Direct synthesis of β-ketophosphonates and vinyl phosphonates from alkenes or alkynes catalyzed by CuNPs/ZnO

Article abstract of DOI:10.1039/c5ra10223e

Copper nanoparticles (CuNPs) supported on ZnO have been shown to effectively catalyze the direct synthesis of β-ketophosphonates from alkenes or alkynes, and that of vinyl phosphonates from alkynes and diethylphosphite, under air and in the absence of any additive or ligand. When using alkynes as starting materials, the selectivity proved to be dependent on the nature of the alkyne. Thus, alkynes conjugated with an aromatic ring or a carbon-carbon double bond gave β-ketophosphonates as the main reaction products, whereas aliphatic alkynes or alkynes conjugated with a carbonyl group led to the formation of the corresponding vinyl phosphonates.

Full text of DOI:10.1039/c5ra10223e

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Direct synthesis of β-ketophosphonates and vinyl phosphonates
from alkenes or alkynes catalyzed by CuNPs/ZnO.
Victoria Gutierrez,a,† Evangelina Mascaró,a,† Francisco Alonso,b Yanina Moglie,a,* and Gabriel
Radivoy.a,*
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
Copper nanoparticles (CuNPs) supported on ZnO have been shown to effectively catalyze the direct synthesis of β-
ketophosphonates from alkenes or alkynes, and that of vinyl phosphonates from alkynes and diethylphosphite, under air
and in the absence of any additive or ligand. When using alkynes as starting materials, the selectivity proved to be
dependent on the alkyne nature. Thus, alkynes conjugated with an aromatic ring or a carbon-carbon double bond gave β-
ketophosphonates as the main reaction products, whereas aliphatic alkynes or alkynes conjugated with a carbonyl group
led to the formation of the corresponding vinyl phosphonates.
www.rsc.org/
mercury salts in combination with acids or bases. Although
recently published procedures based on the use of Pd10 or Au11
catalysts for the hydration of alkynylphosphonates circumvent
Introduction
Phosphorus containing organic compounds are of widespread
interest in synthetic organic chemistry. This is due to the
remarkable biological activities of many phosphorus
derivatives which make them of potential interest and
application in diverse fields, ranging from medicinal chemistry
to the agrochemical industry. Phosphonic acids and esters are
widely known as extremely important structural analogues to
the corresponding carboxylic acids and esters.1 Among this
the use of toxic reagents, there is still a need for the
development of direct synthetic methodologies to access
β
-
ketophosphonates from simple and readily available starting
materials. In this regard, the transition metal-catalysed
oxyphosphorylation of alkynes with H-phosphonates has very
recently been tackled by two independent research groups. In
one of these works, Zaho et al.12 reported a one-pot strategy
for
the
synthesis
of
β
-ketophosphonates
using
family of organophosphorus compounds, β-ketophosphonates
AgNO3/CuSO4·5H2O as catalyst and K2S2O8 as oxidant additive.
The reactions are conducted under air and in CH2Cl2-H2O as
have received considerable attention in recent years, not only
due to their varied biological activities2 and metal-complexing
abilities,3 but also because they are valuable precursors for the
solvent. In
a
more recent paper, Song et al.,13 have
communicated the oxyphosphorylation of alkynes or alkynyl
carboxylic acids with H-phosphonates, catalysed by
CuOTf/FeCl3 in DMSO, under O2 atmosphere, in the presence
of Et3N as base.
construction of
Wadsworth-Emmons reaction)4 and for the synthesis of chiral
-amino-5 and -hydroxy6 phosphonic acids.
Several methods for the synthesis of -ketophosphonates can
be found in the scientific literature.7 The most common
approaches are based in the condensation between carboxylic
acid derivatives and alkyl phosphonates,8 and in the hydration
of alkynyl phosphonates,9 both protocols having some
important drawbacks; while condensation reactions often
need for the use of strong bases and/or cryogenic conditions,
many of the hydration-based methods require the use of toxic
α,β-unsaturated compounds (Horner-
β
β
β
On the other hand the copper/iron co-catalyzed
oxyphosphorylation of alkenes with dioxygen and H-
phosphonates published by Wei and Ji,14 is, to the best of our
knowledge, the only transition metal-catalyzed direct synthesis
of β-ketophosphonates from alkenes that has been published
so far.
Even though the above mentioned transition metal-catalysed
methodologies are useful and attractive, in most cases long
reaction times (24 h), oxygen atmosphere and/or the use of
different additives is required.
a.Instituto de Química del Sur, INQUISUR (CONICET-UNS), Departamento de
Química, Universidad Nacional del Sur, Av. Alem 1253, 8000 Bahía Blanca,
Argentina.
Vinyl phosphonates represent another prominent member of
the family of phosphorous derivatives, they are well known as
important synthetic intermediates15 and have diverse
applications as monomers and co-monomers in polymeric
materials.16 Most of the existing methods for P-C(vinylic) bond
formation are based on palladium-catalyzed reactions,1,17
which usually require the use of phosphine ligands.
b.Instituto de Síntesis Orgánica (ISO) , and Departamento de Química Orgánica,
Facultad de Ciencias, Universidad de Alicante, Apdo. 99, E-03080, Alicante, Spain.
*gradivoy@criba.edu.ar
Electronic Supplementary Information (ESI) available: Detailed experimental
procedures, characterization data, and copies of 1H, 13C and 31P NMR spectra of all
phosphonate products. Full characterization of catalyst is also included. See
DOI: 10.1039/x0xx00000x
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Alternatively, the use of Cu(I)18 or Ni(II)19 catalysts have also 1). The lower conversions obtained when using any of the
been reported but both methodologies need for harsh other supports listed in Table 1, could suggest the necessity for
reaction conditions or phosphine ligands to give the desired the presence of Lewis acid (Zn2+) and/or Lewis basic (O2-) sites
vinyl phosphonates in reasonable yields.
on the support for the reaction to take place at a reasonable
In the last years we have actively been working in the rate.
development of new and mild methodologies based on the use
Table 1. Screening of different CuNPs-based catalystsa
of bare or supported copper nanoparticles (CuNPs) for their
application in the construction of C-C and C-heteroatom
bonds.20 During the course of our investigations about CuNPs-
catalysed C-P coupling reactions, we have found that the
reaction between aryl acetylenes or terminal alkenes with
commercial diethyl phosphite, catalysed by CuNPs supported
Entry
1
Catalyst
Conversion (%)b
CuNPs/ZnO
86
83c
69d
on ZnO, led to the direct formation of β-ketophosphonates.
Notably, when aliphatic alkynes were reacted under the same
reaction conditions, the corresponding vinyl phosphonates
were obtained instead as the major products. We want to
present herein our results on the development of a new and
2
3
4
5
6
7
8
9
CuNPs/CeO2
CuNPs/PVP
52
42
simple methodology that allow the direct synthesis of
β-
ketophosphonates and vinyl phosphonates from alkenes or
alkynes as simple and readily available starting materials,
under air atmosphere and mild reaction conditions, catalysed
by CuNPs/ZnO.
CuNPs/cellulose
CuNPs/Celite®
CuNPs/MWNT
CuNPs/MCM-41
CuCl2/ZnO
28
14
40
38
83e
39e
Results and Discussion
CuCl/ZnO
We started our study by choosing phenylacetylene (1a) as
model substrate to optimize the reaction conditions. The
reactions were performed under air atmosphere and in the
absence of any other additive or ligand. Initially, the reaction
of 1a with (EtO)2P(O)H was tested in the presence of CuNPs
supported on a variety of organic and inorganic materials using
acetonitrile as the solvent (Table 1). All the CuNPs based
catalysts were prepared according to the methodology
previously reported by us,20 the CuNPs (3-6 nm in size) being
synthesized by fast reduction of anhydrous CuCl2 with an
excess of lithium sand and a catalytic amount of DTBB (4,4’-di-
tert-butylbiphenyl) as electron carrier. Figure 1 shows a TEM
image and size distribution graphic for CuNPs/ZnO catalyst
(see Supporting Information for experimental details and
characterization of the catalyst). As can be seen, well dispersed
spherical copper nanoparticles with an average particle size of
6.0 ± 0.5 nm are obtained.
aReaction conditions: phenylacetylene (1 mmol), diethyl phosphite (2 mmol),
catalyst (40 mg, 1.7 mol % Cu), in acetonitrile (2 mL) at 70˚ C under air
atmosphere, 6 h. bDetermined by GC using an internal standard. cReaction
performed using 60 mg of catalyst. dReaction performed using 20 mg of catalyst.
eConversion obtained at 24 h of reaction time.
The optimal amount of catalyst was found to be 40 mg (see
Table 1, footnotes c and d), giving a copper loading of 1.7
mol% referred to the starting alkyne. Interestingly, we found
that when using CuCl2 as copper source, a similar conversion to
the β-ketophosphonate product was obtained, although in a
significantly longer reaction time (Table 1, entry 8). On the
contrary, the use of CuCl/ZnO as catalyst demonstrated to be
less effective (Table 1, entry 9).
Control experiments carried out, both in the absence of the
CuNPs/ZnO catalyst or in the presence of the support or the
CuNPs alone, gave no conversion of the starting
phenylacetylene to the desired product.
Then, the effect of the solvent, added bases and reaction
atmosphere was studied. Among the different solvents tested
acetonitrile demonstrated to be the solvent of choice. Other
solvents
such
as
methanol,
dimethyl
sulfoxide,
dichloromethane, toluene, acetone and tetrahydrofuran gave
almost no conversion of the starting material, whereas a 15%
conversion to the alkyne homocoupling product was observed
when water was used as the reaction medium. The reaction
carried out under N2 atmosphere gave low conversion to the
desired product 2a (near 15%). The addition of a base (Cs2CO3,
Na2CO3, TMDA or triethylamine) proved counterproductive for
the reaction, giving no conversion of the starting alkyne after
24 h of reaction time.
Figure 1. TEM image and size distribution graphic of CuNPs in CuNPs/ZnO catalyst.
As shown in Table 1, the best results were obtained by working
at 70˚ C and using ZnO as support for the CuNPs (Table 1, entry
2 | J. Name., 2012, 00, 1-3
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Another interesting observation was that the suspension of When aliphatic alkynes were subjected to the same reaction
the catalyst in the solvent was kept for those cases in which no conditions, the anti-Markovnikov vinyl phosphonates 2i-m
conversion was measured. On the contrary, for those reactions (Table 2) were formed as the main reaction products, together
which progressed to the desired products, the catalyst was with
completely dissolved in the reaction media, forming a single ketophosphonates. In all cases, an inseparable mixture of E/Z
clear phase. isomers was obtained. It must be pointed out that alkyne 1m
minor amounts of the
corresponding
β-
,
Under the optimized conditions, a series of aromatic and which is not aliphatic but conjugated with a C=O, gave the
aliphatic terminal alkynes were then tested. As can be seen in corresponding vinylphosphonate 2m as the main reaction
Table 2, terminal aryl acetylenes gave the corresponding
β
ketophosphonates 2a-h as the major reaction products in good conjugated with a C=C bond gave the corresponding
-
product, whereas, as above mentioned, alkyne 1h which is
β
to excellent yields. Other dialkyl phosphites such as dimethyl- ketophosphonate product (2h). This selectivity dependent on
-
or dibutyl phosphite, were also suitable phosphorylating the alkyne nature has not been observed in previously
agents (Table 2, compounds 2a
ethynylcyclohex-1-ene gave
′
and 2a
″
). Interestingly, 1- reported copper-catalysed oxyphosphorylation of alkynes, and
the corresponding
β
ketophosphonate in good yield (Table 2, compound 2h), thus catalyst. On the other hand, when internal alkynes were
-
represents very important feature of this CuNPs/ZnO
a
suggesting that the presence of a conjugated C=C in the tested, both diaryl- and dialkyl alkynes, as well as aryl alkyl
starting alkyne is mandatory for the formation of the
ketophosphonate products.
β
-
ones, low conversions to a complex mixture of products were
obtained.
Then, we decided to test the reaction of alkenes with diethyl
phosphite under the same optimized reaction conditions. We
observed that only terminal alkenes were converted to the
Table 2. Synthesis of β-ketophosphonates and vinyl phosphonates
from terminal alkynesa,b
corresponding β-ketophosphonates (Table 3). It is worthy of
note that the CuNPs/ZnO catalyst demonstrated not to be
compatible with the presence of hydroxyl or carboxylic acid
groups in the starting alkyne or alkene. These functional
groups could form strong hydrogen-bonds with the Lewis basic
sites at the catalyst support, thus preventing its participation
in the reaction pathway. All of the above experimental
observations would suggest that the ZnO support could be
playing a non-innocent role in the catalytic system, probably
through the P-H bond activation.21
Table 3. Synthesis of β-ketophosphonates from alkenes
aIsolated yield after chromatographic purification (Hexane/AcOEt).
We conducted a series of additional experiments in order to
get some information about the reaction mechanism involved
in each of the transformations studied. Initially, based on our
experimental observations and previous reports, we studied
the effect of the addition of TEMPO as radical scavenger.
Under the optimized conditions, the presence of TEMPO
aIsolated yield after chromatographic purification (Hexane/AcOEt).
bE/Z isomeric ratio determined by GC/MS.
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inhibited the formation of
β
from phenylacetylene (1a) or styrene (3a), suggesting a radical intermediate to the C
-ketophosphonates, both starting the phosphorus radical III (Figure 2). Addition of this radical
C or C=C bond, and subsequent reaction
≡
pathway for the mechanism of these reactions. On the with an active-oxygen copper complex, formed by reaction of
contrary, the transformation of 1-octyne into the CuNPs with dioxygen present in air, would led to reactive
corresponding vinyl phosphonate 2i, was not affected by the hydroperoxide intermediates.12,13 Finally, these reactive
addition of TEMPO to the reaction mixture. On the other hand, intermediates would evolve to the corresponding
β-
the reaction of 1-octyne under the optimized conditions but ketophosphonate products, through a keto-enol taumerism in
carried out under N2 atmosphere, gave the vinyl phosphonate the case of alkynes, and by elimination of water in the case of
product 2i with almost the same conversion and in a similar alkenes.
reaction time to that of the same reaction conducted under On the other hand, the observed formation of vinyl
air. As above mentioned, the synthesis of β-ketophosphonate phosphonates from aliphatic alkynes, which was not inhibited
2a from phenylacetylene failed when it was carried out in the by the presence of TEMPO (and also works in the absence of
absence of air. The use of an O2 atmosphere, both for the air), should be occurring through a non-radical process,
reaction of 1-octyne and phenylacetylene, proved probably due to the lower stability of the corresponding vinyl
counterproductive.22
radical intermediate. Instead, a copper-catalysed anti-
With the aim to get information on the oxidation state of Markovnikov hydrophosphorylation of the aliphatic alkyne
copper in the catalyst, XPS analyses were performed, leading to the corresponding vinyl phosphonates, could take
unfortunately the XPS spectra obtained were not conclusive, place. It is noteworthy that most of the reported methods for
mainly due to a low signal-to-noise ratio that could be the metal-catalysed hydrophosphorylation of alkynes are
attributed to the low concentration of copper in the catalyst. based on the use of expensive and/or toxic palladium, nickel or
Despite this, based on our previous works20 and the results rhodium catalysts,17c-e whereas copper-based ones have
showed in Table 1 (entries 8 and 9), we assume that copper(II) remained almost unexplored to date.23 With the aim to
is most likely to be the active species in the catalyst.
confirm this hypothesis, we carried out the reaction by using 1-
Although the exact mechanism involved in the transformations deuterio-oct-1-yne as starting alkyne. As expected, the
studied is not clear enough at this stage, based on our corresponding deuterated-vinyl phosphonate product was
experimental observations and previous reports by other obtained, thus showing that, in the case of aliphatic alkynes,
authors,12,13 we suppose that a radical oxyphosphorylation copper acetylides would not be formed under the reaction
process is more likely to occur in the synthesis of
β
ketophosphonates. As shown in Fig. 2, Cu(II) species in copper-catalysed hydrophosphorylation process.
-
conditions and the reaction is more likely to occur via a
combination with ZnO would be promoting the formation of
Zn2+ O2ꢀ
H
Zn2+ O2ꢀ
H
air
Cu(II)
O
O
Cu(I)
O
ZnO
(EtO)2P
(II)
(EtO)2P
(I)
(EtO)2P
H
Zn2+ O2ꢀ
OH
[ZnL4]x [(EtO)2P(O)O]y
O
CuNPs/ZnO
Ar
Cu H
(EtO)2P
(III)
R
Ar
O
O
R
Ar
(EtO)2P
(EtO)2P
air
air
.
.
Cu(I)
Cu(II) ( OOH)
Cu(II) ( OOH)
Cu(I)
H
H
O
O
O
O
R
O
O
Ar
(EtO)2P
(EtO)2P
O
(EtO)2P
O
H
H2O
(EtO)2P OH
HO
O
O
R
O
(EtO)2P
O
O
Ar
Ar
(EtO)2P
(EtO)2P
4 | J. Name., 2012, 00, 1-3
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Figure 2. Proposed mechanistic pathway for the synthesis of β-ketophosphonates from aromatic alkynes and alkenes catalysed by CuNPs/ZnO.
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In conclusion, we have developed a new mild, simple and
economical methodology for the direct synthesis of
β-
ketophosphonates and vinyl phosphonates from
commercial or readily available starting materials, catalysed
by CuNPs/ZnO. The catalyst showed to be very efficient
working under air atmosphere and in the absence of any
additive or ligand. Alternative copper sources such as CuCl2
in combination with ZnO, can also be utilized, however
longer reaction times are needed. Although the exact
mechanistic pathway is difficult to ascertain at this stage,
based on our experimental observations, we propose that a
copper-catalysed radical oxyphosphorylation mechanism
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would be involved in the formation of
whereas non-radical
β
-ketophosphonates,
copper-catalysed
a
hydrophosphorylation process would be more likely to
occur in the formation of vinyl phosphonates. Furthermore,
it should not be ruled out a bifunctional mode of action by
the CuNPs/ZnO catalyst, where the CuNPs could be
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Acknowledgements
This work was generously supported by the Consejo
Nacional de Investigaciones Científicas
y
Técnicas
(CONICET), Agencia Nacional de Promoción Científica y
Tecnológica (ANPCyT) and Universidad Nacional del Sur
(UNS) from Argentina. V.G. thanks the CONICET for a
postdoctoral fellowship.
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18 (a) D. Gelman, L. Jiang, S. L. Buchwald, Org. Lett. 2003,
2315. (b) S. Thielges, P. Bisseret, J. Eustache, Org. Lett.
2005, , 681.
5,
7
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DOI: 10.1039/C5RA10223E
ARTICLE
Journal Name
19 (a) G. Trostyanskaya, D. Y. Titskiy, E. A. Anufrieva, A. A.
Borisenkko, M. A. Kazankova, I. P. Beletskaya, Russ. Chem.
Bull., Int. Ed. 2001, 50, 2095. (b) L. B. Han, C. Zhang, H.
Yazawa, S. Shimada, J. Am. Chem. Soc. 2004, 126, 5080.
20 For some recent works, see: (a) F. Nador, M. A. Volpe, F.
Alonso, A. Feldhoff, A. Kirschning, G. Radivoy, Appl. Catal.
A: Gen. 2013, 455, 39. (b) F. Alonso, Y. Moglie, G. Radivoy,
M. Yus, J. Org. Chem. 2013, 78, 5031. (c) F. Nador, M. A.
Volpe, F. Alonso, G. Radivoy, Tetrahedron 2014, 70, 6082.
21 M. Hosseini-Sarvari, M. Tavakolian, New J. Chem. 2012,
36, 1014.
22 As suggested by one referee, the reaction under O2
atmosphere was tested. When oct-1-yne was used as
starting alkyne, after 8 h of reaction time, a very low
conversion to octanoic acid as the only organic product
was observed, together with
diethylphosphate, produced
a
by
large amount of
oxidation of
diethylphosphite. On the other hand, when the reaction
was carried out using phenylacetylene as starting alkyne,
a
30% conversion to the corresponding
β-
ketophosphonate was observed, together with benzoic
acid and other phosphorylated by-products whose
structures could not be elucidated.
23 I. G. Trostyanskaya, I. P. Beletskaya, Tetrahedron 2014,
70, 2556.
6 | J. Name., 2012, 00, 1-3
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DOI: 10.1039/C5RA10223E
Direct synthesis of -ketophosphonates and vinyl phosphonates from
alkenes or alkynes catalyzed by CuNPs/ZnO.
Victoria Gutierrez,a,† Evangelina Mascaró,a,† Francisco Alonso,b Yanina Moglie,a,* and Gabriel Radivoy.a,*