Pd-catalysed carbonylative annulation of salicylaldehydes with benzyl chlorides using N-formylsaccharin as a CO surrogate

Article abstract of DOI:10.1039/C8NJ03173H

A convenient and highly efficient Pd-catalysed carbonylative annulation of salicylaldehydes with benzyl chlorides to afford the corresponding 3-arylcoumarins in good to excellent yields has been developed. Importantly, the protocol utilizes a commercially available, low cost, solid and easy to handle N-formylsaccharin as an alternative to the highly toxic CO gas.

Full text of DOI:10.1039/C8NJ03173H

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Jason B. Benedict et al.
The role of atropisomers on the photo-reactivity and fatigue of
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Pd-catalysed carbonylative annulation of salicylaldehydes
with benzyl chlorides using N-formylsaccharin as a CO
surrogate†
weceived 00th Wanuary 20xx,
!ccepted 00th Wanuary 20xx
5hL: 10.1039/x0xx00000x
Vinod K. Yadav, Vishnu P. Srivastava and Lal Dhar S. Yadav*
www.rsc.org/
A convenient and highly efficient Pd-catalysed carbonylative annulation of salicylaldehydes with benzyl chlorides to afford
the corresponding 3-arylcoumarins in good to excellent yields has been developed. Importantly, the protocol utilizes a
commercially available, low cost, solid and easy to handle N-formylsaccharin as an alternative to the highly toxic CO gas.
availability in solid form, stability, ease of handling and high
reactivity, N-formylsaccharin is more advantageous for Pd-
Introduction
Over the past several years, palladium-catalysed carbonylation
reaction of organohalides has emerged as a powerful tool for
organic synthesis both in academia and industry.1 Thus, the
reaction has found application in the synthesis of various
pharmaceuticals, agrochemicals and their intermediates.1 The
success of this synthetic strategy is based on the pioneering work
of Heck and Schoenberg,2 who revealed the Pd-catalysed
carbonylation of haloarenes with carbon monoxide (CO).
Basically, these carbonylation reactions rely on the properties of
CO to undergo insertion into carbon-palladium bond and
demonstrate their high impact in the field of Pd catalysis.
Generally, in carbonylation reaction CO gas is used as a reagent
but its high toxicity, inflammability and difficulty in storage,
handling and transportation pose serious safety concerns. In order
to avoid the use of gaseous CO as a carbonylating reagent, a
number of CO surrogates such as a alcohols,3 formic acid,4a-f
formamide,4g-i formates,5a-f including the recently reported
catalysed carbonylation reactions than the other available CO
surrogates,3-7 hence we opted to use it in the present work.
Coumarins (2H-chromen-2-ones), 3-arylcoumarins in
particular, constitute a ubiquitous class of compounds featuring
in a variety of natural products, bioactive molecules and organic
materials.9 Many natural and synthetic coumarins exhibit diverse
biological and pharmaceutical properties including anti-HIV-1,
antibiotic, anti-inflammatory, antidiabetic, antioxidant anticancer,
anticoagulant and antidepressant activities.10 Moreover,
coumarins have found applications as laser dyes,11 organic light-
emitting diodes (OLED)12 and optical brighteners.13 The broad
application potential of coumarins has placed them among the
focal points of studies in synthetic organic chemistry.
Traditionally, 3-arylcoumarins are prepared by condensation-
cyclisation type reactions such as Knoevenagel condensation,14
Wittig,15 Pechmann,16 and Perkin reactions17 using phenols or
aromatic carbonyl compounds. Several alternative methods
involving transition metal-catalysed reactions have been
developed for the synthesis of 3-arylcoumarins.18 Among these,
Pd-catalysed 3-arylation of the coumarin scaffold with aryl halides
or arylbronic acid1a,f,g,n,o,19,20 and Pd-catalysed carbonylative
annulations reactions1m,21 of 2-iodophenols (Scheme 1a)21n or 2-
vinylphenols (Scheme 1b)21c are of particular importance.
Coumarins have also been synthesised from salicylaldehyde and
cinnamaldehyde via N-heterocyclic carbene catalysed unpolung
reactions.22 However, this methods is applicable to the synthesis
of 3-benzylcoumarin but not suitable for the synthesis of 3-
arylcoumarins. Lu and co-workers modified these methods for the
synthesis of 3-arylcoumarins by replacing cinnamaldehyde with
2-chloro-2-arylacetaldehydes.23 Although these methods have
their individual advantages, they suffer from one or more
drawbacks such as the use of strong acids, high temperatures,
harsh reactions conditions, toxic reagents and sometimes
multistep preparation of requisite starting materials. Some years
benzene-1,3,5-triyl triformate (TFBen),5g formaldehyde,6a-g
6i
hexaketocyclohexane octahydrate (C6O6.8H2O),6h
biomass,3b and carbon dioxide7 have been developed.
Mo(CO)6,
In 2013, Manabe and co-workers utilized N-formylsaccharin as
an advantageous and efficient CO surrogate for conducting Pd-
catalysed reductive carbonylation and fluorocarbonylation of aryl
and alkenyl halides.1h,j Recently, the research group of Fleischer1b
and our own8 have also used N-formylsaccharin as a convenient
CO source for alkoxycarbonylation of alkenes and
azidocarbonylation of haloarenes, respectively. Owing to its easy
Green Synthesis Lab, Department of Chemistry, University of Allahabad, Allahabad-
211002, India.
E-mail: ldsyadav@hotmail.com; Fax: +915322460533; Tel: +91 5322500652
†Electronic supplementary information (ESI) available: Experimental details,
characterization data and copies of 1H and 13C spectra for the products. See DOI:
10.1039/b000000x
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ago, Wu, Beller and co-workers have reported the same method
(Scheme 1c)24 for the synthesis of coumarins from
salicylaldehydes and benzyl chlorides as the method reported
herein (Scheme 1d) but their method utilizes CO gas, which is
highly toxic and requires special care in handling.
Table
1
Optimization
of
reaction
conditionsa
In view of the above facts and our focus on the methodology
development employing metal catalysis,25 we have devised a
convenient Pd-catalysed synthesis of 3-arylcoumarins from
salicylaldehydes and benzyl chlorides utilizing N-formylsaccharin
as a solid alternative to the highly hazardous CO gas (Scheme 1d).
Entry Catalyst
(mol%)
Lingand
(mol%)
Solvents base
(mL)
Temp. Time Yield
(mmol) ( oC)
(h)
15
10
10
10
24
15
15
15
10
10
15
15
15
15
15
10
18
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
(%)b
n.d.
61
1
Pd(OAc)2 Xantphos
Pd(OAc)2 Xantphos
Pd(OAc)2 Xantphos
Pd(OAc)2 Xantphos
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMF
Na2CO3 rt
Na2CO3 70
Na2CO3 85
Na2CO3 100
2
3
87
4
87
5
œ
œ
œ
85
n.d.
59
6
Pd(acac)2 Xantphos
Pd(TFA)2 Xantphos
Na2CO3 85
Na2CO3 85
Na2CO3 85
Na2CO3 85
Na2CO3 85
Na2CO3 85
Na2CO3 85
Na2CO3 85
Na2CO3 85
Na2CO3 85
Na2CO3 85
Na2CO3 85
Na2CO3 85
Na2CO3 85
7
45
8
PdCl2
Xantphos
54
9
Pd(OAc)2 Xantphos
Pd(OAc)2 Xantphos
Pd(OAc)2 PPh3
56c
87d
51
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
Pd(OAc)2 DPPM
60
Scheme 1 Pd-catalysed carbonylative synthesis of 3-arylcoumarins.
Pd(OAc)2 DPEphos
Pd(OAc)2 DPPE
75
40
Pd(OAc)2 DPPP
59
Results and discussion
Pd(OAc)2 Xantphos
Pd(OAc)2 Xantphos
Pd(OAc)2 Xantphos
Pd(OAc)2 Xantphos
Pd(OAc)2 Xantphos
Pd(OAc)2 Xantphos
Pd(OAc)2 Xantphos
Pd(OAc)2 Xantphos
Pd(OAc)2 Xantphos
Pd(OAc)2 Xantphos
Pd(OAc)2 Xantphos
Pd(OAc)2 Xantphos
Pd(OAc)2 Xantphos
Pd(OAc)2 Xantphos
Pd(OAc)2 Xantphos
Pd(OAc)2 Xantphos
Pd(OAc)2 Xantphos
Pd(OAc)2 Xantphos
Pd(OAc)2 Xantphos
Pd(OAc)2 Xantphos
Pd(OAc)2 Xantphos
60e
87f
76
To realize our designed synthesis and optimize the reaction
conditions a series of control experiments were performed with
salicylaldehyde 1a and benzyl chloride 2a using N-
formylsaccharin 4 as a CO surrogate and the results are
summarized in Table 1. Initially, when the reaction was conducted
at rt for 15 h, the desired product 3a was not obtained (Table 1,
entry 1). On conducting the reaction at 70 oC, the desired product
3a was obtained in 61% yield (Table 1, entry 2). Thus, we
optimized the temperatures and 85 oC was found to be the
optimum temperature to give the maximum yield (Table 1, entries
3 and 4). Then, we optimized various Pd catalysts such as
Pd(OAc)2, Pd(acac)2, Pd(TFA)2 and PdCl2, and Pd(OAc)2 was
found to be the best in terms of time and yield (Table 1, entry 3 vs
6-8). The optimum amount of the catalyst Pd(OAc)2 was found to
be 3 mol% because the yield was decreased on decreasing its
amount, but was unaffected on increasing the amount to 4 mol%
(Table 1, entry 3 vs 9 and 10). Next, we tested several ligands such
as xantphos, PPh3, DPPM, DPEphos, DPPE and DPPP, and
xantphos was found to be the best in terms of time and yield (Table
1, entry 3 vs 11-15). A decrease in the loading of xantphos ligand
from 5 mol% to 3 mol% resulted in lower yield of the product
(Table 1, entry 3 vs 16), and on increasing the amount of xantphos
ligand from 5 mol% to 7 mol%, the yield of the product remained
unchanged (Table 1, entry 1 vs 17).
THF
75
Toluene Na2CO3 85
CH3CN Na2CO3 85
60
52
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
K2CO3 85
Cs2CO3 85
81
77
NEt3
85
64
DABCO 85
Na2CO3 85
Na2CO3 85
Na2CO3 85
Na2CO3 85
Na2CO3 85
Na2CO3 85
Na2CO3 85
Na2CO3 85
Na2CO3 85
Na2CO3 85
Na2CO3 85
58
24g
35h
21i
42j
31k
33l
n.d.m
53n
67o
56p
48q
After these observations, we screened several solvents and found
that DMF was the best among DMSO, DMF, THF, toluene and
CH3CN (Table 1, entry 3 vs 18-21). Then, bases Na2CO3, K2CO3,
Cs2CO3, Et3N and DABCO were optimized and Na2CO3 was found to
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a
Reaction conditions: salicylaldehyde (1a, 1 mmol), benzyl chloride (2a, addition with benzyl chloride
2
to generate aromatic
1 mmol), N-formylsaccharin 4 as a CO surrogate (2.5 mmol), ligand (5 mol%), organopalladium species 5.24 N-formylsaccharin is decomposed to
Pd-catalyst (3 mol%), base (3 mmol), solvent (3 mL), N2 atmosphere, at rt- CO with Na2CO3, which reacts with aromatic organopalladium
100 oC for 10-24 h. b Isolated yield of 3a; n.d.= not detected.c 2 mol% of species 5 to form acylpalladium complex 6. The nucleophilic
Pd(OAc).d 4 mol% of Pd(OAc)2. e 3 mol% of xantphos.f 7 mol% of xantphos.g reaction of salicylaldehyde 1 with acylpalladium complex 6
2.5 mmol of formic acid was used instead of 4. h 2.5 mmol of phenyl formate
was used instead of 4. i 2.5 mmol of DMF was used instead of 4. j 2.5 mmol of Table 2 Substrate scope for the synthesis of 3-arylcoumarins from
benzene-1,3,5-triyl triformate (TFBen) was used instead of 4. k 2.5 mmol of
salicylaldehydes and benzyl chloridesa
hexaketocyclohexane octahydrate (C6O6.H2O) was used instead of 4. l 2.5
mmol of Mo(CO)6 was used instead of 4. m In the absence of 4. n Benzyl iodide
o
p
was used instead of 2a. Benzyl bromide was used instead of 2a. Benzyl
tosylate was used instead of 2a. q Benzyl carbonate was used instead of 2a.
work most efficiently in terms of yield (Table 1, entry 3 vs 22-25).
The feasibility of this reaction was also tested using other CO
surrogates such as formic acid, phenyl formate, DMF, TFBen,
C6O6.H2O and Mo(CO)6 but none of these was found as effective
as N-formylsaccharin (Table 1, entry 3 vs 26-31). A controlled
experiment showed that the product 3a was not formed in the
absence of N-formylsaccharin as the CO surrogate (Table 1, entry
32). The release of CO from N-formylaccharin under the present
reaction conditions could also be easily detected with a chemical
spot detector containing PdCl2, which goes black on exposure to
CO. It was found that the best yield (87%) of 3a was obtained
with 2.5 equiv of the N-formylsaccharin as the CO surrogate
(Table 1, entry 3). When other benzyl sources such as benzyl
iodide, benzyl bromide, benzyl tosylate and benzyl carbonate were
used in the place of benzyl chloride, the yield of 3a was
considerably decreased (Table 1, entry 3 vs 33-36). Thus, the
synthesis of coumarin 3a was conducted employing the optimized
reaction conditions with 1a (1 mmol), 2a (1 mmol), Pd(OAc)2 (3
mol%), xantphos (5 mol%), N-formylsaccharin (2.5 mmol) and
o
Na2CO3 (3 mmol) in DMSO (3 mL) at 85 C under stirring to
afford 87% yield of the desired product (Table1, entry 3).
Encouraged by the above studies, we explored the generality
and scope of the reaction by using diverse salicylaldehydes 1 and
a variety of benzyl chlorides 2 under the optimized conditions and
results are summarized in Table 2. The results show that both
electron-withdrawing and -donating groups could be tolerated in
salicylaldehydes 1 as well as benzyl chlorides 2 as they reacted to
give good to excellent yields of the desired products 3. A variety
of functional groups such as Me, OMe, tertiary butyl, Br, Cl, and
F
are compatible with the present protocol. However,
salicylaldehydes 1 or benzyl chlorides 2 with an electron-donating
group afforded slightly higher yields (Table 2, entries 3b, 3c, 3d,
3f, 3g, 3k, 3l and 3p) as compared to those bearing an electron-
withdrawing group (Table 2, entries 3e, 3h, 3i and 3j). The present
carbonylative annulation method also works well with 2-hydroxy-
1-naphthaldehyde, 3,5-di-tertiary butyl salicylaldehyde, and 1-
chloromethylnaphthalene (Table 2, entries 3mœo). Moreover, the
reaction
is
also
satisfactorily
applicable
to
chloromethylheteroarenes (Table 2, entries 3q and 3r). The
exclusive formation of products 3a-r (Table 2) demonstrates the
high regioseletivity of the present carbonylative annulation
reactions.
a Reaction conditions: salicylaldehyde 1a (1 mmol), benzyl chloride
2 (1
mmol), N-formylsaccharin as a CO surrogate (2.5 mmol), xantphos (5
mol%), Pd(OAc)2 (3 mol%), Na2CO3 (3 mmol), DMSO (3 mL), N2
o
atmosphere, at 85 C for 10-11 h. (See the ESI for a general procedure
and characterization of the products 3
). b All compounds are known and
On the basis of the above observations and the literature were characterized by comparison of their spectral data with those
reported in the literature.23,24,26 Yields of the pure isolated products
reported.
3 are
precedents,1b,h,j,8,21m,24 we propose a plausible mechanism for the
formation of 3-arylcoumarins 3 as depicted in Scheme 2.
According to the previously reported mechanism, palladium
acetate is reduced to Pd0 catalyst, which undergoes oxidative
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Eur. J. Org. Chem., 2013, 1228; (j) T. Ueda, H. Konishi, and K.
Manabe, Org. Lett., 2013, 15, 5370; (k) F, M. Miloserdov, V. V.
Grushin, Angew. Chem. Int. Ed. 2012, 51, 3668; (l) X. F. Wu, J.
Schranck, H. Neumann, and M. Beller, ChemCatChem, 2012, 4,
69; (m) X. F. Wu, H. Neumann, and M. Beller, Adv. Synth. Catal.,
2011, 353, 788; (n) X. F. Wu, H. Neumann, and M. Beller, Org.
Biomol. Chem., 2011, 9, 8003; (o) Q. Liu, H. Zhang, and A. Lei,
Angew. Chem. Int. Ed., 2011, 50, 10788; (p) X. F. Wu, H.
Neumann, and M. Beller, Chem. Soc. Rev., 2011, 40, 4986; (q) X.
F. Wu, H. Neumann, and M. Beller, Tetrahedron Lett., 2010, 51,
6146; (r) A. Brennführer, H. Neumann, and M. Beller, Angew.
Chem. Int. Ed., 2009, 48, 4114.
eliminates 2-formylphenyl phenylacetate 7, which in situ
undergoes the intramolecular condensation27 to afford the desired
3-arylcoumarins 3.
2. (a) A. Schoenberg, I. Bartoletti, and R. F. Heck, J. Org. Chem.,
1974, 39, 3318; (b) A. Schoenberg, and R. F. Heck, J. Org. Chem.,
1974, 39, 3327; (c) A. Schoenberg, and R. F. Heck, J. Am. Chem.
Soc., 1974, 96, 7761.
3. (a) S. H. Christensen, E. P. K. Olsen, J. Rosenbaum, and R.
Madsen, Org. Biomol. Chem., 2015, 13, 938; (b) J. J. Verendel, M.
Nordlund, and P. G. Andersson, ChemSusChem, 2013, 6, 426; (c)
E.-A. Jo, J.-H. Lee, and C.-H. Jun, Chem. Commun., 2008, 5779.
4.
(a) L.-B. Jiang, R. Li, H.-P. Li, X.; Qi, and X.-F. Wu,
ChemCatChem, 2016, 8, 1788; (b) X. Qi, C.-L. Li, L.-B. Jiang, W.-
Q. Zhang, and X.-F. Wu, Catal. Sci. Technol., 2016, 6, 3099; (c) X.
Qi, C.-L. Li, X.-F. Wu, Chem. Eur. J., 2016, 22, 5835; (d) X. Qi,
L.-B. Jiang, H.-P. Li, and X.-F. Wu, Chem. Eur. J., 2015, 21,
17650; (e) X. Qi, L.-B. Jiang, C.-L. Li, R. Li, and X.-F. Wu, Chem.
Asian J., 2015, 10, 1870; (f) M. G. Mura, L. D. Luca, G.
Giacomelli, and A. Porcheddu, Adv. Synth. Catal., 2012, 354, 3180.
(g) J. Chen, J.-B. Feng, K. Natte, and X.-F. Wu, Chem. Eur. J.,
2015, 21, 16370; (h) J. Chen, K. Natte, and X.-F. Wu, Tetrahedron
Lett., 2015, 56, 6413; (i) S. Ding, N. Jiao, Angew. Chem. Int. Ed.,
2012, 51, 9226.
Scheme 2 A plausible mechanism for the formation of 3-arylcoumarins.
5. (a) B. Li, S. Lee, K. Shin, and S. Chang, Org. Lett., 2014, 16, 2010;
(b) Y. Wang, W. Ren, J. Li, H. Wang, and Y. Shi, Org. Lett., 2014,
16, 5960; (c) D.-S. Kim, W.-J. Park, C.-H. Lee, and C.-H. Jun, J.
Org. Chem., 2014, 79, 12191; (d) I. Profir, M. Beller, and I.
Fleischer, Org. Biomol. Chem., 2014, 12, 6972; (e) I. Fleischer, R.
Jennerjahn, D. Cozzula, R. Jackstell, R. Franke, and M. Beller,
ChemSusChem, 2013, 6, 417; (f) H. Konishi, T. Ueda, T. Muto, and
K. Manabe, Org. Lett., 2012, 14, 4722; (g) L.-B. Jiang, X. Qi, and
X.-F. Wu, Tetrahedron Lett., 2016, 57, 3368.
6. (a) Q. Liu, K. Yuan, P.-B. Arockiam, R. Franke, H. Doucet, R.
Jackstell, and M. Beller, Angew. Chem., Int. Ed., 2015, 54, 4493;
(b) W. Li, and X.-F. Wu, Adv. Synth. Catal., 2015, 357, 3393; (c)
W. Li, and X.-F. Wu, J. Org. Chem., 2014, 79, 10410; (d) A.
Kopfer, B. Sam, B. Breit, and M. Krische, J. Chem. Sci., 2013, 4,
1876; (e) M. Uhlemann, S. Doerfelt, and A. Börner, Tetrahedron
Lett., 2013, 54, 2209; (f) E. Cini, E. Airiau, N. Girard, A. Mann, J.
Salvadori, and M. Taddei, Synlett, 2011, 199; (g) G. Makado, T.
Morimoto, Y. Sugimoto, K. Tsutsumi, N. Kagawa, and K.
Kakiuchi, Adv. Synth. Catal., 2010, 352, 299; (h) R. B. Wyrwas,
and C. C. Jarrold, J. Am. Chem. Soc., 2006, 128, 13688; (i) L. R.
Odell, F. Russo, and M. Larhed, Synlett, 2012, 685.
Conclusions
In conclusion, we have developed a novel and highly efficient
one-pot
Pd-catalysed
carbonylative
cyclisation
of
salicylaldehydes with benzyl chlorides to afford 3-arylcoumarins
using N-formylsaccharin as a CO surrogate. The protocol offers a
superior alternative to access 3-arylcoumarins, mainly because it
utilizes a solid, readily available, and easy to handle N-
formylsaccharin as the CO source in the present carbonylative
annulation reaction.
Conflicts of interest
There are no conflicts of interest to declare.
Acknowledgement
7. (a) L. Wu, Q. Liu, I. Fleischer, R. Jackstell, and M. Beller, Nat.
Commun., 2014, 5, 3091; (b) Q. Liu, L. Wu, I. Fleischer, D. Selent,
R. Franke, R. Jackstell, and M. Beller, Chem.œEur. J. 2014, 20,
6809; (c) T. G. Ostapowicz, M. Schmitz, M. Krystof, J.
Klankermayer, and W. Leitner, Angew. Chem., Int. Ed., 2013, 52,
12119; (d) K. Tsuchiya, J.-D. Huang, and K.-i. Tominaga, ACS
Catal., 2013, 3, 2865.
We sincerely thank SAIF, Punjab University, Chandigarh, for
providing spectra. V.K.Y. is grateful to the CSIR, New Delhi, for
the award of a Junior Research Fellowship (Ref. No: 22/06/2014
(i) EU-V).
8. V. K. Yadav, V. P. Srivastava, and L. D. S. Yadav, Synlett, 2016,
27, 2826.
9. (a) F. Borges, F. Roleira, N. Milhazes, L. Santana and E. Uriarte,
Curr. Med. Chem., 2005, 12, 887; (b) L. Santana, E. Uriarte, F.
Roleira, N. Milhazes and F. Borges, Curr. Med .Chem., 2004, 11,
3239; (c) R. W. Van De Water and T. R. R. Pettus, Tetrahedron,
2002, 58, 5367; (d) T. Rosenau, A. Potthast, T. Elder and P. Kosma,
Org. Lett., 2002, 4, 4285; (e) S. R. Angle, J. D. Rainier and C.
Woytowicz, J. Org. Chem., 1997, 62, 5884; (f) Coumarins:
Biology, Applications and Mode of Action; R. O‘Kennedy, R. D.
Thornes, Eds.; John Wiley & Sons: Chichester, 1997; (g) P. Wan,
B. Barker, L. Diao, M. Fischer, Y. Shi and C. Yang, Can. J. Chem.,
1996, 74, 465; (h) G. J. Zlabinger, C. Nohammer, G. A. Bohmig
and J. E. Menzel, J. Cancer Res. Clin. Oncol., 1994, 120, S17; (i)
Notes and references
1. (a) C. F. J. Barnard, Organometallics, 2008, 27, 5402; (b) P. H.
Gehrtz, V. Hirschbeck, I. Fleischer, Chem. Commun., 2015, 51,
12574; (c) L. Wu, Q. Liu, R. Jackstell, and M. Beller, Angew.
Chem. Int. Ed., 2014, 53, 6310; (d) S. T. Gadge, B. M. Bhanage,
RSC Adv., 2014, 4, 10367; (e) F, M. Miloserdov, C. L. McMullin,
M. M. Belmonte, J. B. Buchholz, V. I. Bakhmutov, S. A.
Macgregor, and V. V. Grushin, Organometallics, 2014, 33, 736; (f)
X. F. Wu, H. Neumann, and M. Beller, Chem. Rev., 2013, 113, 1;
(g) X. F. Wu, H. Neumann, and M. Beller, ChemSusChem, 2013,
6, 229; (h) T. Ueda, H. Konishi, K. and Manabe, Angew. Chem. Int.
Ed., 2013, 52, 8611; (i) K. Dahl, M. Schou, N. Amini, C. Halldin,
Çhis journal is © Çhe woyal {ociety of /hemistry 20xx
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Wournal bame
!wÇL/[9
Y. Y. Stoilov and S. P. Bazhulin, Kvantovaya Elektronika, 1986,
Zhang, and S. J. Takahashi, Chem. Soc. Perkin Trans. 1, 1998, 477;
(h) B. M. Trost, and F. D. Toste, J. Am. Chem. Soc., 1996, 108,
6305; (i) M. Catellani, G. P. Chuisoli, M. C. Fagnola, and G. Solari,
Tetrahedron Lett., 1994, 35, 5919; (j) M. Catellani, G. P. Chiusoli,
M. C. Fagnola, and G. Solari, Tetrahedron Lett., 1994, 35, 5923;
(k) Z. An, M. Catellani, and G. P. Chiusoli, Gazz. Chim. Ital,. 1990,
120, 383.
13, 633; (j) P. W. Lequesne, J. Am. Chem. Soc., 1983, 105, 6536;
(k) P. Zboril, J. Holasova and V. Dadak, Collect. Czech. Chem. C.,
1970, 35, 2983; (l) A. S. Douglas, Brit. Med. Bull., 1955, 11, 39.
10. S. J. Lee, U. S. Lee, W. J. Kim, S. K. Moon, Mol. Med. Rap. 2011,
4, 337; (b) K. V. Sashidhara, A. Kumar, M. Chattarjee, K. B. Rao,
S. Singh, A. K. Varma and G. Palit, Bioorg. Med. Chem. Lett.,
2011, 21, 1937; (c) J. F. Vasconcelos, M .M. Teixeira, J. M.
Baebosa-Filho, M. F. Adra, X. P. Nunes, A. M. Giulietti, R.
Ribeiro-dos-Santosh and M. B. P. Soares, Eur. J. Phar, acol., 2007,
609, 126; (d) C. Kontogiorgis, D. J. Hadjipavlou-Litina, Enzyme
Inhib. Med. Chem., 2003, 18, 63; (e) I. Kempen, D. Papapostolou,
N. Thierry, L. Pochet, S. Counerotte, B. Masereel, J. M. Foidart,
M. J. Reboud-Ravaux, A. Noel, and B. Pirotte, Br. J. Cancer 2003,
88, 1111; (f) R. A. O‘Reilly, P. M. Aggeler, and L. S. Leong, J.
Clin. Invest. 1963, 42, 1542.
11. (a) A. R. Jagtap, V. S. Satam, R. N. Rajule, and V. R. Kanetkar,
Dyes Pigm., 2009, 82, 84; (b) R. S. Koefod, and K. R. Mann, Inorg.
Chem., 1989, 28, 2285; (c) G. Jones, W. R. Jackson, C. Choi, and
W. R. Bergmark, J. Phys. Chem., 1985, 89, 294.
12. (a) C. H. Chang, H. C. Cheng, Y. J. Lu, K. C. Tien, H. W. Lin, C.
L. Lin, C. J. Yang, and C. C. Wu, Org. Electron., 2010, 11, 247;
(b) T. Z. Yu, P. Zhang, Y. L. Zhao, H. Zhang, J. Meng, and D. W.
Fan, Org. Lett., 2009, 10, 653; (c) M. T. Lee, C. K. Yen, W. P.
Yang, H. H. Chen, C. H. Liao, C. H. Tsai, and C. H. Chen, Org.
Lett., 2004, 6, 1241; (d) S. A. Swanson, G. M. Wallraff, J. P. Chen,
W. J. Zhang, L. D. Bozano, K. R. Carter, J. R. Salem, R. Villa, and
J. C. Scott, Chem. Mat., 2003, 15, 2305.
19. X.-F. Wu, H. Neumann, and M. Beller, Chem. Rev., 2013, 113, 1.
20. (a) B. Willy, and T. J. J. Müller, Curr. Org. Chem., 2009, 13, 1777;
(b) E. Merkul, T. Oeser, and T. J. J. Müller, Chem. Eur. J., 2009,
15, 5006; (c) B. Willy, and T. J. J. Müller, Synthesis, 2008, 293; (d)
B. Willy, and T. J. J. Müller, Eur. J. Org. Chem. 2008, 4157; (e) D.
M. D‘Souza, and T. J. J. Müller, Chem. Soc. Rev. 2007, 36, 1095;
(f) E. Merkul, and T. J. J. Müller, Chem. Commun., 2006, 4817; (g)
L. F. Tietze, G. Brasche, and K. Gericke, Domino Reactions in
Organic Synthesis, Wiley-VCH, Weinheim, 2006; (h) A. V.
Rotaru, I. D. Druta, T. Oeser, and T. J. J. Müller, Helv. Chim. Acta,
2005, 88, 1798; (i) A. S. Karpov, E. Merkul, T. Oeser, and T. J. J.
Müller, Chem. Commun., 2005, 2581; (j) A. S. Karpov, T. Oeser,
T. J. J. Müller, Chem. Commun., 2004, 1502; (k) L. F. Tietze,
Chem. Rev., 1996, 96, 115.
21. (a) X. F. Wu, M. Zhang, H. Jiao, H. Neumann, and M. Beller, Asian
J. Org. Chem., 2013, 2, 135; (b) X. F. Wu, M. Sharif, K. Shoaib,
H. Neumann, A. Pews-Davtyan, P. Langer, and M. Beller, Chem.
Eur. J. 2013, 19, 6230; (c) J. Ferguson, F. Zeng, and H. Alper, Org.
Lett., 2012, 14, 5602; (d) X. F. Wu, H. Jiao, H. Neumann, and M.
Beller, Chem. Eur. J., 2012, 18, 16177; (e) X. F. Wu, H. Neumann,
S. Neumann, and M. Beller, Chem. Eur. J., 2012, 18, 13619; (f) X.
F. Wu, H. Neumann, and M. Beller, Chem. Eur. J., 2012, 18,
12595; (g) X. F. Wu, H. Neumann, S. Neumann, and M. Beller,
Chem. Eur. J., 2012, 18, 8596; (h) J. Schranck, X. F. Wu, H.
Neumann, and M. Beller, Chem. Eur. J., 2012, 18, 4827; (i) X. F.
Wu, J. Schranck, H. Neumann, and M. Beller, Chem. Eur. J., 2011,
17, 12246; (j) X. F. Wu, H. Neumann, M. Beller, Eur. J. Org.
Chem., 2011, 4919; (k) X. F. Wu, B. Sundararaju, P. Anbarasan, H.
Neumann, and P. H. Dixneuf, M. Beller, Chem. Eur. J., 2011, 17,
8014; (l) D. V. Kadnikov, and R. C. Larock, J. Organomet. Chem.,
2003, 687, 425; (m) D. V. Kadnikov, and R. C. Larock, J. Org.
Chem. 2003, 68, 9423; (n) D. V. Kadnikov, and R. C. Larock, Org.
Lett., 2000, 2, 3643.
13. (a) S. S. Keskin, N. Aslan, and N. Bayrakceken,
Spectrochim. Acta, Part A 2009, 72, 254; (b) A. Dorlars, C.
W. Schellhammer, and J. Schroeder, Angew. Chem., Int.
Ed., 1975, 14, 665.
14. (a) A. Kakehi, S. Ito, H. Suga, and K. Yasuraoka, Heterocycles,
2001, 54, 185; (b) D. Bogdal, J. Chem. Res. Synop., 1998, 468; (c)
A. Bojilova, R. Nikolova, C. Ivanov, N. A. Rodios, A. Terzis, and
C. P. Raptopoulou, Tetrahedron, 1996, 52, 12597; (b) R. S. Mali,
and S. G. Tilve, Synth. Commun., 1990, 20, 1781.
15. R. S. Mali, and P. P. Joshi, Synth. Commun., 2001, 31, 2753.
16. (a) L. Santana, H. González-Díaz, E. Quezada, E. Uriarte, M.
Yáñez, D. Viña, and F. Orallo, J. Med. Chem., 2008, 51, 6740; (b)
S. Vilar, E. Quezada, L. Santana, E. Uriarte, M. Yanez, N. Fraiz, C.
Alcaide, E. Cano, and F. Orallo, Bioorg. Med. Chem. Lett., 2006,
16, 257; (c) L. M. Wang, J. J. Xia, H. Tian, C. T. Qian, and Y. Ma,
Indian J. Chem., Sect. B., 2003, 42, 2097; (d) M. C. Laufer, H.
Hausmann, and W. Holderich, J. Catal., 2003, 218, 315; (e) D. S.
Bose, A. P. Rudradas, and M. H. Babu, Tetrahedron Lett., 2002,
43, 9195; (f) N. Hans, M. Singhi, V. Sharma, and S. K. Grover,
Indian J. Chem., Sect B: Org. Chem. Incl. Med. Chem., 1996, 11,
1159; (g) Y. Ming, and D. W. Boykin, Heterocycles I, 1987, 26,
3229; (h) S. Sethna, and R. Phadke, Org. React., 1953, 7, 1.
17. (a) M. J. Matos, D. Viña, E. Quezada, C. Picciau, G. Delogu, F.
Orallo, L. Santana, and E. Uriarte, Bioorg. Med. Chem. Lett., 2009,
19, 3268; (b) M. J. Matos, D. Viña, C. Picciau, F. Orallo, L.
Santana, and E. Uriarte, Bioorg. Med. Chem. Lett., 2009, 19, 5053;
(c) L. M. Kabeya, A. A. de Marchi, A. Kanashiro, N. P. Lopes, da
C. H. da Silva, Bioorg. Med. Chem., 2007, 15, 1516; (d) S.
Mashraqui, D. Vashi, and H. D. Mistry, Synth. Commun., 2004, 34,
3129; (e) C. Khiri, F. Ladhar, El R. Gharbi, and Y. Le Bigot, Synth.
Commun., 1999, 29, 1451; (f) K. K. Vijayan, Indian J. Heterocycl.
Chem., 1998, 8, 1; (g) J. A. Mahling, and R. R. Schmidt, Liebigs.
Ann. 1995, 467; (h) M. E. Langmuir, J. R. Yang, A. M. Moussa, R.
Laura, and K. A. Lecompte, Tetrahedron Lett. 1995, 36, 3989; (i)
S. Mohanty, J. K. Makrandi, and S. K Grove, Indian J. Chem., Sect
B: Org. Chem. Incl. Med. Chem., 1989, 28, 766; (j) Johnson, J. R.
Org. React., 1942, 1, 210.
22. Y. Jiang, W. Chen, and W. Lu, RSC Adv., 2012, 2, 1540.
23. Y. Jiang, W. Chen, and W. Lu, Tetrahedron, 2013, 69, 3669.
24. X.-F. Wu, L. Wu, R. Jackstell, H. Neumann, and M. Beller, Chem.
Eur. J., 2013, 19, 12245.
25. (a) V. K. Yadav, V. P. Srivastava, and L. D. S. Yadav, Synlett,
2016, 27, 427; (b) T. Keshari, R. Kapoor, and L. D. S. Yadav, Eur.
J. Org. Chem., 2016, 2695; (c) A. K. Yadav, and L. D. S. Yadav,
Tetrahedron Lett., 2016, 56, 686; (d) A. K. Yadav, and L. D. S.
Yadav, Synlett, 2015, 26, 1026; (e) A. K. Yadav, and L. D. S.
Yadav, Org. Biomol. Chem., 2015, 13, 2606; (f) A. K. Yadav, V. P.
Srivastava, and L. D. S. Yadav, RSC Adv., 2014, 4, 24498; (g) A.
K. Yadav, V. P. Srivastava, and L. D. S. Yadav, Tetrahedron Lett.,
2014, 55, 1788; (h) V. P. Srivastava, L. D. S. Yadav, Synlett, 2013,
24, 2758.
26. (a) J. Liu, X. Zhang, L. Shi, M. Liu, Y. Yue, F. Li and K. Zhuo
Chem. Commun., 2014, 50, 9887; (b) T. Yu, S. Yang, J. Meng, Y.
Zhao, H. Zhang, D. Fan, X. Han, Z. Liu, Inorg. Chem. Commun.
2011, 14, 159; (c) J. Meng, M. Shen, D. Fu, Z. Gao, R. Wang, H.
Wang, and T. Matsuura, Synthesis, 1990, 719.
27. (a) K. Taksande, D. S. Borse, and P. Lokhande, Synth. Commun.,
2010, 40, 2284; (b) G. Sabitha, and A. V. S. Rao, Synth. Commun.,
1987, 17, 341; (c) P. P. Rao, and G. Srimannarayana, Synthesis,
1981, 887.
18. (a) N. Van T, S. Debenedetti, and N. De Kimpe, Tetrahedron Lett.,
2003, 44, 4199; (b) T. Kitamura, K. Yamamoto, M. Kotani, J.
Oyamada, C. Jia, and Y. Fujiwara, Bull. Chem. Soc. Jpn., 2003, 76,
1889; (c) D. V. Kadnikov, and R. C. Larock, J. Org. Chem., 2003,
68, 9432; (d) C. Jia, D. Piao, J. Oyamada, W. Lu, T. Kitamura, and
Y. Fujiwara, Science, 2000, 287, 1992; (e) C. Jia, D. Piao, T.
Kitamura, and Y. Fujiwara, J. Org. Chem,. 2000, 65, 7516; (f) D.
K. Rayabarapu, T. Sambaiah, and C.-H. Cheng, Angew. Chem. Int.
Ed., 2001, 40, 1286; (g) E. Yoneda, T. Sugioka, K. Hirao, S.-W.
Çhis journal is © Çhe woyal {ociety of /hemistry 20xx
W. bame., 2013, 00, 1-3 | 5
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Graphical Abstract
Pd-catalysed carbonylative annulation of salicylaldehydes with benzyl
chlorides using N-formylsaccharin as a CO surrogate
Vinod K. Yadav, Vishnu P. Srivastava and Lal Dhar S. Yadav
A highly efficient synthesis of 3-arylcoumarins by Pd-catalysed carbonylative cyclisation of
salicylaldehydes with benzyl chlorides using N-formylsaccharin as a CO source is developed.