Synthesis of α,β-alkynyl ketones via the nickel catalysed carbonylative Sonogashira reaction using oxalic acid as a sustainable C1 source

Article abstract of DOI:10.1039/c9ob01064e

An efficient and economic nickel-dppb catalyzed, carbonylative Sonogashira cross-coupling reaction was demonstrated to provide rapid access to various α,β-alkynyl ketones from aryl iodides and terminal alkynes using oxalic acid as the ex situ C1 source in a double vial (DV) system. Notably, the role of the ligand in combination with the Ni catalyst for the selective formation of carbonylative Sonogashira products was investigated and supported with control experiments. Yet, no reports are available for carbonylative Sonogashira coupling by using a CO-surrogate under Ni-catalyzed conditions. In this process, for the first time, oxalic acid is used as an ex situ solid, bench stable, easy to handle and efficient CO surrogate in a DV-system for the carbonylative Sonogashira coupling reaction with vast substrate scope.

Full text of DOI:10.1039/c9ob01064e

View Article Online
View Journal
Organic &
Biomolecular
Chemistry
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: P. Das, S. Kang, S.
Ram and V. Thakur, Org. Biomol. Chem., 2019, DOI: 10.1039/C9OB01064E.
Volume 15
Number 47
21 December 2017
Pages 9945-10124
This is an Accepted Manuscript, which has been through the
Royal Society of Chemistry peer review process and has been
accepted for publication.
Organic &
Biomolecular
Chemistry
Accepted Manuscripts are published online shortly after acceptance,
rsc.li/obc
before technical editing, formatting and proof reading. Using this free
service, authors can make their results available to the community, in
citable form, before we publish the edited article. We will replace this
Accepted Manuscript with the edited and formatted Advance Article as
soon as it is available.
You can find more information about Accepted Manuscripts in the
Information for Authors.
Please note that technical editing may introduce minor changes to the
text and/or graphics, which may alter content. The journal’s standard
Terms & Conditions and the Ethical guidelines still apply. In no event
ISSN 1477-0520
PAPER
I . J. Dmochowski et al.
Oligonucleotide modifi cations enhance probe stability for
shall the Royal Society of Chemistry be held responsible for any errors
single cell transcriptome in vivo analysis (TIVA)
or omissions in this Accepted Manuscript or any consequences arising
from the use of any information it contains.
rsc.li/obc

Please do not adjust margins
Organic & Biomolecular Chemistry
Page 1 of 5
View Article Online
DOI: 10.1039/C9OB01064E
ARTICLE
Synthesis of α, β-alkynyl ketones via nickel catalysed carbonylative
Sonogashira reaction using oxalic acid as a sustainable C1 source
Shaifali,a,b Shankar Ram,a,b Vandna Thakur a,b and Pralay Das*,a,b
Received 00th January 20xx,
Accepted 00th January 20xx
An efficient and economic nickel-dppb catalysed, carbonylative Sonogashira cross-coupling reaction was demonstrated to
provide rapid access to various α, β-alkynyl ketones from aryl iodides and terminal alkynes using oxalic acid as ex situ C1
source in double vial (DV) system. Notably, the role of ligand in combination with Ni catalyst for the selective formation of
carbonylative Sonogashira products was investigated and supported with control experiments. Yet, no report available for
carbonylative Sonogashira coupling by using CO-surrogate under Ni-catalyzed condition. Under this process, first time oxalic
acid was used as ex-situ solid, bench stable, easy to handle and efficient CO surrogate under DV-system for carbonylative
Sonogashira coupling reaction with vast substrate scope.
DOI: 10.1039/x0xx00000x
catalyst.5 Nevertheless, CO insertion, catalyst stability and
selective product formation can be tuned with the help of
ligands. More recently, researchers have also relied on
Introduction
Carbon monoxide is considered as one of the most
indispensable C1 source in transition metal catalysed
carbonylation chemistry for the synthesis of myriad of natural
products, pharmaceuticals, industrially important bulk and fine
chemicals.1 However, the safety hazards associated with
transportation and storage of toxic, odorless and inflammable
gaseous CO along with the need for specially designed high
pressure reaction systems poses serious limitations for its use
in large scale as well as general laboratory practices. Hence, to
achieve CO gas free carbonylation, use of bench stable CO
equivalents has garnered much interest in recent years.2 But,
problems of functional group tolerance, generation of huge
waste and formation of other side products due to use of
stoichiometric amount of additives for evolution of CO from
previously reported CO surrogates remain the major
drawbacks.3 Hence, the use of in-expensive, additive free and
non-toxic CO surrogate is highly desirable. Moreover, contrary
to noble transition metals such as palladium, the use of
economic and easily available nickel (Ni) metal for
carbonylation reactions remains less explored which is
attributed to the high affinity of nickel towards carbon
monoxide resulting in poisoning of catalyst. Wherein, the full
coordination of Ni to Ni(CO)4 restricts the oxidative addition of
aryl halides and migratory insertion of CO in the catalytic cycle.4
Additionally, catalyst deactivation due to formation of inactive
nickel complexes further add to adversity using nickel as a
controlled release of CO from CO surrogates for the stability of
nickel catalysts.[4-7] In recent years, Ni catalysed carbonylation
has been successfully applied for the synthesis of various
molecules such as benzyl alkyl ketones,6c benzophenones,4,6a γ-
lactams,5a α, β-unsaturated carboxylic acid 7a-c, substituted
iodoesters7d and benzylated heteroarenes.7e But, to date, the
synthesis of α, β-alkynyl ketones, the basic scaffolds for various
natural products and biologically important synthetic
molecules,8-9 which are end products of carbonylative
Sonogashira reaction is exclusively reported with palladium
metal catalysts only. Although, the use of nickel metal has not
been known for carbonylative Sonogashira cross-coupling
reaction, but, during the preparation of our manuscript, Chidara
et al. reported the Ni(OAc)2.4H2O catalyzed carbonylative
Sonogashira reaction using CO gas. But, the reaction showed
limited substrate scope for alkynes and also found to be
incompatible with solid or bench stable CO surrogates.10 In
recent years, our group has put tremendous efforts to explore
oxalic acid as bench stable in situ or ex-situ CO, CO2 and H2
source in combination with heterogeneous transition metal
catalysts for various organic transformations.11 Moreover, to
generalize the use of oxalic acid as CO source, herein, first time
we developed NiCl2 catalyzed carbonylative Sonogashira
reaction using oxalic acid as compatible ex situ CO source under
given catalytic conditions.
Results and Discussion
a. Natural Product Chemistry and Process Development Division, CSIR- Institute of
Himalayan Bioresource Technology, Palampur-176061, H.P, India.
pdas@ihbt.res.in, pralaydas1976@gmail.com.
Initially, we targeted the reaction of iodobenzene,
phenylacetylene and (CO2H)2 as in situ CO surrogate or in one
pot fashion in presence of NiCl2.6H2O as catalyst and dppb as
ligand to synthesize the corresponding alkynone 4a. But, to our
dismay reaction did not proceed and we got 5a as major
b. Academy of Scientific and Innovative Research (AcSIR), CSIR-IHBT, Palampur,
India.
† Footnotes relating to the title and/or authors should appear here.
Electronic Supplementary Information (ESI) available: [details of any supplementary
information available should be included here]. See DOI: 10.1039/x0xx00000x
Please do not adjust margins

Please do not adjust margins
Organic & Biomolecular Chemistry
Page 2 of 5
ARTICLE
Journal Name
product. In this context, we employed oxalic acid in DMF as an conditions (Table 1, entry 8). Moreover, other CO sVuierwroAgrtaictleeOsnil.inee.
ex situ carbonyl source in a double vial system (DV) for avoiding N - formylsaccharin, formic acid, paraforDmOaI:ld10e.h10y3d9e/C, 99O-mB0e1t0h6y4lE-
excess exposure of catalytic system to CO atmosphere in order 9H-fluorene-9- carbonyl chloride were also used under similar
to facilitate the formation of active nickel species. At the outset reaction conditions (Table 1, entries 9-12). We got 30% yield of
of our experiment, we have chosen iodobenzene 1a and carbonylative product 4a in case of N-formyl saccharin (Table 1,
phenylacetylene 2a as bench stable model substrates for Entry 9), while others were unable to give desired carbonylative
anticipated carbonylative Sonogashira coupling reaction. We product. Hence, iodobenzene (1 equiv.), phenylacetylene (2
have done exhaustive examination of the reaction parameters equiv.), NiCl2 (0.10 equiv.), dppb (0.05 equiv.), K2CO3 (2 equiv.)
such as catalyst, ligand, base and solvents (Table S1, ESI).
in DMF in inner vial and oxalic acid (6 equiv.) in DMF in outer
Further, we also extended our optimization studies on vial as an ex situ source was found to be the best suited
screening of equivalency of oxalic acid, various CO surrogates conditions for the reaction.
and effect of solvent on decomposition of oxalic acid.
Furthermore, a set of control experiments were also performed
to figure out the role of ligand to reduce byproduct formation,
enhance the yield of the desired product and understanding of
reaction mechanism (Scheme 1).
Table 1. Screening of CO sources
CO
O
C
(ex situ CO Source)
NiCl2, dppb
I
O
C
CO (ex situ from (CO2H)2)
NiCl2,
K2CO3
O
C
OH
+
I
without ligand
DMF, 130 oC, 7 h
(a)
(b)
+
+
K2CO3, DMF
1a
2a
4a
130 o
C
1a
2a
4a
)
5a
(45%)
(25%
Yield%a
32
S.No. CO surrogates (equiv.)
External Solvent
O
O
OH
CO (ex situ from (CO2H)2)
NiCl2,
C
(COOH)2 (3)
(COOH)2 (6)
1
2
DMF
DMF
C
without ligand
70
K2CO3, DMF
5a
4a
130 o
C
(not detected)
50
3
4
5
6
7
8
(COOH)2 (6)
(COOH)2 (6)
(COOH)2 (6)
(COOH)2 (6)
-
NMP
Toluene
O
O
I
CO (ex situ from (CO2H)2)
NiCl2,
COOH
Traces
10
without ligand
+
+
(c)
(d)
K2CO3, DMF
PEG-400
PEG- dioxane (1:1)
DMF
130 o
C
6
7
6
1a
28
O
C
CO2 (Dry Ice)
NiCl2, dppb
I
Traces
Traces
+
K2CO3, DMF
(6)
CH3COOH
DMF
130 o
C
1a
2a
4a
(not detected)
30
Traces
nd
9
N- Formyl Saccharin (6)
Formic acid (6)
DMF
DMF
DMF
CO (in situ from (CO2H)2)
NiCl2, K2CO3
O
C
OH
10
11
I
Paraformaldehyde (6)
+
+
(e)
DMF, 130 o
C
9-Fluorenyl carbonyl
chloride (6)
nd
12
DMF
5a (
50%)
15%
1a
2a
Reaction Condition: Inner vial: Iodobenzene (1 equiv.), phenylacetylene (2 equiv.),
NiCl2 (0.10 equiv.), dppb (0.05 equiv.), K2CO3 (2 equiv.), DMF (2mL); Outer vial; CO
surrogate (6 equiv.) in DMF (0.5mL) at 130 oC for 7h; [a] isolated yields; nd= not
detected
Scheme 1. Set of control experiments done to understand the reaction mechanism
Initially, we have carried out the standard reaction in the
absence of ligand using oxalic acid as ex situ CO source and
obtained 25% carbonylative Sonogashira product (4a) and 45%
of (Z)-3-hydroxy-1,3-diphenylprop-2-en-1-one (5a) (Scheme 1,
entry ‘a’). Further, in order to check the formation of 5a, we
have done the reaction of 4a under similar reaction conditions.
However, we did not detect 5a even in trace amount (Scheme
1, entry ‘b’). This observation ruled out the assumption of
formation of 5a through hydration of 4a under our conditions.
The other possibility of 5a formation may be through
carbonyaltive coupling of iodobenzene (1a) with acetophenone
(6), which may be formed through hydration of phenylacetylene
(Scheme 1, entry ‘c’). To our dismay, we ended up with benzoic
acid (7) and unreacted acetophenone (Scheme 1, entry c).
These observations led us to think that the water occurred
through the decomposition of oxalic acid and may get vaporize
and contaminate with the reaction mixture during the course of
reaction (Figure 1). As per our earlier development and
literature reports, oxalic acid under heating condition
decomposes to give CO, CO2 and H2O. Additionally, fate of CO2
It was found that 6 equiv. of oxalic acid is sufficient for
carbonylative Sonogashira coupling reaction (Table 1, entries 1-
2). The combinations of different solvents and oxalic acid were
also tested and DMF was found to be best (Table 1, entries 3-6).
Interestingly, combination of NMP and oxalic acid was found to
be compatible for evolution of CO during the course of the
reaction, and obtained 50% of product 4a (Table 1, entry 3). This
observation reinforces the fact that oxalic acid act as CO source.
According to literature survey, it is anticipated that dissociation
of oxalic acid is highly favourable in amine containing solvents.12
Besides, assisting in dissociation of oxalic acid boiling point of
DMF is higher than that of decomposition of oxalic acid (>= 130
oC) which further aid in feasibility of the reaction. Further, we
obtained the desired product 5a in traces in absence of oxalic
acid (Table 1, entry 7). Similarly, very less product was formed
on replacing oxalic acid with acetic acid, which rule out the
possibility of decomposition of DMF into CO under acidic
2 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 3 of 5
Organic & Biomolecular Chemistry
Please do not adjust margins
Journal Name
ARTICLE
was also checked, hence we performed reaction of 1a and 2a (stoichiometric) amount of moisture content mVaiyewfAartvicolerOtnhlinies
DOI: 10.1039/C9OB01064E
with CO2 (dry ice) under optimized reaction conditions, but no pathway. This moisture content may be presumably arising
product was detected. However, when the reaction was from on decomposition of oxalic acid vapor. Further, the
subjected under in situ CO source or in one pot fashion, 5a was intermediate D give intermediate E.7b-c The Intermediate E
formed in 50% yield. This may be due to Bronsted acidity of undego intermolecular hydride shift and procure species F.7b,17
oxalic acid or inability of formation of the active nickel species Final step includes release of enol 5a through intermediate F
to form desired carbonylative Sonogashira as major product and regeneration of catalyst in presence of CO and solvent.
(Scheme 1, entry ‘e’). The reaction was found to be insensitive To check the applicability of present protocol, we shifted our
to TEMPO, which rule out free radical pathway.
focus to scrutinize the reaction of various substituted
Hence, based on previous literature and our observations phenylacetylenes with iodobenzene 1a under the optimized
herein, we proposed the best plausible mechanisms for desired conditions. We started our study with 4-ethynyltoluene which
product 4a formation following Path-I whereas in absence of gave desired product 3a in 65% yield. The reaction of 3-, 2-
ligand the same reaction ended with unexpected product 5a ethynyltoluene, 4-, 2-methoxy substituted phenylacetylenes
following Path-II (Figure 1). According to literature, DMF can act afforded the carbonylative products (3b-3e) in good yields i.e.,
as reducing agent13a-c and under the reaction condition 55-60%. It is observed that reaction went smoothly in case of 2-
(DMF/CO) Ni(II) salt may reduce to Ni(0) and further produce ethynyltoluene as compared to 3-ethynyl toluene. Encouraged
Ni-complex (I) with ligand.6a The Ni(0)L (I) species further by this observation, we also tested 4–ethyl, -t-butyl, 4-OPh
undergo oxidative addition with aryl iodides to give substituted phenylacetylenes and obtained the corresponding
intermediate (II).
carbonylative Sonogashira products in 45-70% (3f-3h) yields.
O
C
O
O
C
Table 2. Substrate scope of phenylacetylenes
Ph
Ph
O
C
OH
Ar
KI
Ar'
Ph
Ph
5a
O
C
4a
+
CO
OH
Ph
KHCO
O
C
(ex situ from oxalic acid)
NiCl2
H
Ar'
O
C
Ph
Ni
C
CH
R
(Ref.
3
I
NiII
L
Ar
7b,
Xn
dppb, K2CO3
17)
H
F
K
+
O
C
2 CO
H
DMF, 130 oC, 7-12hrs
+ H
Ph
R
O
3
Ar
3a
1a
2b
Xn
E
O
C
L=dppb
O
C
O
C
O
C
OC
LNiII
Ar
I
Ar'
Ni0L
Ni0Xn
(Ref. 7b-c)
DMF/CO
Path II
ArI
Ligand
I
( )
Ligand
A
H
O
C
H
Path I
III
(
)
ArI
O+
Ar'
H
Ar
a
O
Ni
3d
(60%)
3a
3b (55%)
Ph
(65%)
3c
(57%)
O
Ar
H
Xn
NiCl2
O
C
O
C
O
C
XnNiII
H2O
C
I
Ar
O
D
B
LNiII
II
(Ref. 15, 16, 7c)
Xn
Ar
I
I
Ni
KI+KHCO3
OC
CO
C2H5
OPh
K2CO3
+
C
3e
3g (61%)
a
(55%)
O
C
(70%)
O
O
O
O
O
3f
3h
(45%)
H
Ph
CO2
+
H2O
O
C
CO
+
O
H
C
C
O
O
X= CO and solvent molecule
L= dppb
H
2CO2 + H2
H
O
O
OCH3
N
a
3i (60%)
3j (60%)
3k (62%)
3l
(57%)
Cl
O
O
C
O
C
C
Figure 1. Plausible mechanism for carbonylative Sonogashira in presence and
absence ligand
F
F
OCH3
Then, the intermediate (II) on coordination with CO and alkyne
may produce the intermediate (III). Further, migratory insertion
of CO under the basic condition give ynyl-nickel complex (IV).
Finally, reductive elimination of intermediate (IV) procures
desired alkynones. The ligand complex with nickel in
intermediates III and IV is also playing significant role to restrict
3n (45%)a
3m (76%)
3o
(70%)
O
C
O
C
S
Br
3p
(30%)
3q (20%)
the active site of catalyst and give the desire product 4a even in Reaction Condition: Inner Vial: Iodobenzene (1 equiv.), phenylacetylene (2 equiv.),
NiCl2 (0.10 equiv.), dppb (0.05 equiv.), K2CO3 (2 equiv.), DMF (2mL); Outer vial; CO
surrogate (6 equiv.) in DMF (0.5mL) at 130 oC for 7 h; [a]12 h.
presence of traces of water in the reaction mixture.
Further, based on literature in path II it is proposed that
nickel may produce complex A under DMF solvent and CO
More importantly, tri- and di-substituted phenylacetylenes also
[13a-c]
environment.
Nickel complex A further react with aryl
The
tolerated well under reaction conditions and resulted in
respective alkynones (3i-k) in 60-62% yields. Furthermore, -
N(CH3)2, 2-ethynyl 6-methoxynapthalene gave carbonylative
Sonogashira products 3l and 3m in 57 and 76% yields
respectively. In case of halogen substituted phenylacetylenes,
we subjected 3, 4- difluoro, 2-Cl and 4-Br substituted
phenylacetylenes under set reaction conditions and isolated
moderate yield of products 3n-p, while low yield was observed
in case of 4-Br. The reaction of 2-Cl also went smoothly and
procured good yield of product 3o in 70%. The substrate scope
iodide for oxidative addition and afford complex B.
intermediate B may undergo coordination with CO to afford
intermediate C. The intermediate C undergo alkyne insertion
under the assistance of base.14 It is predicted that the
intermediate C found to be susceptible to attack with water as
15
oxonium ion
with ligand or any substrate from reaction
mixture replacement,16 which may get restricted in Path I due
to presence of ligand and give intermediate D.7c It is speculated
that slow release of CO from oxalic acid and presence of small
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
Please do not adjust margins

Please do not adjust margins
Organic & Biomolecular Chemistry
Page 4 of 5
ARTICLE
Journal Name
was further extended to 3-ethynylthiophene and yielded may exist as their enol tautomer.18 Herein, we have applied
View Article Online
DOI: 10.1039/C9OB01064E
product in 20% (detected by ESI-MS). In case of electron oxalic acid as ex situ C1 source under ligand free Ni catalyzed
withdrawing substituents, -CF3, -CN and aliphatic alkynes, the conditions for the synthesis of substituted (Z)-3-hydroxy-1,3-
reaction was found to be sluggish.
diphenylprop-2-en-1-one. The reaction of -H, -CH3, and -F
Further, we have extended the set reaction conditions on substituted aryl iodides and phenylacetylenes using oxalic acid
electron donating and electron withdrawing aryl iodides to as ex situ CO source gave (Z)-3-hydroxy-1,3-diphenylprop-2-en-
check the functional group tolerance and specificity of given 1-one 5a-c as major products and carbonylative Sonogashira 4a-
methodology, results summarized in Table 4. The reaction of c as minor products, results summarized in Table 5.
electronically rich compounds 4-, 3- and 2- iodoanisoles with
Table 4. Synthesis of 3-hydroxy-1, 3-diphenylprop-2-en-1-one
model alkyne afforded the corresponding carbonylative
Sonogashira products (4b-4d) in 65-55% yields.
(COOH)2 as Ex situ source
O
O
C
OH
NiCl2
C
I
Without ligand
R
+
+
R
K2CO3, DMF
130 oC, 7 h
Table 3. Substrate scope of aryl iodides
R
4a-c (Minor)
5a-c (Major)
CO
Yield%
Minor
( ex situ from oxalic acid)
Product
S.No.
R
Major
O
C
NiCl2
dppb, K2CO3
I
O
C
OH
O
C
OH
+
O
OH
DMF, 130 oC, 7h-12h
R
R
C
4a-m
1a
2b
F
O
C
O
C
O
C
O
C
5a
(45%, 25%)
5b
5c
(50%, 18%)
(55%, 28%)
H3CO
OCH3
OCH3
4c
4b(65%)c
4a(70%)
(57%)
4d
(55%)
Reaction Condition: Inner vial; Iodobenzne (1 equiv.), phenylacetylene (2 equiv.),
NiCl2 (0.10 equiv.), K2CO3 (2 equiv.), DMF (2mL); Outer vial: oxalic acid (6 equiv.) in
DMF (0.5 mL) at 130 oC, 7 h
O
C
O
C
O
C
O
C
H3C
H2N
F
4g (
70%)
a
4h
(55%)
4e
4i
(65%)
4f (71%)
O
C
O
C
O
C
O
C
S
Conclusions
Br
Cl
F3C
In summary, for the first time the Ni-dppb catalytic system was
applied successfully with CO surrogate conditions for
carbonylative Sonogashira coupling reaction and more
specifically with bench stable and economic oxalic acid as CO
source. Herein, additive free and sustained ex situ
decomposition of oxalic acid in DMF provides better selectivity
and efficiency to the catalytic system. The Ni-dppb complex was
found to be highly selective under the moisture condition and
inhibits the by-product formation. This methodology is
applicable to series of substituted aryl iodides and
phenylacetylenes and procured moderate to good yields of
alkynones. Further, the same method under ligand free Ni
catalyzed condition performed differently and ended with (Z)-
3-hydroxy-1,3-diphenylprop-2-en-1-one products in a selective
manner.
c
(57%)
4l (
38%)
b
4k (42%)c
4j
(41%)
O
C
4m
(50%)
Reaction Condition: Inner Vial; Iodobenzne (1 equiv.), phenyla-cetylene (2 equiv.),
NiCl2 (0.10 equiv.), dppb (0.05 equiv.), K2CO3 (2 equiv.), DMF (2mL); Outer vial:
oxalic acid (6 equiv.) in DMF (0.5 mL) at 130 oC, 7 h. [a] 5 h, [b] 8 h, [c]12 h
It was found that 2,3-methoxy substituted aryl iodides gave
carbonylative product in lower yield as compare to 4-
iodoanisole. These results indicated the effect of electronic and
steric factor respectively. In case of 4-iodotoluene and 1-
iodonaphthalene the respective alkynones 4e and 4f were
obtained in 65% and 71% yields. Furthermore, 4-iodoaniline
gave the corresponding product in 70% yield while 2-iodoaniline
did not participate in the reaction under set conditions.
Intriguingly, halogen substituted aryl iodides were also
tolerated well in the reaction. It was found that 4-F, Cl, and Br
substituted aryl iodides gave 55, 57 and 41% yield respectively
(Table 4, 4h-j). Moreover, high selectivity of the reaction was
noticed during the course of reaction for iodo-substrate (Table
4, entry 4j). The reaction of heteroaryl iodide i.e. 2-
iodothiophene procured the corresponding product 4k in 42%
yield. We also subjected the electronically deficient 4-CF3
substituted aryl iodide and procured the respective
carbonylative product 4l in moderate yield. Interestingly,
reaction of 2-iodofluorene delivered the carbonylative product
4m in considerably good yield.
Conflicts of interest
“There are no conflicts to declare”.
Acknowledgements
Authors are grateful to Director CSIR-IHBT for providing
necessary facilities during the course of the work. The authors
thank CSIR project MLP0203 for financial support. S., S.R., and
V.T. thank UGC and CSIR, New Delhi for awarding fellowship.
Notes and references
‡ Footnotes relating to the main text should appear here. These
might include comments relevant to but not central to the matter
Earlier, diversely substituted 1,3-diketones were prepared by
carbonylative α-arylation of acetone and acetophenones, which
4 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 5 of 5
Organic & Biomolecular Chemistry
Please do not adjust margins
Journal Name
ARTICLE
under discussion, limited experimental and spectral data, and 11 (a) A. K. Shil, S. Kumar, C. B. Reddy, S. Dadhwal, V. Thakur, and
View Article Online
crystallographic data.
P. Das, Org. Lett., 2015, 17, 5352−5D35O5I:;10(b.1)03V9./CT9hOaBk0u1r0,64AE.
Kumar, N. Sharma, A. K. Shil, and P. Das, Adv. Synth. Catal.,
2018, 360, 432–437; (c) N. R. Guha, V. Thakur, D.
Bhattacherjee, R. Bharti, and P. Das, Adv. Synth. Catal., 2016,
358, 3743–3747; (d) R. Bharti, C. B. Reddy, and P. Das
ChemistrySelect, 2017, 2, 4626–4629 (e) V. Thakur, A. Sharma,
Yamini, N. Sharma, and P. Das, Adv. Synth. Catal., 2019, 361,
426–431; (f) C. B. Reddy, S. Ram, A. Kumar, R. Bharti, and P.
Das, Chem. Eur. J., 2019, 25, 4067 –4071.
§
§§
etc.
1
(a) B. Cornils and W. A. Herrmann, Applied Homogeneous
Catalysis with Organometallic Compounds, A Comprehensive
Handbook in Three Volumes, Wiley-VCH Verlag GmbH, 65
2002; (b) P. Knochel and G. A. Molander, Comprehensive
Organic Synthesis (Second Edition), Elsevier Ltd., 2014 (c) M.
Beller,; X. -F. Wu, Transition Metal Catalyzed Carbonylation 12 L. W. Clark, J. Phys. Chem. 1957, 61, 5, 699-701.
Reactions, Carbonylative Activation of C-X Bonds, Springer, 13 (a) I. Pastoriza-Santos and L. M. Liz-Marza´n Adv. Funct.
Amsterdam, 2013 (d) M. Beller, Catalytic Carbonylation
Reactions, Springer Berlin Heidelberg, 2006 (e) L. Kollar,
Modern Carbonylation Methods, WILEY VCH Verlag GmbH,
2008.
(a) P. Gautam and B. M. Bhanage, Catal. Sci. Technol., 2015,
5, 4663-4702; (b) T. Morimoto and K. Kakiuchi, Angew. Chem.
Mater., 2009, 19, 679–688; (b) Y. Feng, K. Zhang, B. Yan, S. Li,
and Y. Du, Catalysts., 2016, 6, 103; (c) J. Muzart, Tetrahedron.,
2009, 65, 8313–8323.
14 A. M. Mak, Y. H. Lim, H. Jong, Y. Yang, C. W. Johannes, E. G.
Robins, and M. B. Sullivan, Organometallics, 2016, 35,
1036−1045.
2
3
Int. Ed., 2004, 43, 5580–5588; (c) L. R. Odell, F. Russo, and M. 15 (a) O. Israelsohn, K. Peter, C. Vollhardt and J. Blum, J. Mol.
Larhed, Synlett., 2012, 5, 685-698; (d) S. D. Friis, A. T.
Lindhardt and T. Skrydstrup, Acc. Chem. Res., 2016, 49,
594−605.
Catal. A: Chem., 2002, 184, 1–10; (b) W. Baidossi, M. Lahav
and J. Blum, J. Org. Chem., 1997, 62, 669-672.
16 J. A. Casares, P. Espinet, J. M. Martı´nez-Ilarduya, J. J.
Mucientes and G. Salas, Inorg. Chem., 2007, 46, 1027-1032
(a) P. Hermange, A. T. Lindhardt, R. H. Taaning, K. Bjerglund,
D. Lupp, and T. Skrydstrup, J. Am. Chem. Soc., 2011, 133, 17 K. Ogata, H. Murayama, J. Sugasawa, N. Suzuki, and S.-i.
6061–6071; (b) X. F. Wu, X. Fang, L. Wu, R. Jackstell, H.
Fukuzawa, J. Am. Chem. Soc., 2009, 131, 3176–3177.
Neumann, and M. Beller, Acc. Chem. Res., 2014, 47, 18 J. Schranck, Dr. A. Tlili, P. G. Alsabeh, Dr. H. Neumann, Prof.
1041−1053.
Dr. M. Stradiotto and Prof. Dr. M. Beller, Chem. Eur. J., 2013,
19, 12624–12628; (b) T. M. Gøgsig, H. R. Taaning, T. A.
Lindhardt, and T. Skrydstrup, Angew. Chem. Int. Ed., 2012, 51,
798 –801.
4
5
J. B. Peng, F. P. Wu, D. Li, X. Qi, J. Yingc and X. F. Wu, J. Org.
Chem., 2018, 83, 6788–6792.
(a) Y. Hoshimoto, K. Ashida, Y. Sasaoka, R. Kumar, K.
Kamikawa, X. Verdaguer, A. Riera, M. Ohashi, and S. Ogoshi,
Angew. Chem., 2017, 129, 8318–8322; (b) Q. Wang, C. Chen,
Tetrahedron Lett., 2008, 49, 2916–2921.
6
7
(a) Y. Li, D. H. Tu, B. Wang, J. Y. Lu, Y. Y. Wang, Z. T. Liu, Z. W.
Liu, and J. Lu, Org. Chem. Front., 2017, 4, 569–572; (b) X. Wu,
Y. Zhao, and H. Ge, J. Am. Chem. Soc., 2015, 137, 4924–4927;
(c) T. L. Andersen, A. S. Donslund, K. T. Neumann, and T.
Skrydstrup, Angew. Chem. Int. Ed., 2018, 57, 800 –804.
(a) J. Hou, M.-L. Yuan, J.-H. Xiea, and Q.-L. Zhou, Green Chem.,
2016, 18, 2981–2984; (b) M.-C. Fu, R. Shang, W.-M. Cheng,
and Y. Fu, ACS Catal., 2016, 6, 2501−2505; (c) X. Wang, M.
Nakajima, and R. Martin. J. Am. Chem. Soc., 2015, 137,
8924−8927. (d) J. B. Peng, F. P. Wu, C. Xu, X. Qi, J. Ying, and X.
F. Wu, iScience, 2018, 8, 175–182; (e) J. B. Peng, F. P. Wu, X.
Qi , J. Ying, and X. F. Wu, Commun. Chem., 2018 1:87, DOI:
10.1038/s42004-018-0091-2.
8
9
(a) C., Chowdhury, and N. G. Kundu, Tetrahedron lett., 1999,
55, 7011; (b) B. M. Trost, and Z. T. Ball, J. Am. Chem. Soc.,
2004, 126, 13942; (c) C. A. Quesnelle, P. Gill, M. Dodier, D. St.
Laurent, M. Serrano-Wu, A. Marinier, A. Martel, C. E.
Mazzucco, T. M. Stickle, J. F. Barrett, D. M. Vyas, and B. N.
Balasubramanian, Bioorg. Med. Chem. Lett., 2003, 13, 519–
524.
(a) J. D. Kirkham, S. J. Edeson, S. Stokes, and J. P. A. Harrity,
Org. Lett., 2012, 14, 5354–5357; (b) A. V. Kel’in, and V. J.
Gevorgyan, Org. Chem., 2002, 67, 95; (c) J. H. Shen, G. L.
Cheng, and X. L. Cui, Chem. Commun., 2013, 49, 10641–
10643; (d) H. Liu, H. Jiang, M. Zhang, W. Yao, Q. Zhu and Z.
Tang, Tetrahedron Lett., 2008, 49, 3805–3809; (e) E. Awuah,
and A. Capretta, Org. Lett., 2009, 11, 3210– 3213; (f) L.
Åkerbladh, P. Nordeman, M. Wejdemar, L. R. Odell, and M.
Larhed, J. Org. Chem., 2015, 80, 1464−1471; (g) M. S. M.
Ahmed, K. Kobayashi, and A. Mori, Org. Lett., 2005, 7, 4487–
4489; (h) A. V. Kel′in, A. W. Sromek, and V. Gevorgyan, J. Am.
Chem. Soc., 2001, 123, 2074–2075.
10 R. Charugandla, M. S. Vangala, S. Chidara and R. B. Korupolu
Tetrahedron Lett., 2018, 59, 3283–3287.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 5
Please do not adjust margins