A practical and efficient green synthesis of β-aminophosphoryl compounds via the aza-michael reaction in water

Article abstract of DOI:10.1080/10426507.2010.511358

Application of water as a solvent (without any cosolvent) promotes the aza-Michael reaction of diethyl vinylphosphonate and diphenylvinylphosphine oxide with a wide range of N-nucleophiles. The solubility of the starting phosphorus substrate in water does not play a crucial role in the reaction course, decreasing to some extent the reaction rate. The reaction can be performed either at room temperature or under reflux to afford the corresponding β-aminophosphonates and β-aminophosphine oxides in excellent yields and of high purity via a simple freeze-drying isolation procedure. Application of basic catalysts makes possible the addition of weak nucleophiles such as a-amino acids and their phosphorus analogues; that is, a-aminophosphonic acids. The aqueous aza-Michael reaction allowed us to easily perform double phosphorylation of primary amines including polyamines using a reactant ratio (phosphorus substrate: amine) of 2:1. Copyright Taylor & Francis Group, LLC.

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Phosphorus, Sulfur, and Silicon and the
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A Practical and Efficient Green Synthesis
of β-Aminophosphoryl Compounds via
the Aza-Michael Reaction in Water
Ekaterina V. Matveeva a , Anatoly E. Shipov a & Irina L. Odinets a
a A. N. Nesmeyanov Institute of Organoelement Compounds, Russian
Academy of Sciences, Moscow, Russia
Version of record first published: 25 Apr 2011.
To cite this article: Ekaterina V. Matveeva, Anatoly E. Shipov & Irina L. Odinets (2011): A Practical
and Efficient Green Synthesis of β-Aminophosphoryl Compounds via the Aza-Michael Reaction in
Water, Phosphorus, Sulfur, and Silicon and the Related Elements, 186:4, 698-706
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Phosphorus, Sulfur, and Silicon, 186:698–706, 2011
Copyright ꢀC Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426507.2010.511358
A PRACTICAL AND EFFICIENT GREEN SYNTHESIS
OF β-AMINOPHOSPHORYL COMPOUNDS VIA THE
AZA-MICHAEL REACTION IN WATER
Ekaterina V. Matveeva, Anatoly E. Shipov, and Irina L. Odinets
A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy
of Sciences, Moscow, Russia
Abstract Application of water as a solvent (without any cosolvent) promotes the aza-Michael
reaction of diethyl vinylphosphonate and diphenylvinylphosphine oxide with a wide range of
N-nucleophiles. The solubility of the starting phosphorus substrate in water does not play a
crucial role in the reaction course, decreasing to some extent the reaction rate. The reaction
can be performed either at room temperature or under reflux to afford the corresponding
β-aminophosphonates and β-aminophosphine oxides in excellent yields and of high purity
via a simple freeze-drying isolation procedure. Application of basic catalysts makes possible
the addition of weak nucleophiles such as α-amino acids and their phosphorus analogues;
that is, α-aminophosphonic acids. The aqueous aza-Michael reaction allowed us to easily
perform double phosphorylation of primary amines including polyamines using a reactant
ratio (phosphorus substrate: amine) of 2:1.
Keywords β-Aminophosphoryl compounds; aza-Michael reaction; green chemistry; nucle-
ophilic addition; phosphaalkenes; water
INTRODUCTION
The most relevant challenges of modern organic chemistry are atom economy, chi-
rality economy, and performing reactions under environmentally friendly conditions. In
the scope of general problems in making chemistry greener, the problem with solvents
has become the focus. Theoretically, green chemical processes should be performed under
solvent-free conditions, and some organophosphorus reactions, e.g., the Wittig reaction
and the Kabachnik-Fields reaction and its two-component version were successfully per-
formed by this way mainly under microwave assistance.1 However, this approach may be
impossible or unprofitable in a variety of cases, dictating the need for design or adap-
tation of the required technological processes of so-called green solvents such as ionic
liquids (ILs), water, and supercritical liquids as the main alternatives to toxic, flammable,
and hazardous organic solvents. The importance of this area can be demonstrated by the
Received 24 June 2010; accepted 22 July 2010.
This work was supported by the Program of Chemistry and Material Science Division of RAS and program
of the president of the Russian Federation for young Ph.D. scientists (No. MK-425.2010.3).
Address correspondence to E. V. Matveeva, A. N. Nesmeyanov Institute of Organoelement Compounds
RAS, Vavilova str. 28, Moscow 119991, Russia. E-mail: matveeva@gmail.com
698

GREEN SYNTHESIS OF β-AMINOPHOSPHORYL COMPOUNDS
699
continuous increase in the number of papers and patents in recent decades. Indeed, ionic
liquids, due to their ability to dissolve a variety of organic, inorganic, and metal complex
materials and promote a great number of chemical transformations, in addition to their
nonvolatile nature, low toxicity, and potential for recyclability, are finding their way into
a wide variety of industrial applications.2 Similarly, many chemical and related processes
have been developed using the inherent physical and chemical properties of supercritical
fluids.3 Supercritical fluid technology applied to materials processing can play also a great
role in materials science.4 Furthermore, organic reactions in water which is the least expen-
sive, nontoxic solvent (known also as nature’s solvent) until about decade ago were a mere
curiosity for only a few practitioners. Now this area has become very popular and some
excellent reviews on this topic may be found in the literature.5
Nevertheless, the above-mentioned green solvents enter very slowly into organophos-
phorus chemistry compared to general organic synthesis, apparently because of common
warnings pertaining to the instability of organophosphorus compounds. The known exam-
ples of application of ionic liquids and water as alternative media able to promote some
principle organophosphorus reactions leading to the substances of practical and research
importance were reviewed by us recently.6
Among those, our own results dealing with the aza-Michael additions of amines to
vinylphosphonates in water (without any catalyst or cosolvent) as an effective, simple,
and ecologically friendly approach to biologically active β-aminophosphonates were men-
tioned. In this article we outline the advantages and limitations of this method for both
soluble and insoluble in water substrates. The results have been partially published7,8 and
some are communicated preliminarily in this article.
RESULTS AND DISCUSSION
The aza-Michael reaction is one of the most general and widely used methods for
building up new carbon–nitrogen bonds, especially in the synthesis of a variety of β-
aminocarbonyl compounds and their analogues, which possess biological activity and
useful are as intermediates in further synthesis of β-aminoalcohols, amino acids, lactames,
etc. In the organophosphorus area, a similar approach using vinylphosphonates as the
starting substrates and yielding β-aminophosphonates was firstly applied by A. N. Pudovik
in 1951.9 This methodology provided a wide range of β-aminophosphonates (note that β-
aminophosphonic acid is a natural compound isolated from Celiate protozoa by Horiguchi
and Kandatsu10 in 1959) possessing diverse biochemical properties such as antibacterial,
anti-HIV, and protease-inhibiting activities11 that are useful as synthetic nonviral vector-
mediated gene transfer agents.12 These compounds also possess complexing properties13
that are advantageous for selective ionophores or membrane carrier design.11b Moreover,
β-aminophosphine oxides are useful building blocks in the synthesis of the corresponding
P,N-ligands bearing phosphine donor moieties.14
In the nonphosphorus version of the aza-Michael addition to α,β-unsaturated car-
boxylic acid esters, nitriles, or amides, the process was accelerated by a wide range of
catalysts including bases,15 Lewis,16 or Brønstead17 acids, coordination compounds of plat-
inum group,18 tributylphosphine,19 copper nanoparticles,20 sugars,21 N-methylimidazole,22
poly(N-vinylimidazole),23 and so on, as well as via using ionic liquids,24 biphasic systems
IL/water,25 and water26 as promoting media. In contrast, before the beginning of our works,
the reactions of vinylphosphonates or vinylphosphine oxides were commonly performed
using the excess amine (either neat or in combination with a solvent) and basic catalysts,

700
E. V. MATVEEVA ET AL.
such as EtONa or metal sodium, under elevated temperatures over prolonged reaction times.
Therefore, such severe conditions do not avoid the polymerization of the starting vinyl sub-
strates, substantially decreasing the yields of the desired products. The known attempts to
optimize the synthesis of β-aminophosphoryl compounds were limited by using MeOH14b
as a protic solvent and a combination of the excess amine with water (closed ampoule,
110◦C, 7 days),13b which were performed in both cases using diphenylvinylphosphine
oxide as a starting substrate.
In order to develop an efficient green synthesis of β-aminophosphoryl compounds of
doubtless practical importance, first of all, we estimated the possibility to use imidazolium
ILs as the promoting media for the aza-Michael reaction since nucleophilicity of amines
in ionic liquids are known to increase comparing with that in common organic solvents.27
The reactions of diethyl vinylphosphonate 1 and diphenylvinylphosphine oxide 2 with
morpholine and butylamine were used as a model (Scheme 1). The difference in chemical
shifts of the phosphorus substrates (17.2 and 24.3 ppm for 1 and 2, respectively) and the
corresponding products (ca. 30–31 ppm) allowed easy monitoring of the reaction course
by 31P-NMR spectroscopy. To our surprise, in contrast to the reported data concerning the
acceleration of the aza-Michael addition for nonphosphorus activated alkenes, the reactions
in ILs differing in anion nature were either too sluggish (2–9% yield over 45 min at rt) or
do not proceed at all under the above conditions.8
O
R1
EtO
EtO
P
R1
R2
HN
1
2
O
P
R2
20°C
N
R
R
O
P
Ph
Ph
3
R1
R2
n
=
N
O
N
, Bu(H)N
Scheme 1
Addition of water to ionic liquid, that is, using the mixture IL/H2O in a 1:2 ratio (by
weight) resulted in a drastic increase of the reaction rate. Under these conditions morpho-
line was more reactive compared to nBuNH2. The ILs with hydrophobic tetrafluoroborate
and hexafluorophosphate anions were less effective for vinylphosphonate 1, whereas for
phosphine oxide 2 the reaction proceeds faster in [bmim]BF4. Note that the electronic
factors for these compounds are close to each other (σP is 0.965 and 0.955 for Ph2P(O)
and (EtO)2P(O) groups, respectively28) and steric factors at the remote phosphorus centers
should not interfere with the reaction. Therefore, one may assume that the influence of the
phosphorus substrate structure on the reaction rate is apparently connected with the specific
solvatation of the latter in the mixed solvent in use.
Nevertheless, despite mild reaction conditions (rt, 30 min to 3 h depending on the na-
ture of both components) and excellent yields of β-aminophosphoryl compounds obtained,
according to the 31P-NMR data in the IL/water systems, a substantial loss of a product was
observed over its extraction with organic solvents.
At the same time, if water was used as the sole medium without any cosolvent
or catalyst, the addition of both amines to diethyl vinylphosphonate 1 proceeded with a

GREEN SYNTHESIS OF β-AMINOPHOSPHORYL COMPOUNDS
701
Figure 1 Yields of β-aminophosphonates
3 (indicated above the columns) obtained in reaction of
(EtO)2P(O)CH CH2 1 with different amines in water (20◦C, 45 min).
reaction rate commensurable with that observed in the case of the optimal biphasic system
[bmim]Br/H2O. Even in the case of insoluble in water diphenylvinylphosphine oxide 2,
for which the reaction proceeds in water slower than in the [bmim]BF4/H2O system, the
prolonged reaction time allowed complete addition at room temperature. Isolation of the
final products in quantitative yields after the removal of a solvent (lyophilization) makes
the method really green, very simple, and efficient.7,8
Detailed investigation of the aza-Michael addition has revealed that the nucleophilic-
ity of amine is the main factor influencing the reaction rate for both phosphorus substrates;
that is, it decreased in the series: Alk2NH > AlkNH2 > ArCH2NH2. The steric proper-
ties of amine are the second crucial factor. As an illustration, Figure 1 shows the yields
of β-aminophosphonates obtained in the reaction of 1 with different amines over 45 min
at room temperature. As one can see, the cyclic secondary amines are more active than
the linear ones (note that the reaction with piperidine completed after 7 min), exclud-
ing less nucleophilic piperid-4-one bearing the carbonyl function. The yield of 2-(tert-
butylamino)ethylphosphonate is significantly lower comparing to that for its analogue with
n-butyl group. Note that aromatic amines did not enter the reaction.
In general, in the case of water-soluble vinylphosphonate 1, a longer reaction time
(up to 48 h in the reaction with ethylenediamine) provided a complete conversion at
room temperature, but in the case of phosphine oxide 2, it took days. However, no side
reactions were observed upon performing the reactions at reflux. Hence, the elevated
temperatures were used to reduce the reaction time and the quantitative yields of β-
aminoethylphosphine oxides were achieved over 30 min for more reactive secondary amines
and in a few hours in other cases. Optimized conditions, that is, under ambient conditions
for the reactions of vinylphosphonate 1 with more reactive amines and at 100◦C in the case
of less reactive amines and for addition to diphenylvinylphosphine oxide 2,7,8 were used
for the synthesis of a wide range of β-aminophosphoryl compounds (Scheme 2) isolated
after lyophilization with purity >95% according to multinuclear NMR spectral data. It
should be noted that if more than one amine functionality was present in the N-nucleophile,
as in ethylenediamine, meta-xylylenediamine, and tris(2-aminoethyl)amine, the addition

702
E. V. MATVEEVA ET AL.
O
R
R
P
1,2
H2O
R1
N(CH2NH2)3
O
H2N
X
NH2
HN
N
R2
R1
O
P
NH
R
R
R
H
N
H
N
O
P
O
R
P
R
P
R
O
P
X
R
R
R
R
N
R2
4
N
H
NH
3
O
R
R
P
5
R1
R2
nBu(H)N, tBu(H)N, nHex(H)N, nOct(H)N, PhCH2(H)N, D,L-PhCH(H)N,
N
=
CH3
, Et N, nOct N
O
N ,
N ,
O
N
2
2
X = (CH2)2, H2C-C6H4-CH2
Scheme 2
in water proceeded readily with participation of all of the amine functionalities using an
appropriate ratio of the reactants.
When the starting reactants were used in a 1:1 ratio, only mono adducts were formed in
the reactions with primary amines and no traces of the corresponding bis-addition products
were observed via the 31P-NMR spectroscopy. However, use of the reactants in the ratio
R2P(O)CH CH2/amine = 2:1 allowed double phosphorylation of primary amines. In
other words, β-aminophosphoryl compounds formed may serve as suitable N-nucleophiles
for addition to vinylphosphonate and vinylphosphine oxide in water. To the best of our
knowledge, no examples of such reactions have been observed previously for diethyl
vinylphosphonate 1, whereas for diphenylvinylphosphine oxide 2 double phosphorylation
was performed previously only under severe conditions.13a,14b,29 It should be emphasized
that for nonphosphorylated activated alkenes the double addition to primary amines was
not observed in water as a reaction medium.26 According to 31P-NMR monitoring of
the reaction course, the reaction proceeded via a stepwise process, giving firstly the mono
adducts followed by the addition to a second molecule of the corresponding vinylphosphoryl
compound. Indeed, introduction of the phosphorylethyl moiety to the nitrogen atom of
hexylamine reduces the basicity by 3 pKa units (pKa is equal to 10.4 and 7.4 for HexNH2
and HexNH-CH2CH2P(O)(OEt)2, respectively, as measured in water/i-PrOH (1:1) mixed
solvent).
Therefore, taking into account the difference in reactivity of vinylphosphoryl
compounds 1,2 in water, we performed the target syntheses of oligo(phosphorylethyl)-
substituted amines 6–9, which are useful as complexing agents for different metals at room
temperature for phosphonate 1 and at 100◦C for vinylphosphine oxide 2 (Scheme 3). As
in the above cases, all compounds bearing two phosphorylethyl moieties at the same ni-
trogen atom were isolated in quantitative yields with high purity (>95%) after a simple
lyophilization procedure.

GREEN SYNTHESIS OF β-AMINOPHOSPHORYL COMPOUNDS
703
P(O)R2
P(O)R2
P(O)R2
P(O)R2
N
O
P
N
N
H2O
H2O
H2O
R
R
R1NH
+
2
2
(EtO)2(O)P
P(O)(OEt)2
N
N
R=OEt, Ph
1,2
Bu
6
R2(O)P
R2(O)P
H2O
9
P(O)(OEt)2
P(O)(OEt)2
(EtO)2(O)P
(EtO)2(O)P
P(O)(OEt)2
P(O)(OEt)2
(EtO)2(O)P
(EtO)2(O)P
N
N
N
N
7
8
Scheme 3
Furthermore, the growing interest in new excitatory amino acid antagonists, in par-
ticular selective antagonists of the N-methyl-d-aspartate (NMDA) subtype of glutamate
receptors combining in the molecular structure the phosphonate moiety and the residue of
some amino acids useful for treatment of neurodegenerative disorders,30 prompted us to
involve amino acid derivatives as N-nucleophiles into the aqueous aza-Michael addition.
However, neither amino acid esters nor free acids reacted with vinylphosphoryl compounds
in the absence of a catalyst, possibly due to a decrease in their nucleophilic properties and
formation of zwitterionic species in the case of free acids. Catalytic amounts of tertiary
amines (10 mol% Et3N, iPr2NEt, or 5 mol% DMAP) accelerated the reaction of vinylphos-
phonate 1 with D,L-alanine used as a representative example; however, the conversion was
only ∼30% after 3 days at room temperature. Although an increase in the proportion of
tertiary amine (Et3N) up to 1 molar equivalent provided the complete conversion over 24
h in the same reaction and over 6 h in the reaction with D,L-proline, we failed to isolate
free phosphorylated amino acids 10 by the crystallization or chromatography technique.
These drawbacks were avoided in the addition to vinylphosphoryl compounds 1,2 of amino
acid sodium salts formed in situ, which proceeded readily and provided excellent yields
of the desired phosphonates and phosphine oxides 10,11 isolated after acidification and
removal of water in vacuo, followed by treatment with ethanol to remove the precipitated
sodium chloride (Scheme 4). After optimization, optically active L- or D-amino acids were
R1
COOH
*
H
N
O
P
L- or D-
NH2
COOH
R
R
*
R1
10,
O
P
> 92%
R
R
1. H2O/NaOH
2. H+
*
1,2
COOH
*
L-
N
COOH
NH
R = OEt, Ph
P
R1 = CH3, CH2Ph,iPr, CH2CH2SCH3, CH2COOH
O
R
R
11,
> 95%
Scheme 4

704
E. V. MATVEEVA ET AL.
involved in the reaction. Because the chiral carbon atom is not affected over the reaction
course, using optically active starting materials, the phosphorylated amino acids 10,11 were
obtained in optically pure form.
As one may expect, the reactivity of amino acids decreased in the series proline > ala-
nine > phenylalanine; that is, the regularities are similar to those found for nonsubstituted
amines where the secondary amine is more reactive than the primary one and steric hin-
drances decrease the reaction rate. Note that in contrast to other amino acids, the addition of
glycine in a 1:1 molar ratio of the reactants afforded a mixture of the corresponding mono-
and diphosphorylated products in a 6:4 ratio (12 and 13, respectively, Scheme 5). Using a
stoichiometric ratio of the reactants resulted in bis(phosphorylethyl)-substituted glycine in
a yield close to the quantitative one. We managed to perform the double phosphorylation
of D-alanine in 85% yield only over 2 days at 70◦C.
O
EtO
EtO
P
H2N
COOH
H
N
O
P
O
P
EtO
EtO
EtO
EtO
1.H2O/NaOH
2. H+
COOH
O
P
N
+
COOH
EtO
EtO
1
12
13
Scheme 5
A similar approach allowed us to carry out the addition of α-aminophosphonic acid
to vinylphosphonate 1 to afford the hybrid molecule of α,β-aminophosphonates (Scheme
6).
O
H
N
O
O
P
O
P
1.H2O/NaOH
2. H+
P(OH)2
EtO
EtO
H2N
P(OH)2
EtO
EtO
+
Ph
Ph
1
14
Scheme 6
Finally, β-aminophosphonates including those bearing the residues of amino acids
can be easily converted to the free phosphonic acids via the treatment with Me3SiBr in
acetonitrile followed by methanolysis of the intermediate silyl esters (Scheme 7).
H
N
H
N
O
P
O
P
1. Me3SiBr/CH3CN
2. aqMeOH
COOH
COOH
HO
HO
EtO
EtO
*
*
R
R
15,
> 90%
10
*
*
COOH
COOH
N
N
1. Me3SiBr/CH3CN
2. aqMeOH
P
P
O
OEt
O
OH
HO
OEt
11
16,
> 90%
Scheme 7

GREEN SYNTHESIS OF β-AMINOPHOSPHORYL COMPOUNDS
705
CONCLUSION
It seems reasonable that acceleration of the aza-Michael addition in ionic liquids
in the presence of water or in water alone is promoted by hydrogen bond formation
between the H-atom of water with the oxygen atom of the phosphoryl moiety, increasing
the electrophilic character of the β-carbon atom, and between the H-atom of the amine
with the oxygen atom of water, resulting in increased amine nucleophilic properties. The
higher reaction rate in the IL/water biphasic systems in the case of vinylphosphine oxide 2,
which is nonsoluble in water, may be explained by the possibility of IL to serve as a phase
transfer agent. Although the rate of the aza-Michael addition in water for vinylphosphoryl
compounds is lower than that for more electrophilic α,β-unsaturated carboxylic acid esters,
nitriles, or amides, it proceeds much faster compared to the known procedures for the
synthesis of β-aminophosphoryl compounds, providing excellent yields of both mono- and
diphosphorylated products, including the amino acid derivatives, requiring at the same time
a very simple isolation procedure. Such an effective, cheap, and green approach offers
wide possibilities to prepare a variety of biologically active substances, complexing agents,
or molecular sensors. In general, the wide scope in aqueous synthesis of a variety of β-
aminophosphoryl compounds including optically active ones, which provide 100% atom
economy using readily available starting materials, proceeds in a natural solvent under
mild reaction conditions and results in the desired compounds in high yields without any
by-products after a very simple isolation procedure, satisfying all of the stringent criteria
for classification as a click reaction.31
REFERENCES
1. (a) Balema, V. P.; Wiench, J. W.; Pruski, M.; Pecharsky, V. K. J. Am. Chem. Soc. 2002, 124,
6244–6245; (b) Kabachnik, M. M.; Zobnina, E. V.; Belezkaya, I. P. Synlett 2005, 1393–1396;
(c) Kabachnik, M. M.; Villemson, E. V.; Belezkaya, I. P. Russ. J. Org. Chem. 2008, 44, 1580–1584;
(d) Keglevich, G.; Szekre´nyi, A.; Sipos, M.; Luda´nyi, K.; Greiner, I. Heteroat. Chem. 2008, 19,
207–210.
2. Plechkova, N. V.; Seddon, K. R. Chem. Soc. Rev. 2008, 37, 123–150 (and references cited
therein).
3. (a) Desimone, J. M.; Tumas, W. Green Chemistry Using Liquid and Supercritical Carbon
Dioxide; McGraw-Hill: Oxford, UK, 2003; (b) Kerton, F. M. Alternative Solvents For Green
Chemistry; RSC: Cambridge, UK, 2009.
4. Aymonier, C.; Loppinet-Serani, A.; Revero´n, H.; Garrabos, Y.; Cancell, F. The Journal of Super-
critical Fluids 2006, 38, 242–251.
5. (a) Grieco, P. A. Organic Synthesis in Water; Blackie Academic and Professional: London, 1998;
(b) Li, C.-J.; Chan, T.-H. Comprehensive Organic Reactions in Aqueous Media; Wiley & Sons:
New York, 2007; (c) Li, C.-J. Chem. Rev. 2005, 105, 3095–3166.
6. Odinets, I. L.; Matveeva, E. V. Curr. Org. Chem. 2010, 14(12), 1171–1184.
7. Matveeva, E. V.; Petrovskii, P. V.; Odinets, I. L. Tetrahedron Lett. 2008, 49, 6129–6133.
8. Matveeva, E. V.; Petrovskii, P. V.; Klemenkova, Z. S.; Bondarenko, N. A.; Odinets, I. L. Compt.
Rendus Chem. 2010, 13, 964–970.
9. Pudovik, A. N. Dokl. Akad. Nauk USSR 1951, 80, 65–71.
10. Horiguchi, M.; Kandatsu, M. Nature 1959, 184, 901–902.
11. (a) Palacios, F.; Alonso, C.; de los Santos, J. M. Chem. Rev. 2005, 105, 899–926 (and references
cited therein); (b) Gumienna-Kontecka, E.; Galezowska, J.; Drag, M.; Lataika, R.; Kafarski, P.;
Kozlowski, H. Inorg. Chim. Acta 2004, 357, 1632–1636; (c) Rahman, M. S.; Oliano, M.; Kuok,
H. Tetrahedron: Asymmetry 2004, 15, 1835–1840.

706
E. V. MATVEEVA ET AL.
12. Gue´nin, E.; Herve´, A.-C.; Floch, V.; Loisel, S.; Yaouanc, J.-J.; Cle´ment, J.-C.; Ferec, C.; des
Abbayes, H. Angew. Chem. Int. Ed. 2000, 39, 629–631.
13. (a) Turanov, A. N.; Karandashev, V. K.; Bondarenko, N. A.; Urinovich, E. M.; Tsvetkov, E.
N. Russ. J. Inorg. Chem. 1996, 41, 1658–1663; (b) Maj, M.; Pietrusiewicz, K. M.; Suisse, I.;
Agbossou, F.; Mortreux, A. Tetrahedron: Asymmetry 1999, 10, 831–836.
14. (a) Hii, K. K.; Thornton-Pett, M.; Jutand, A.; Tooze, R. P. Organometallics 1999, 18, 1887–1896;
(b) Rahman, M. S.; Steel, J. W.; Hii, K. K. Synthesis 2000, 1320–1326.
15. (a) Xu, J.-M.; Qian, C.; Liu, B.-K.; Wu, Q.; Lin, X.-F. Tetrahedron 2007, 63, 986–990; (b) Yang,
L.; Xu, L.-W.; Zhou, W.; Li, L.; Xia, C.-G. Tetrahedron Lett. 2006, 47, 7723–7726.
16. (a) Bhanushali, M. J.; Nandurkar, N. S.; Jagtap, S. R.; Bhanage, B. M. Catal. Comm. 2008, 9,
1189–1195; (b) Alleti, R.; Oh, W. S.; Perambuduru, M.; Ramana, C. V.; Reddy, V. P. Tetrahedron
Lett. 2008, 49, 3466–3470.
17. (a) Azad, S.; Kobayashi, T.; Nakano, K.; Ichikawa, Y.; Kotsuki, H. Tetrahedron Lett. 2009, 50,
48–50; (b) Chen, X.; She, J.; Wu, J.; Zhang, P. Synthesis 2008, 3931–3933; (c) Chaudhuri, M.
K.; Hussain, S.; Kantam, M. L.; Neelima, B. Tetrahedron Lett. 2005, 46, 8329–8331.
18. (a) Kobayashi, S.; Kakumoto, K.; Sugiura, M. Org. Lett. 2002, 4, 1319–1322; (b) Kawatsura,
M.; Hartwig, J. F. Organometallics 2001, 20, 1960–1964; (c) Gaunt, M. J.; Spencer, J. B. Org.
Lett. 2001, 3, 25–28.
19. Gimbert, C.; Moreno-Man˜as, M.; Pe´rez, E.; Vallribera, A. Tetrahedron 2007, 63, 8305–8310.
20. Verma, A. K.; Kumar, R.; Chaudhary, P.; Saxena, A.; Shankar, R.; Mozumdar, S.; Chandra, R.
Tetrahedron Lett. 2005, 46, 5229–5232.
21. Lubineau, A.; Auge´, J. Tetrahedron Lett. 1992, 33, 8073–8074.
22. Liu, B. K.; Wu, Q.; Qian, X. Q.; Lv, D. S.; Lin, X. F. Synthesis 2007, 2653–2659.
23. (a) Beletskaya, I. P.; Tarasenko, E. A.; Khokhlov, A. R.; Tyurin, V. S. Russ. J. Org. Chem. 2010,
46, 461–464; (b) Beletskaya, I. P.; Tarasenko, E. A.; Khokhlov, A. R.; Tyurin, V. S. Russ. J. Org.
Chem. 2007, 43, 1733–1736.
24. (a) Ying, A.-G.; Liu, L.; Wu, G.-F.; Chen, G.; Chen, X.-Z.; Ye, W.-D. Tetrahedron Lett. 2009,
50, 1653–1657; (b) Sharma, Y. O.; Degani, M. S. J. Mol. Catal. Chem. 2007, 277, 215–220;
(c) Yadav, J. S.; Reddy, B. V. S.; Basak, A. K.; Narsaiah, A. V. Chem. Lett. 2003, 32, 988–993.
25. Xu, Li.-W.; Li, J.-W.; Zhou, S.-Li; Xia, C.-Gu. New J. Chem. 2004, 28, 183–184.
26. Ranu, B. C.; Banerjee, S. Tetrahedron Lett. 2007, 48, 141–143.
27. Crowhurst, L.; Lancaster, N. L.; Pe´rez Arlandis, J. M.; Welton, T. J. Am. Chem. Soc. 2004, 126,
11549–11555.
28. Kabachnik, M. I.; Mastryukova, T. A.; Aladzheva, I. M.; Kazakov, P. V.; Kovalenko, L. V.;
Matveeva, A. G.; Matrosov, E. I.; Odinets, I. L.; Petrov, E. S.; Terechova, M. I. Teor. Exper.
Khim. 1991, 27, 284–287.
29. Kabachnik, M. I.; Medved’, T. Ya.; Polikarpov, Yu. M.; Yudina, K. S. Izv. Akad. Nauk SSSR Ser.
Khim. 1962, 1584–1589.
30. (a) Bigge, C. F.; Johnson, G.; Ortwine, D. F.; Drummond, J. T.; Retz, D. M.; Brahce, L. J.;
Coughenour, L. L.; Marcoux, F. W.; Probert, A. W., Jr. J. Med. Chem. 1992, 35, 1371–1384;
(b) Bigge, C. F.; Graham, J. U.S. Patent #5,179,085, 1993.
31. Kolb, H. C.; Finn, M. G.; Sharpless, K. B. Angew. Chem. Int. Ed. 2001, 40, 2004–2021.