c Modified conditions: nitroarene (1 equiv), CO2
(balloon), nano Fe (2 equiv), FeCl2 (2 equiv), TMDSO (3 mmol), KI (30 mol %),
DMF (3 ml), 135 oC, 28 h.
In the course of reaction, nitroarene can be transformed to
nitrosoarene, N-aryl hydroxylamine, azoxyarene, azoarene, 1,2-
diaryl hydrazine, and aniline under reductive conditions.18 Thus, the
reactions of these nitrogen-based species under otherwise identical
conditions were examined to probe their roles in formylation
(Scheme 3a). Nitrosobenzene (3a), N-phenyl hydroxylamine (3b),
azoxybenzene (3c) and azobenzene (3d) all reacted to give
formamide 2g in 49-64% yields. Particularly, diphenyl hydrazine (3e)
reacted most efficiently to afford 2g in 70% yield. Presumably,
nitrobenzene is sequentially reduced to 3a, 3b, 3c, 3d, and finally
3e,18 which acts as the ultimate intermediate to participate in the
formylation reaction. Aniline 3f also reacted to give 2g in 44% yield,
The optimized protocol (Table 1, entry 11) proved to be general in
N-formylation of nitroarenes (Scheme 2). Electron-rich (1a-1f),
electron-neutral (1g), and electron-deficient (1h-1m) nitroarenes all
reacted with CO2 to form the corresponding N-aryl formamides in
moderate to high yields. Additionally, both mono- (1a-2i, 1l) and di-
substituted (1j, 1k, 2m-2o) nitroarenes could be incorporated into
the formamide products 2a-2o. The sterically encumbered 1-nitro-
2,4-dimethylbenzene (1o) was also suitable reaction partner.
Notably, a wide range of nitro-substituted heterocycles could be
utilized for formylation, including benzodioxole (1p), pyrrole (1q),
pyridine (1r), N-alkylated indole (1s, 1t), benzofuran (1u),
2 | J. Name., 2012, 00, 1-3
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suggesting that it is likely the minor intermediate to induce the detailed reaction mechanism is subjected to a dedicated study in the
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DOI: 10.1039/D0CC03098H
formylation. Furthermore, when Fe(0) was omitted, the addition of future.
Fe(II) salt, which is a viable oxidized Fe species, could enable the
Under the standard conditions, electron-rich nitro(hetero)arenes
tended to react more efficiently to form higher product yields (~50-
85%) than electron-deficient and sensitive group-bearing
nitroarenes (~40-60%, Scheme 2). We rationalized that the nitrogen-
based intermediates derived from the latter are more unstable,
especially in the reductive reaction conditions and in the presence of
basic by-products (e.g. iron oxides, silanolate ions), and likely
undergo over-reduction and decomposition at varying degrees in the
course of reactions. Additionally, an additional equivalent of Fe(0)
was found advantageous in the reactions of electron-rich
nitro(hetero)arenes but detrimental for electron-deficient ones. We
speculated that the contribution of Fe(0)- and TMDSO-based
reduction steps would vary with respect to the electronic effect of
nitroarenes. The reduction of electron-rich nitro(hetero)arenes
would mainly rely more on highly reducing Fe(0) to deliver more
amide ions. Conversely, the excess Fe(0) would over-reduce the
electron-deficient nitroarenes to less reactive anilines or other side
products, but additional milder reduction given by Fe(II)/TMDSO
system would in turn be more productive for formation of amide ions.
formylation of nitroarene 1a in the presence of excess TMDSO to give
formamide 2a in 45% yield. We surmised that hydrosilane can also
act as a reductant and a hydrogen source for the reduction of
nitroarene via the action of Fe-hydride species,16a,b apart from its
conventional application as CO2-activating agent.6h
Scheme 3. Control experiments for N-formylation.
(a) Reaction of possible nitrogen-containing intermediates
Fe nano powder (2 equiv)
TMDSO (2 equiv)
KI (10 mol %)
DMF, 135 oC, 28 h
H
N
H
Ph
CO2
Ph NX
+
O
3a-3f
2g
Nitrogen-based
species
Nitrogen-based
Isolated yield
2g
Isolated yield
2g
species
(Ph-NX)
(Ph-NX)
of
of
Ph
1/2
57%
55%
49%
3a
)
Ph NO
(
3d
(
)
64%
70%
44%
N
N
Ph
Ph
3b
(
(
)
Ph NHOH
3e
(
)
1/2 HN NH
Ph
Ph
O
3c
)
N
N
3f
( )
1/2
Ph NH2
Ph
(b) Formylation without Fe(0)
Scheme 4. Proposed mechanism of N-formylation.
H
N
H
FeCl2 (2 equiv)
TMDSO (5 equiv)
KI (10 mol%)
DMF, 135oC, 28 h
Fe(0), -Fe3O4
Ar N2-
O
MeO
NO2
+
CO2
MeO
(v)
(iv)
reactive species
2a
, 45%
1a
Ar
(iii)
Fe(0), -Fe(II)
or
Fe(II), TMDSO
Fe(0), -Fe(II)
or
(i)
(ii)
2
Ar NH
Ar NO2
2
Ar NH
HN NH
Ar
reactive species
1
Based on the experimental results, we proposed a plausible
mechanism of the formylation protocol (Scheme 4). Nitroarene 1 is
sequentially reduced to 1,2-diaryl hydrazine via the intermediacy of
nitrosoarene, N-aryl hydroxylamine, azoxyarene, and/or azoarene18
(pathway i). 1,2-Diaryl hydrazine then undergoes facile homolysis
under heating to give aminyl radicals,17g which are then reduced to
amide ion ArNH- (pathways ii and iii). Meanwhile, nitroarene can be
reduced to amide dianion ArN2- followed by ArNH-, whereas Fe(0) is
oxidized to Fe3O419 (pathway iv and v). A small amount of aniline can
also be generated (pathway vi). In the reduction processes, Fe(0) is
likely the major reducing agent, while TMDSO likely acts as both mild
reducing agent and hydrogenating agent. Owing to the strong
nucleophilicity of ArNH- and ArN2-, they likely activate both CO2 and
TMDSO via the transition state TS-1, in which the carbamate ion
formed further activates TMDSO to trigger the hydride attack to
another CO2 (pathway vii). Such transition state is regarded as the
lowest energy pathway for CO2 activation.6h Via TS-1, formoxysilane
is formed with the concomitant regeneration of amide species
(pathway viii). We proposed that iodide ion behaves as a strong
nucleophile in polar aprotic solvent DMF, thereby facilitating the
deformylation of formoxysilane to form a more reactive formyl
iodide in conjunction with silanolate ion (pathway ix). Finally, ArNH-
reacts with both formyl iodide and formoxysilane to deliver the N-
aryl formamide 2 (pathways x and xi). In the same vein, ArNH2-
undergoes nucleophilic substitutions with formyl iodide and
formoxysilane to give amidate ion, which furnishes formamide 2
upon acidic workup (pathways xii and xiii). On the other hand, the N-
formylation based on aniline may proceed but tends to be a minor
pathway due to the attenuated nucleophilicity of aniline. The
Fe(II), TMDSO
(vi)
less reactive species
Ar NH2
O
OR
Si
O
OR
Ar
(vii)
(viii)
O
C
X
H
CO
Me Si H
2
+
Ar
X
+
2
O
Me Me
X = NH or N-
Me
X = NH or N2-
TS-1
O
O
OR
Me Si
H
H
H
Me Si OR
Me
CO2
+
+
Ar
X
H
=
Me Si
Me
O
Si Me
Me
Me
X = NH or N2-
O
OR
O
OR
(ix)
O
Me Si
Me
+
I
O
Me Si
Me
H
+
I
H
O
H
N
(x)
H
I
+
Ar
+
Ar NH
I
H
H
2
O
O
OR
H
N
OR
(xi)
H
O
Me Si
Me
+
O
+
Me Si
Ar
Ar NH
Me
O
2
O
H+
H
N
(xii)
N
H
H
Ar N2-
Ar
Ar
Ar
+
workup
I
H
-
I
O
O
2
H+
O
H
(xiii)
OR
N
H
N
H
Ar
OR
workup
Ar N2-
O
+
Me Si
Me
H
O
O
Me Si
O
2
-
Me
In conclusion, we have developed an alternative strategy to access
formamides via direct N-formylation of nitroarenes with CO2. By
using commercially available Fe powder and 1,1,3,3-
tetramethyldisiloxane as additives, a variety of N-aryl and N-
heteroaryl formamides are synthesized. Mechanistic study suggests
that both Fe metal and hydrosilane can reduce nitroarenes to anionic
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
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S. Bulut, M. Soudania and P. J. Dyson, Chem. Commun., 2016,
nitrogen-based intermediates, which then activate CO2 and
hydrosilane for subsequent formylation.
View Article Online
52, 2497.
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We acknowledged the National Key Research and Development
Program of China (No. 2019YFA0905100) and National Natural
Science Foundation of China (Nos. 21772142, 21971186, and
21961142015) for financial support. We thank Ms Yi-lin Yang (TJU),
Mr Lei Li (TJU) and Mr Shao-Peng Wang (TJU) for assistance in scope
study. We especially thank the anonymous Reviewer for valuable
suggestions to improve the reaction outcomes.
Conflicts of interest
There are no conflicts to declare.
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