Nickel-Catalyzed Deamidative Step-Down Reduction of Amides to Aromatic Hydrocarbons

Article abstract of DOI:10.1021/acscatal.6b03040

To date, cleavage of the C-N bond in aromatic amides has been achieved in molecules with a distorted constitutional framework around the nitrogen atom. In this report, a nickel-catalyzed reduction of planar amides to the corresponding lower hydrocarbon homologue has been reported. This involves a one-pot reductive cleavage of the C-N bond followed by a tandem C-CO bond break in the presence of a hydride source. Substrate scope circumscribes deamidation examples which proceed via oxidative addition of nickel in the amide bonds of nontwisted amides. Mechanistic studies involving isolation and characterization of involved intermediates via different spectroscopic techniques reveal a deeper introspection into the plausible catalytic cycle for the methodology.

Full text of DOI:10.1021/acscatal.6b03040

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Letter
Nickel catalyzed deamidative step-down
reduction of amides to aromatic hydrocarbons
Aniruddha Dey, Sheuli Sasmal, Kapileswar Seth, Goutam Kumar Lahiri, and Debabrata Maiti
ACS Catal., Just Accepted Manuscript • DOI: 10.1021/acscatal.6b03040 • Publication Date (Web): 06 Dec 2016
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Nickel catalyzed deamidative step-down reduction of amides to
aromatic hydrocarbons
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Aniruddha Dey, † Sheuli Sasmal, † Kapileswar Seth, Goutam K. Lahiri* and Debabrata Maiti*
Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai-400076, India.
Supporting Information Placeholder
the amide linkage. Cleavage of the CO−N bond is rendered
problematic owing to conjugation of the lone pair of nitrogen
with the carbonyl group. Also, high basicity of the amine
group makes it a poor nucleofuge. Unequivocally enough,
scission of the CO−N bond had therefore been performed by
the use of nickel, a late transition series metal which is elec-
tropositive and can undergo oxidative addition to bonds.2f,7
Oxidative additions into the CO−N bond followed by a tan-
dem reductive cleavage of the CO−C bond have been report-
ed only for sterically distorted/twisted amides.8 In this re-
port, we present a nickel catalyzed reductive deamidative
cleavage of the CO−C bond of planar amides.
Reduction of amides to the corresponding lower hydrocar-
bon homologue requires elimination of the amine partner
and a concomitant decarbonylation. Use of standard alumin-
ium based reducing agent like LiAlH4 is not helpful as its
greater hydride donating ability reduces amides to amines.
Similarly, reduction to aldehydes occurs in presence of di-
isobutyl aluminium hydride or by other methods.9 We fur-
nish a one-pot direct step-down protocol for conversion of
an amide into a hydrocarbon.
ABSTRACT: Till date, cleavage of the C−N bond in aromatic
amides was found to be possible in molecules with a distort-
ed constitutional framework around the nitrogen atom. In
this report, a nickel catalyzed reduction of planar amides to
the corresponding lower hydrocarbon homologue has been
reported. This involves a one pot reductive cleavage of the
C−N bond followed by a tandem C−CO bond break in pres-
ence of a hydride source. Substrate scope circumscribes de-
amidation examples which proceed via oxidative addition of
nickel in the amide bonds of non-twisted amides. Mechanis-
tic studies involving isolation and characterization of in-
volved intermediates via different spectroscopic techniques
reveal a deeper introspection into the plausible catalytic cy-
cle for the methodology.
Keywords: nickel, amides, deamidation, C−N bond, catalysis,
reduction
The advent of transition metal catalysis in organic transfor-
mations have revamped the synthetic efficacy for chemical
reactions. As novel synthetic routes unfold creating wider
dimensions for retrosynthetic applicability, chemists contin-
ue to pool their efforts leading to discovery of benign proto-
cols time and again. Incorporation of functional groups at
strategic locations within a molecule has now become easier
owing to the availability of diverse C−H functionalization
pathways. Functionalization at both sp2 and sp3 carbon cen-
tres has been performed with transition metals acting as ef-
fective catalyst partners.1 On the contrary, execution of de-
functionalization strategies manifest immense significance
especially when they equate with an admirable degree of
selectivity. Over the decades, ample reports on C−X defunc-
tionalization (X = functional group) validate the competence
of transition metals in overpowering the high bond dissocia-
tion energy of the C−X bond.2 A variety of approaches such
as deformylation, decyanation, desulfurization, decarboxyla-
tion, dehalogenation, etc. therefore delineated the tale of
metal mediated defunctionalization.3 Extending the similar
approach towards amides would mean confrontation with
three distinct possibilities of bond disconnection (Scheme 1).
First, cleavage of the N(amide)−aryl bond, as was demon-
strated by Chatani in presence of nickel catalyst.4 Second,
cleavage of the CO(amide)−N(amine) bond, as was per-
formed by Szostak and Garg.5 The final possibility was the
reductive cleavage of the CO−C bond that has however re-
mained less explored.6
Scheme 1. Various modes of amide bond scission.
In order to execute a successful oxidative addition of nickel
into the CO−N bond, controlling the electron donation from
nN to π*CO was a supreme need. This necessitated amides
with destabilized ground-state. Commencement was there-
fore made with twisted amides where barrier to rotation is
controlled by geometrical factors.5f,10 An attempt for execu-
tion of deamidative cleavage of the benzamide (Scheme 2, 1,
3) failed to produce any desired result. Increase of π-electron
density by introduction of naphthyl/naphthol ring on the
acyl portion of the amide was not helpful (Scheme 2, 2). In-
crease of the CO−N twist angle was thought to improve the
A challenging aspect with the chemistry involving amides
has been the generation of acyl electrophile from cleavage of
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C−N bonds.8b Electrophilic character of the attached carbon-
situation since this would reduce planarity and decrease elec-
tronic delocalization. However, it remained unchanged even
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yl would hence increase. Moreover, a substantial screening of
the ligands was also performed (Table 1) in order to obtain
better reactivity with the metal catalyst. With Ni(cod)2 as the
catalyst, EtPPh2 as the associated ligand and tetramethyl-
disiloxane as the hydride donor, a successful reductive de-
amidation of the amide (Scheme 2, 7) was obtained with
formation of the corresponding hydrocarbon. N atom of the
pyrazole was presumed to have a positive effect in coordina-
tion to catalyst since controlled experiments with a pyrrole
amide derivative did not undergo any deamidation (Scheme
2, 5). No products were formed in absence of the exogenous
ligand. Hydride donating role of siloxanes were limited only
to reduction of carbonyl group in presence of amides thereby
leading to formation of amines from amides.11 We report an
exclusive reduction of the aryl group, i.e, controlled cleavage
of the C(aryl)−CO(carbonyl) bond, without any competitive
acyl reduction in presence of the silylhydride source.11 A fur-
ther optimization of the reaction condition under nitrogen
atmosphere and at a temperature of 130 oC provided 87%
isolated (GC yield, 98%) yield of the desired products. Aro-
matic π-conjugation was perceived to be important for the
protocol as systems lacking unconjugated π-frameworks like
amide derivatives of benzoic acid (scheme 2, 1, 3, 6) did not
effectively qualify for the reaction. Similarly, primary amines
did not serve to be as effective.
With the optimized condition we surveyed the scope of the
substrates. Planar amides with electronically deficient heter-
ocyclic amine partners qualified successfully for the reaction
condition (Scheme 3, 6a-j). Functional group tolerance to-
wards ethers was obtained with pyrazolamide of 2-
ethoxynaphthoic acid (Scheme 3, 6e).3e,12 Halogens such as
fluoro and bromo groups within the naphthyl ring proved to
be quite successful (Scheme 3, 6h, i). Efficacy of the reaction
protocol was further established with biphenyl systems
(Scheme 4, 8a-h, k, l). Both electron donating and electron
withdrawing groups were functionally tolerant (Scheme 4,
8e-h, l). Amides with bulky substituents at the ortho- posi-
tion underwent deamidation without any steric problem.
These include substrates with ortho-substituted phenyl ring
as well as heterocycles (8a-d). Biphenyls containing electron
donating substituents like methoxy, benzyloxy and phenoxy
groups were found to undergo deamidation with good yields
irrespective of the location of the alkoxy groups (8e-g, l).
Cleavage of the amide bond was performed selectively with-
out any competitive cleavage of the ether linkages.3e,12 Highly
electron withdrawing groups like −CF3 were also tolerated
(8h). Also, stilbene systems exhibited deamidation with good
to excellent yields (8i, j).
after attaching phenyl ring to N (Scheme 2, 4).
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Scheme 2. Screening of twisted vs planar amide conformations
for deamidation. GC yields are reported.
We envisaged a system with coplanar CO−N bond plane but
with an electronically deficient amine partner. However,
coplanar pyrrole amide derivatives gave no useful results
(Scheme 2, 5). Consequently, a pyrazole moiety was ligated
to the carbonyl center which would inturn activate the C−N
bond. This would ensure a destabilized ground state which
was crucial for the defunctionalisation chemistry involving
A regioselective oxidative addition of metal to the CO−N
bond was crucial for the process to be executed. Nickel with
relatively smaller atomic radius and an excess of d-electrons
allowed easy donation to the π-acceptor ligands (viz. carbon-
yl group).7d Oxidative addition in form of Ni(II) is reversible
in nature.13 Both PPh3 or EtPPh2 were successful ligands for
the reaction. These basic ligands prevented the possibility of
decarbonylative coupling between the amine and the acid
group.13 Interaction of Ni-catalyst with substrate was moni-
tored through observing CO bond stretching frequency. Up-
on addition of stoichiometric Ni(cod)2 and ligand to the am-
ide substrate, the –CO peak shifted from 1699 cm-1 to 1935
and 1995 cm-1 (Figure 1).14 This indicated the absence of am-
ide CO−N bond and formation of Ni−CO bond during reac-
Table 1: Optimization of the ligands by GC yields. See See Sup-
porting Information.
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tion. The carbon monoxide produced from the reaction may
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either remain ligated to the intermediate complexes or may
be trapped by other zero-valent Ni species.13
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Scheme 4. Deamidative reductive cleavage of various biphenyl
and stilbene based amide derivatives. Isolated yields are re-
ported.
Scheme 3. Deamidative reductive cleavage of various conjugat-
ed amides. Isolated yields are reported.
the intermediate (Naph)Ni(II)(amine)(EtPPh2)2 into C10H8
and C10H6 in 1:1 molar ratio along with release of free amine
and Ni(EtPPh2)n(CO)n or (b) reductive elimination of hydride
In this case, CO was found incorporated into
Ni(CO)n(EtPPh2)2 complex that was isolated from the reac-
tion mixture in absence of hydride source and was character-
ized by X-ray crystallography (Figure 2, a). This isolated
Ni(0) complex yielded 60% of naphthalene product on re-
peating reaction with TMDSO. Formation of final product
could be traced to two possibilities: (a) disproportionation of
coordinated
Ni(II)
intermediate
to
generate
Ni(CO)n(EtPPh2)2 in presence of in situ CO.13 In the absence
of hydride source, Ni(CO)n(EtPPh2)2 alongwith negligible
amount of C10H8 was formed but C10H6 was not detected. No
1:1 ratio was obtained for them. Reaction with TMDSO yield-
ed naphthalene product and Ni(CO)n(EtPPh2)2. Thus, final
production of naphthalene could be attributed to a reductive
elimination from (Naph)Ni(II)(H)(EtPPh2)2 and not by dis-
proportionation reaction (Scheme 5).
Scheme 5. Competitive step for final product formation.
Aerial atmosphere may lead to oxidation proceeding through
a carboxylate intermediate (isolated, Figure 2, b) and was
unfavourable. In order to further substantiate the hydride
transfer step, isotope labelling experiments were conducted
with deuterated hydride source. A 69% of deuterium-
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incorporation was observed in final deamidated product
form I. Following this, Ni(0) undergoes oxidative addition
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(Figure 3). This could be ascribed to the possibility of a rapid
H/D exchange occurring between Ph2SiD2 and the C−H
bonds present in toluene (See Supporting Information, Fig-
ure S5).4 Kinetic studies showed first order dependency on
the amide substrates (Figure 4). Moreover, a zero-order de-
pendence of the reaction rate on the amount of TMDSO was
observed which was indicative of the fact that Ni(I)-silyl spe-
cies were not involved in the reaction (Figure 5).3e,k
across CO−N bond leading to C−N bond activation II (con
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5
10
15
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Time (hour)
Figure 5. Kinetics plot for with respect to silylhydride. Black-
line: 0.1 mmol, Red line: 0.2 mmol.
firmed by ESI-MS; See Supporting Information). After that β-
migration of CO leads to formation of III. Following this,
hydride transfer occurs from TMDSO to the nickel centre
leading to formation of the hydride intermediate IV. Release
of the free amine at this stage was confirmed when reaction
of 6b yielded 3-phenylpyrazole in 60% yield. This is followed
by reductive elimination and Ni(CO)n(EtPPh2)2 formation by
reacting with the in situ generated CO which then continues
the catalytic cycle.
Figure 1. IR data of (a) amide, 6c (blue), (b) reaction mixture
involving 6c showing formation of Ni(CO)2(EtPPh2)2 (red).
Figure 2. X-ray structures for intermediates.
Figure 3. Deuterium incorporation experiment for naphtha-
lene by NMR characterization.
0.36
0.30
0.24
0.18
0.12
0.06
Scheme 6. Mechanistic cycle for deamidative reductive cleav-
age.
In summary, we report the first deamidative tandem reduc-
tive cleavage of the C(aryl)−CO linkage following the scission
of CO−N(amine) bond in amides. Exercise of effective con-
trol over the reaction condition allowed a selective reduction
in presence of the hydride donor. A further development of
the above reaction protocol would assist in the introduction
of other nucleophiles to the acyl ring following the elimina-
tion of the amide linkage.
0
5
10
15
20
Time (hour)
Figure 4. First order reaction kinetics plot for amide substrate.
Black line: 0.1 mmol, Red line: 0.2 mmol substrate.
Based on the experimental observations, a plausible mecha-
nism can be proposed (Scheme 6). At the beginning of the
cycle, Ni(cod)2 undergoes ligand exchange with EtPPh2 to
ASSOCIATED CONTENT
Supporting Information
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K. N.; Garg, N. K. Angew. Chem. Int. Ed. 2016, 55, 2810-2814. (o)
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Information is available free of charge on the ACS publica-
tions website.
Procedure and analytical data. (PDF, CIF file)
AUTHOR INFORMATION
Corresponding Author
*lahiri@chem.iitb.ac.in
*dmaiti@chem.iitb.ac.in
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Author Contributions
‡Both have contributed equally.
ACKNOWLEDGMENT
This activity is supported by CSIR, India (funding to DM,
CSIR, 02(0242)/15/EMR-II). Financial support received from
DST-India (fellowship to K.S. YSS/2015/000736) is gratefully
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ACS Catalysis
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Nickel catalyzed deamidative step-down reduction of amides to
aromatic hydrocarbons
Aniruddha Dey, † Sheuli Sasmal, † Kapileswar Seth, Goutam K. Lahiri* and Debabrata Maiti*
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Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai-400076, India.
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