Hydrotalcite-supported palladium nanoparticles as catalysts for the hydroarylation of carbon-carbon multiple bonds

Article abstract of DOI:10.1039/c7nj04046f

Palladium nanoparticles supported on Mg/Ca hydrotalcites catalyze the hydroarylation reaction of different alkynes and alkenes with aryl iodides under air in MeCN. The reaction of tertiary propargylic alcohols (1) with aryl iodides (2) yields, stereoselectively, γ,γ-diarylallylic alcohols (3) in moderate to high yields and high selectivity. Also, the HT/Pd hydroarylation reaction with aryl iodides was attempted on norbornene and α,β-unsaturated ketones affording, respectively, exo-aryl bicyclo[2.2.1]heptanes and β-aryl ketones in moderate to high yields. All the reactions described benefit from using a heterogeneous catalyst with evident advantages in terms of reaction purification and recyclability of the catalyst.

Full text of DOI:10.1039/c7nj04046f

View Article Online
View Journal
NJC
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: L. Rossi, A. Arcadi,
A. Di Nicola, K. Gallucci and V. Mucciante, New J. Chem., 2017, DOI: 10.1039/C7NJ04046F.
This is an Accepted Manuscript, which has been through the
Volume 40 Number
1 January 2016 Pages 1–846
Royal Society of Chemistry peer review process and has been
accepted for publication.
NJC
Accepted Manuscripts are published online shortly after
New Journal of Chemistry
www.rsc.org/njc
A journal for new directions in chemistry
acceptance, 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
author guidelines.
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, outlined
in our author and reviewer resource centre, still apply. In no
event shall the Royal Society of Chemistry be held responsible
for any errors or omissions in this Accepted Manuscript or any
consequences arising from the use of any information it contains.
ISSN 1144-0546
PAPER
Jason B. Benedict et al.
The role of atropisomers on the photo-reactivity and fatigue of
diarylethene-based metal–organic frameworks
rsc.li/njc

Please do not adjust margins
New Journal of Chemistry
Page 1 of 7
View Article Online
DOI: 10.1039/C7NJ04046F
Journal Name
ARTICLE
Hydrotalcite-Supported Palladium Nanoparticles as Catalyst for
the Hydroarylation of Carbon-Carbon Multiple Bond
A. Di Nicola,a A. Arcadia*, K. Gallucci,b V. Mucciantea and L. Rossia*
Received 00th January 20xx,
Accepted 00th January 20xx
Palladium nanoparticles supported on Mg/Ca hydrotalcites catalyze the hydroarylation reaction of different alkynes and
alkenes with aryl iodides under air in MeCN. The reaction of tertiary propargylic alcohols (1) with aryl iodides (2) yields,
stereoselectively, γ,γ-diarylallylic alcohols (3) in moderate to high yields and high selectivity. Also, the HT/Pd
hydroarylation reaction with aryl iodides was attempted on norbornene and α,β-unsaturated ketones affording,
respectively, exo-aryl bicyclo[2.2.1]heptanes and β-aryl ketones in moderate to high yields. All the reactions described
benefit from using an heterogeneous catalyst with evident advantages in term or reaction purification and recyclability of
DOI: 10.1039/x0xx00000x
www.rsc.org/
the
catalyst.
developed for the Suzuki-Miyaura-,17,18a Heck-,17f,18
Sonogashira-, and Stille-type17f coupling reactions of aryl
halides. Hydrotalcite-supported Pd-Au nanocatalysts were also
found to be efficient heterogeneous catalysts for Ulmann
homocoupling reactions of aryl bromides or chlorides at low-
temperature.19 Moreover, Pd nanoparticles on hydrotalcite
have been explored for selective reduction of carbon-carbon
Introduction
In recent years, great focus has been devoted by academic
and industrial research groups to the development of
sustainable chemistry.1 Because of their great importance,
carbon-carbon cross-coupling reactions are among the most
widely studied synthetic transformations. In particular,
transition-metal catalyzed couplings have become a reliable
and indispensable tool for the synthesis of fine chemicals and
pharmaceuticals.2 Homogeneous catalysts based on simple or
sophisticated palladium-complexes resulted the catalysts of
choice in many applications.3 However, most of the highly
active catalytic systems use homogeneous palladium species
with air-sensitive, expensive and environmentally unfriendly
phosphine ligands. Consequently, alternative catalysts4 are
emerging as a more sustainable alternative to conventional
homogenous catalysts by taking advantage of their interesting
properties, such as high surface area and high catalytic
activity.5 Also, immobilization of catalytically active palladium
species on heterogeneous supports has drawn significant
interest.6 Different materials such as silica,7 alumina,8
graphene,9 modified graphene,10 graphene oxide,11 reduced
graphene oxide,12 carbon/other-carbon-based materials13
zeolites,14 metal-organic frameworks,15 and other were used
as effective supports. Applications of palladium nanocatalysis
are growing in importance in organic synthesis.16 In this field
hydrotalcite-supported palladium catalysts have been
multiple bonds.20 Strategies
for the controllable
characterization and functionalities of Pd/hydrotalcite
catalysts have been reported.21 Since the initial disclosure by
Cacchi
and
co-workers,22
the
palladium-catalyzed
hydroarylation of carbon-carbon multiple bonds with aryl
halides has been well-exploited23 and widely used in natural
products synthesis.24 Hydrotalcite docked Rh-phosphines
complexes showed good catalytic activity in the hydroarylation
of alkynes25 and 2-cyclohexen-1-one26 with aryl boronic acids.
However, to the best of our knowledge, there is no report
available on the hydrotalcite-supported phosphine-free
palladium nanoparticles as catalysts for the hydroarylation of
carbon-carbon multiple bond with aryl halides. Considering
that boronic acids usually were produced from aryl halides,
their replacement with these latter derivative is attractive for
industrial synthetic transformations. Moreover, it is highly
desirable the application of palladium nanocatalysts as a
valuable alternative to the use of the more conventional air-
sensitive homogeneous palladium complexes in the
hydroarylative process.
In this article, we report that the readily available HT-PdCl2 and
HT-Pd are very effective catalysts for the hydroarylation of
alkynes/alkenes with aryl iodides under air. The catalytic
process is not completely heterogeneous; rather, the reaction
involves substantial homogeneous catalysis.
Results and discussion
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 1
Please do not adjust margins

Please do not adjust margins
New Journal of Chemistry
Page 2 of 7
View Article Online
DOI: 10.1039/C7NJ04046F
ARTICLE
Journal Name
Our study started by choosing the reaction of 1- a model system to explore the suitability of phosphine-free
(phenylethynyl)cyclohexan-1-ol 1a with 4-iodoanisole 2a in the palladium nanocatalysts for the hydroarylation of unsaturated
presence of hydrotalcite-supported palladium nanoparticles as organic
scaffolds
(Table
1).
Table 1. Optimization of the reaction conditions of HT-Pd-catalyzed hydroarylation of propargylic alcohol 1a with 4-Iodoanisole
2a
OCH3
H3CO
I
HT/[Pd]
+
OH
OH
+
HCOOH
HO
Piperidine
OCH3
1a
2a
4a
3a
Entry
1
HT-Pd
HT-Pd
Solvent
DMF
Temp/time (°C/h) Overall Yield (%) Isomeric Ratio 3a/4a
100/17
120/24
80/7
45
--
94:6
--
Mg/Al = 2/1
HT-Pd
2
3
4
5
EtOH/H2O (1/1)
CH3CN
Mg/Al = 2/1
HT-Pd
84
93
92
92:8
93:7
95:5
Mg/Al = 2/1
HT-Pd
CH3CN
80/16
80/8
Mg/Al = 3/1
HT-PdCl2
CH3CN
Mg/Al = 2/1
It was previously reported that arylethynyl, dialkyl carbinols
1
resulted CH3CN which accomplished the formation of the
in the presence of the tri- or dialkylammonium desired 3a in higher yield at a lower temperature (Table 1,
formate/Pd(OAc)2[P(Ph3)]2 can provide a convenient approach entry 3). The HT-Pd catalyst with Mg/Al ratio of 3/1 showed
to the regioselective formation of γ -diaryl allylic alcohols
,
γ
3.
slightly higher activity than that with Mg/Al of 2/1 (Table 1,
The isomeric -diaryl allilic alcohols 4 were isolated in only 5- entry 4), though the differences were not substantial. A good
β
,γ
10% yield.27 The reaction was highly stereoselective leading to performance was also observed with the HT-PdCl2 (Mg/Al =
the syn addition product.28 Steric and coordinating effects 2/1) catalyst that very likely is prone to undergo fast
played a major role in controlling the regioselectivity. In conversion in HT-Pd under the reaction conditions. Catalyst
general, other reaction parameters such as solvents, the recycling tests were conducted. After the reaction, catalyst HT-
presence or the absence as well as the features of ligands, the Pd (Mg/Al = 1/2) was isolated by filtration, washed, and dried
nature of the
Csp2-donor were found to influence the at a low pressure for reuse. No significant loss of activity was
regiochemical outcome of the hydroarylation of observed after two re-uses (Table 2).
unsymmetrical alkynes.29 Indeed the palladium-catalyzed
hydroarylation of propargylic alcohols provided better results
in room temperature ionic liquids than in molecular solvents in Table 2. HT-Pd (Mg/Al = 2/1) catalyst recycling in the
terms of regioselectivity and/or reactivity.30 Accordingly, the hydroarylation reaction of 1a with 2a
key role of the solvent also in the HT-palladium catalyzed
1st run [overall
yield (% )]
84
2nd run [overall
yield (% )]
84
3rd run [overall
yield (% )]
84
hydroarylation of 1a with 2a is highlighted in entries 1-3 of
Table 1. The reaction was carried out in the presence of 1.0
mol % of Pd, 2.4 eq. of the aryl iodide 2a, 2.64 eq. of HCOOH
and 3.4 eq. of piperidine. By contrast with the results observed
in the Pd(OAc)2P(Ph2)2 catalyzed reaction under homogeneous
conditions,27 DMF resulted a poor one in the presence of HT-
Pd nanocaltalyst. In our study of the influence of the solvent
simultaneously with that of the temperature, we failed to
obtain the hydroarylation product with hydroxylated solvent
which have been reported to be beneficial for the HT-Pd
catalyzed Suzuki-Miyaura couplings.17 The solvent of choice
To establish unambiguously whether the reaction proceeds
exclusively on the heterogeneous surface, in the homogeneous
phase or partly on the heterogeneous surface/homogeneous
phase, the reaction of 1a with 2a in CH3CN at 80 °C in the
presence of HT-Pd or HT-PdCl2 was stopped at
a low
conversion level, and while the reaction mixture was still hot,
2 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Please do not adjust margins
New Journal of Chemistry
Page 3 of 7
View Article Online
DOI: 10.1039/C7NJ04046F
Journal Name
ARTICLE
the catalyst was rapidly filtered, and the reaction was allowed C-I bond32 than the carbopalladation step leading to the
to proceed overnight. The results obtained, under these formation of the corresponding allylic alcohol.
conditions, revealed that the filtrate was catalytically active With the secondary propargylic alcohol and the less branched
and the reaction continued in the absence of the HT-palladium primary propargylic alcohol, according to the results observed
catalyst. This indicates that partial leaching of Pd from the under homogeneous conditions,
a
worsening of the
solid catalyst to the solution should involve substantial regioselectivity occurs. Furthermore, with the secondary
homogeneous catalysis. Nevertheless, HT-Pd catalyst could be propargylic alcohol 1g, in addition to the isomeric alcohol 4g, a
reused and is able to remain catalytically active in the E/Z mixture of the
hydroarylation reaction albeit subject to leaching. Very likely, significant yield. The formation of this latter derivative can be
cooling the reaction mass causes fast deposition of accounted by assuming that the -elimination of HPdI species
nanoparticles onto the hydrotalcite support, achieving the is faster than the iodide formate exchange in the intermediate
efficient recycle of the catalyst. A. The subsequent isomerization of the resultant allenyl
On the basis of the above studies, the hydroarylation reaction alcohol generates . A reversion of the regioselective outcome
α,β-unsaturated ketone 5 was isolated in
β
5
was extended to other propargylic alcohols and aryl iodides. prevailed with the less branched primary propargylic alcohol
According to previous findings28,30 and related reactions,31 1h. In this case, the phenyl group of the starting alkyne, rather
tertiary propargylic alcohols gave, as the main product, the
γ
,
γ
diarylallylic alcohols containing the new carbon-carbon bond addition of the arylpalladium iodide over the C-C triple bond
-
than the hydroxyl group, apparently directs the regioselective
3
close to the aryl substituent of the starting alkyne as (Scheme 2).
consequence of the prevailing of the directing effect of the The formation of the diarylacetylene derivatives was also
tertiary hydroxyl group (Scheme 1). The isomeric
diarylallylic alcohols were obtained only in 1-15 % yield. trimethylsilylacetylenes in the presence of an excess of sodium
Variable amounts of the starting alkyne were recovered. methoxide under refluxing methanol by using Pd(PPh3)4 as the
Hydroarylation products were obtained in similar yields with catalyst.33 As expected, the formation of the trisubstituted
those observed by carrying out the reaction in the presence of alkene occurred in good yield by reacting the
homogeneous palladium catalysts. Aryl iodides bearing strong diphenylacetylene with the 4-iodotoluene 2f under the
β
,γ
-
previously reported to occur by reacting aryl iodides with
1
7
6
withdrawing substituents are prone to undergo, under the present reaction conditions (Scheme 3).34
above mentioned reaction conditions, faster reduction of the
Z
Z
Z
HT/Pd
HCOOH
Y
+
+
Piperidine
CH3CN 100°C
OH
R1
OH
R2
OH
R1
R2
I
R2
R1
Y
Y
3
2
4
1
H3CO
H3CO2C
H3CO
H3CO
Cl
OH
OH
OH
OH
OH
OH
H3CO2C
H3CO2C
3a (7h)
3b (12h)
(65%; 3b/4b = 98/2)
3c (12h)
(65%; 3c/4c = 91/9)
3d (7h)
(20%; 3d/4d = 92/8)
3e (12h)
(92%; 3e/4e = 99/1)
3f (12h)
(80%; 3f/4f = 85/15)
(84%; 3a/4a = 92/8)
Scheme 1. HT/Pd catalyzed hydroarylation of tertiary propargylic alcohols with aryl iodides.
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
New Journal of Chemistry
Page 4 of 7
View Article Online
DOI: 10.1039/C7NJ04046F
ARTICLE
Journal Name
H3CO
HT/Pd
HCOOH
+
Piperidine
CH3CN 100°C
OH
I
HO
H3CO
2b
1g
A
+
+
O
HO
HO
H3CO
H3CO
H3CO
3g (trace)
4g (21%)
5 (40%)
H3CO
OCH3
OCH3
HT/Pd
HCOOH
+
+
Piperidine
CH3CN 100°C
6h
OH
OH
I
OH
1h
2a
3h (15%)
4h (40%)
Scheme 2. HT-Pd catalyzed hydroarylation of secondary and primary propargylic alcohols with aryl iodides.
The palladium catalyzed hydroarylation of norbornenes with
aryl halides,35 triflates,36 and arenediazonium salts37 has
X
X
HT/Pd
HCOOH
proved to be an effective method for the synthesis of
bicyclo[2.2.1]heptanes and related compounds with an aryl
substituent in the exo- position.38
+
Piperidine
CH3CN 100°C
9
8
I
9a X = H (57%)
9b X = OMe (92%)
9c X = Me (79%)
9d X = Cl (90%)
2
Ph
Ph
HT/Pd
HCOOH
Ph
Ph
+
Piperidine
CH3CN 80°C, 12 h
6
Scheme 4. HT-Pd Catalyzed Hydroarylation of Norbornenes
with Aryl Iodides
8
I
2
.
2f
7 (85%)
The significant interest towards the development of practical
approach to the conjugate addition type reaction of aryl
Scheme
3.
HT-Pd
Catalyzed
Hydroarylation
of
iodides with
exploration of the HT-Pd catalyzed version. The HT-Pd catalytic
42b
α,β
-unsaturated ketones,42 encouraged our
Diphenylacetylene 6 with 4-Iodotoluene 2f.
It has been used in the total synthesis of the potent nonopiate
analgesic alkaloid epibatedine,39 a compound isolated from the
skin of the Ecuadorian frog, Epipedobates tricolor, as well as in
different approaches to its analogues.40 Enantioselective
hydroarylations of norbornene derivatives have also been
described.41 We envisaged that the use of palladium
naoparticles as alternative catalysts would widen significantly
its synthetic scope. Indeed, the HT-Pd catalyzed hydroarylation
of norbornene with aryl iodides resulted a very effective
procedure leading stereoselectively to the targed adducts
(Scheme 4).
activity is comparable with that of Pd(OAc)2
catalysts (Scheme 5).42c
and Pd-NHC
Conclusions
In conclusions, we have developed a new methodology for the
palladium catalysed hydroarylation reaction of carbon-carbon
multiple bonds. The method implies the use of hydrotalcite-
supported palladium nanoparticles with all the evident
advantages derived by the use of a heterogeneous catalyst.
4 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Please do not adjust margins
New Journal of Chemistry
Page 5 of 7
View Article Online
DOI: 10.1039/C7NJ04046F
Journal Name
ARTICLE
2
3
A. O. King, N. Yasuda, Palladium-catalyzed Cross-Coupling
Reactions in the Synthesis of Pharmaceuticals. In
Organometallics in Process Chemistry, Larsen, R. D. Ed.;
Springer: Berlin, Germany, 2004; pp. 205.
(a) C. C. C. J. Seechurn, M. O. Kitching, T. J. Colcot, V.
Snieckus, Angew. Chem. Int. Ed. 2012, 51, 5062. (b) J.
Magano, J. R. Dunetz, Chem. Rev. 2011, 111, 2177.
V. Polshettiwar, R. S. Varma, Green Chem. 2010, 12, 743.
V. Polshettiwar, R. Luque, A. Fihri, H. Zhu, M. Bouhrara, J. M.
Basset, Chem. Rev. 2011, 111, 3036.
(a) J. C. Park, E. Heo, A. Kim, M. Kim, K. H. Park, H. Song, J.
Phys. Chem. C 2011, 115, 15772; (b) J. Zhi, D. Song, Z. Li, X.
Lei, A. Hu, Chem. Commun. 2011, 47, 10707.
(a) X. Chen, Y. Hou, H. Wang, Y. Cao, J. He, J. Phys. Chem. C
2008, 112, 8172; (b) B. Cornelio, G. A. Rance, M. Laronze-
Cochard, A. Fontana, J. Sapi, A. N. Khlobystov, J. Mater.
Chem. A 2013, 1, 8737.
X
X
O
HT/Pd
DIPEA
+
Ph
R1
NMP, 80°C
O
10
Ph
R1
I
4
5
11
2
11a R1 = Me; X = OMe (92%)
11b R1 = Me; X = Me (87%)
11c R1 = Me; X = F (90%)
11d R1 = Me; X = H (98%)
11e R1 = Ph; X = OMe (77%)
O
6
7
OCH3
11f (53%)
8
9
(a) A. M. S. Hossain, A. Balbín, R. S. Erami, S. Prashar, M.
Fajardo, S. Gómez-Ruiz, Inorg. Chim. Acta 2017, 455, 645; (b)
A. P. Kumar, B. P. Kumar, A. B. V. K. Kumar, B. T. Huy, Y. -I.
Lee, Appl. Surface Sci. 2013, 265, 500.
(a) M. Gómez-Martínez, E. Buxaderas, I. M. Pastor, D. A.
Alonso, J. Mol. Catal. A: Chem. 2015, 404–405, 1; (b) A. R.
Siamaki, A. E. R. S. Khder, V. Abdelsayed, M. S. El-Shall, B. F.
Gupton, J. Catal. 2011, 279, 1.
Scheme 5. HT-Pd Catalyzed Hydroarylation of
Ketones 10 with Aryl Iodides
α,β-Unsaturated
2.
Reaction yields and selectivity are, in general, very goods. The
methods is very versatile and the reaction can be carried out
on primary, secondary and tertiary propargyl alcohols,
10 (a) S. K. Movahed, R. Esmatpoursalmani, A. Bazgir, RSC Adv.
2014, 4, 14586; (b) H. Joshi, K. N. Sharma, A. K. Sharma, A. K.
Singh, Nanoscale 2014, 6, 4588.
diphenylacetilene, norbornene and
compounds.
α,β-unsaturated carbonyl
11 S.-I. Yamamoto, H. Kinoshita, H. Hashimoto, Y. Nishina,
Nanoscale 2014, 6, 6501.
12 J. Lin, T. Mei, M. Lv, C. Zhang, Z. Zhao, X. Wang, RSC Adv.
2014, 4, 29563.
Experimental
13 (a) T. Hattori, A. Tsubone, Y. Sawama, Y. Monguchi, H. Sajiki,
Catalysts 2015, 5, 18. (b) A. Corma, H. Garcia, A. Leyva, Appl.
Catal. A 2002, 236, 179; (c) K. Okumura, T. Tomiyama, S.
Okuda, H. Yoshida, M. Niwa, J. Catal. 2010, 273, 156.
14 (a) F. X. L. Xamena, A. Abad, A. Corma, H.Garcia, J. Catal.
2007, 250, 294; (b) H. Choudhary, S. Nishimura, K. Ebitani, J.
Mater. Chem. A 2014, 2, 18687; (c) A. Dhakshinamoorthy, A.
M. Asiri, H. Garcia, Chem. Soc. Rev. 2015, 44, 1922.
15 (a) C. Ornelas, J. Diallo, A. K. Ruiz, D. Astruc, Adv. Synth.
Catal. 2009, 351, 2147; (b) M. Lamblin, L. Nassar-Hardy, J.-C.
Hierso, E. Fouquet, F.-X. Felpin, Adv. Synth. Catal. 2010, 352,
33.
16 R. S. Erami, D. Díaz-García, S. Prashar, A. Rodríguez-Diéguez,
M. Fajardo, M. Amirnasr, S. Gómez-Ruiz, Catalysts 2017, 7,
76.
17 (a) H. Choudhary, J. Jia, S. Nishimura, K. Ebitani, Asian J. Org.
Chem. 2017, 6, 274; (b) M. I. Burrueco, M. Mora, C. Jiménez-
General
All commercially available reagents were used without further
purification unless otherwise stated. Reactions were
monitored by analytical thin-layer chromatography (TLC) using
silica gel 60 F254 precoated glass plates (0.25 mm thickness)
and visualized using UV light, iodide, and vanillin reagent. Flash
column chromatography was performed on a silica gel (230–
400 mesh). 1H NMR and 13C NMR were recorded on a 400 MHz
nuclear magnetic resonance spectrometer (400 MHz for 1H
NMR and 100 MHz for 13C NMR).
Synthesis of HT/Pd (Mg/Al 2:1) and HT/Pd (Mg/Al 3:1)
HT were prepared according to ref.17b (Mg/Al2:1) and ref.43
HT/Pd (palladium content 1.0%w/w)was obtained according to
ref.17b using PdCl2 as palladium source.
Sanchidrián, J. R. Ruiz, Applied Catalysis A: General 2014
,
General Procedure for the Hydroarylation Reaction
485, 196; (c) M. Mora, C. Jiménez-Sanchidrián, J. R. Ruiz, J.
Mol. Catal. A: Chemical 2008, 285, 79; (d) M. Mora, C.
Jiménez-Sanchidrián, J. R. Ruiz, J. Colloid and Interface Sience
2006, 302, 568; (e) C. Jiménez-Sanchidrián, M. Mora, J. R.
Ruiz, Catal. Comm. 2006, 7, 1025; (f) B. M. Choudary, S.
Madhi, N. S. Chowdari, M. L. Kantam, B. Sreedhar, J. Am.
Chem. Soc. 2002, 124, 14127; (g) B. Van Vaerenbergh, K. De
Vlieger, K. Claeys, G. Vanhoutte, J. De Clercq, P. Vermeir, A.
Verberckmoes, Appl. Catal. A-Gen. 2018, 550, 236.
To a stirred solution of aryl iodide (2.54mmol) and piperidine
(3.57 mmol) in MeCN (2 mL) were added propargylic alcohol
(1.0 mmol), HT/Pd(0) (20 mg) and formic acid (2.77 mmol). The
mixture was stirred at 80° C for the required time, then the
mixture was filtered on celite with AcOEt and concentrated.
The residue was purified by flash chromatography.
18 (a) M. Martínez, R. Ocampo, L. A. Rios, A. Ramírez, O.
Giraldo, J. Braz. Chem. Soc. 2011, 22, 2322; (b) H. Zhou, G. L.
Zhuo, X. Z. Jiang, J. Mol. Catal. A: Chemical 2006, 248, 26; (c)
T. H. Bennur, A. Ramani, R. Bal, B. M. Chanda, S. Sivasanker,
Catal. Comm. 2002, 3, 493.
Conflicts of interest
There are no conflicts of interest to declare
19 J. Wang, A. Xu, M. Jia, S. Bai, X. Cheng, B. Zhaorigetu, New J.
Chem., 2017, 41, 1905.
References
1
R. A. Sheldon, Green Chem. 2017, 19, 18.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 5
Please do not adjust margins

Please do not adjust margins
New Journal of Chemistry
Page 6 of 7
View Article Online
DOI: 10.1039/C7NJ04046F
ARTICLE
Journal Name
20 (a) Y. He, J. Fan, J. Feng, C. Luo, P. Yang, D. Li, J. Catal. 2015
331, 118; (b) M. Lakshimi Kantam, T. Parsharamulu, S. V. J.
Manorama, Mol. Catal. A: Chemical 2012, 365, 115.
21 (a) Z. Wu, Q. Zhu, C. Shen, T. Tan, ACS Omega 2016, 1, 498;
(b) D. Naresh, V. P. Kumar, M. Harisekhar, N. Nagarju, B.
,
Sakuraba, T. Okada, T. Morimoto, K. Achiwa, Chem. Pharm.
Bull. 1995, 43, 927; (d) X.-Y. Wu, H.-D. Xu, Q.-L. Zhoua, A. S.
C. Chan, Tetrahedron: Asymmetry 2000, 11, 1255; (e) X.-Y.
Wu, H.-D. Xu, F.-Y. Tang, Q.-L. Zhou, Tetrahedron: Asymmetry
2001, 12, 2565.
Putrakumar, K. V. R. Chary, Applied Surface Science 2014
314, 199.
,
42 (a) S. Mannathan, S. Raoufmoghaddam, J. N. H. Reek, J. G. de
Vries, A. J. Minnaard, ChemCatChem. 2017, 9, 551; (b)
Mannathan, S.; Raoufmoghaddam, S.; Reek, J. N. H.; de Vries
J. G.; Minnaard, A. J. ChemCatChem. 2015, 7, 3923; (c) S.
Raoufmoghaddam, S. Mannathan, A. Minnaard, J. G. de
Vries, J. N. H. Reek, Chem. Eur. J. 2015, 21, 18811; A. L.
Gottumukkala, J. G. de Vries, A. Minnaard, Chem. Eur. J.
2011, 17, 3091; (d) A. Amorese, A. Arcadi, E. Bernocchi, S.
Cacchi, S. Cerrini, M. Fedeli, G. Ortar, Tetrahedron 1989, 45,
813; (e) S.; Cacchi, A. Arcadi, J. Org. Chem. 1983, 48, 4236.
43 Qi. Tao, Y. Zhang, X. Zhang, P. Yuan, H. He, J. Solid State
Chem. 2006, 179, 3, 708.
22 (a) S. Cacchi, A. Arcadi, J. Org. Chem. 1983, 48, 4236; (b) A.
Amorese, A. Arcadi, E. Bernocchi, S. Cacchi, S. Cerrini, W.
Fedeli, G. Ortar, Tetrahedron 1989, 45, 813; (c) S. Cacchi,
Pure Appl. Chem. 1990, 62, 713; (d) A. Arcadi, S. Cacchi, G.
Fabrizi, F. Marinelli, P. Pace, Tetrahedron 1996, 52,6983.
23 (a) S. Raoufmoghaddam, S. Mannathan, A. J. Minnaard, J. G.
de Vries, J. N. H. Reek, Chem. Eur. J. 2015, 21, 18811; (b) A. L.
Gottumukkala, J. G. de Vries, A. J. Minnaard, Chem. Eur. J.
2011, 17, 3091.
24 For selected examples, see: (a) S. Diethelm, E. M. Carreira, J.
Am. Chem. Soc. 2013, 135, 8500; (b) J. Chen, J. Xie, D. Bao, S.
Liu, Q. Zhou, Org. Lett. 2012, 14, 2714; (c) P. Gao, S. P. Cook,
Org. Lett. 2012, 14, 3340; (d) R. Peng, M. S. Van Nieuwenhze,
Org. Lett. 2012, 14, 1962; (e) A. B. Dounay, P. G. Humphreys,
L. E. Overman, A. D. Wrobleski, J. Am. Chem. Soc. 2008, 130,
5368; (f) Z. Li, E. B. Watkins, H. Liu, A. G. Chittiboyina, P. B.
Carvalho, M. A. Avery, J. Org. Chem. 2008, 73, 7764; (g) M.
Ichikawa, M. Takahashi, S. Aoyagi, C. Kibayashi, J. Am. Chem.
Soc. 2004, 126, 16553; (h) B. M. Trost, O. R. Thiel, H.-C. Tsui,
J. Am. Chem. Soc. 2002, 124, 11616; (i) K. Lee, , J. K. Cha, J.
Am. Chem. Soc. 2001, 123, 5590; (j) D. Solé, J. Bonjoch, S.
García-Rubio, E. Peidrl, J. Bosch, Angew. Chem. Int. Ed. 1999
38, 395; (k) B. M. Trost, F. D. Toste, J. Am. Chem. Soc. 1999
121, 3543; (l) S. C. Clayton, A. C. Regan, Tetrahedron Lett.
1993 34, 7493; (m) B. Schmidt, H. M. R. Hoffmann,
,
,
,
Tetrahedron 1991, 47, 9357.
25 F. Neaţu, M. Ciobanu, L. E. Ştoflea, L. Frunză, V. I, Părvulescu,
V. Michelet, Catalysis Today 2015, 247, 155.
26 F. Neaţu, M. Besnea, V. G. Komvokis, J.-P. Genêt, V. Michelet,
K. S. Triantafyllidis, V. I. Părvulescu, Catalysis Today 2008
139, 161.
,
27 A. Arcadi, S. Cacchi, F.Marinelli Tetrahedron 1985, 41, 5121.
28 A. Arcadi, S. Cacchi, S. Iannelli, F. Marinelli, M. Nardelli, Gazz.
Chim. It. 1986, 116, 725.
29 L. H. Hay, T. M. Koenig, F. O. Ginah, J. D. Copp, D. Mitchell, J.
Org. Chem. 1998, 63, 5050.
30 S. Cacchi, G. Fabrizi, A. Goggiamani J. Mol. Catal. A: Chemical
2004, 214, 57.
31 (a) A. Arcadi, S. Cacchi, G. Fabrizi, F. Marinelli, P. Pace, Eur. J.
Org. Chem. 1999, 3305; (b) A. Arcadi, E. Bernocchi, A. Burini,
S. Cacchi, F. Marinelli, B. Pietroni, Tetrahedron Lett. 1989, 30,
3465; (c) A. Arcadi, E. Bernocchi, A. Burini, S. Cacchi, F.
Marinelli, B. Pietroni, Tetrahedron 1988, 44, 481.
32 N. A. Cortese, R. F. Heck, J. Org. Chem. 1977, 42, 3491.
33 M.-J. Wu, L.-M. Wei, C.-F. Lin, S.-P. Leou, L.-L. Wei,
Tetrahedron 2001, 57, 7839.
34 S. Cacchi, M. Felici, B. Pietroni, Tetrahedron Lett. 1984, 3137.
35 (a) A. Arcadi, F. Marinelli, E. Bernocchi, S. Cacchi, G. Ortar, J.
Organomet. Chem. 1989, 368, 249. (b) R. C. Larock, P. L.
Johnson, Chem. Commun. 1989, 1368.
36 P. Mayo, W. Tam, Tetrahedron 2002, 58, 9527.
37 G. Bartolo, S. Cacchi, G. Fabrizi, A. Goggiamani, Synlett 2008
,
2508.
38 A. Wållberg, G. Magnusson, Tetrahedron 2000, 56, 8533.
39 S. C. Clayton, A. C. Regan, Tetrahedron Lett. 1993, 34, 7493.
40 (a) F. I. Carroll, L. E. Brieaddy, H. A. Navarro, M. I. Damaj, B.
R. Martin, J. Med. Chem. 2005, 48, 7491; (b) A. Kasyan, C.
Wagner, M. E. Maier, Tetrahedron 1998, 54, 8047; (c) D. Bai,
R. Xu, G. Chu, X. Zhu, J. Org. Chem. 1996, 61, 4600.
41 (a) H. Brunner, K. Kramler, Synthesis 1991, 1121; (b) S.
Sakuraba, K. Awano, K. Achiwa, Synlett 1994, 291; (c) S.
6 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 7 of 7
New Journal of Chemistry
View Article Online
DOI: 10.1039/C7NJ04046F
Hydrotalcite-Supported Palladium Nanoparticles as Catalyst for the Hydroarylation of
Carbon-Carbon Multiple Bond
Z
Z
Z
Y
HT/Pd
HCOOH
OH
R2
+
+
Piperidine
CH3CN 100°C
OH
R1
OH
R1
R1
I
R2
R2
Y
Y
Palladium nanoparticles supported on hydrotalcites catalyze the hydroarylation reaction of
Carbon-Carbon Multiple Bond.