Contribution of I. p. Beletskaya in the twentieth year successful Russian-French cooperation in catalytic syntheses Текст научной статьи по специальности «Химические науки»

Advances Достижения

Макрогэтэроцмклы

http://macroheterocycles.isuct.ru

Microreview Миниобзор

DOI: 10.6060/mhc180175a

Contribution of I. P. Beletskaya in the Twentieth Year Successful Russian-French Cooperation in Catalytic Syntheses

Anton S. Abel,a and Alexei D. Averinab@

aLomonosov Moscow State University, Department of Chemistry, 119991 Moscow, Russia hA.N. Frumkin Institute of Physical Chemistry and Electrochemistry RAS, 119991 Moscow, Russia @Corresponding author E-mail: alexaveron@yandex.ru

The review covers the research conducted during last two decades and French collaborators in the field of application of the catalysis by transition metal complexes to organic synthesis. It includes the formation of C-N, C-C and C-P bonds, asymmetric catalysis, immobilization of the catalysts on solid supports. A special attention is paid to the application of the Pd-catalyzed amination reaction to the synthesis of versatile N- and O-containing macrocycles and polymacrocycles.

Keywords: Catalysis, macrocycles, amination, porphyrins, phosphonation.

Вклад И. П. Белецкой в двадцатилетнее успешное российско-французское сотрудничество в каталитических синтезах

А. С. Абель,а А. Д. АверинаЬ@

Московский государственный университет им. М.В. Ломоносова, Химический факультет, 119991 Москва, Россия ьИнститут физической химии и электрохимии им. А.Н. Фрумкина РАН, 119991 Москва, Россия ®Е-шаИ: alexaveron@yandex.ru

Обзор посвящен исследованиям, проводившимся в течение 20 последних лет совместными усилиями группы академика И. П. Белецкой и французскими коллегами в области использования катализа комплексами переходных металлов для органического синтеза. Рассмотрены реакции образования связей СС-С и С-Р, асимметрический катализ, иммобилизация катализатора на твердые подложки. Особое внимание уделено применению Pd-катализируемого аминирования в синтезе разнообразных азот- и кислородсодержащих макроциклов и полимакроциклов.

Ключевые слова: Катализ, макроциклы, аминирование, порфирины, фосфонирование.

Beginning from 1970s, since the origins of this prominent and extremely fruitful trend in organic chemistry, Professor I. P. Beletskaya has been always deeply interested in the studies of transition metal catalysis and its application to the synthesis of various organic compounds. This mini-review covers a restricted but nevertheless very important and interesting sphere of her investigations, namely, the research in catalysis carried out in a close cooperation with French partners. It is needless to say that international connections contribute much in enhancing efficiency

and versatility of the research, and the material present below will undoubtedly support this idea.

Prof. Beletskaya started her mutual investigations with the reactions of the catalytic C-P bonds formation. Together with Prof. Genet (that time working at Chimie Paris Tech) the conditions for the phosphonation of terminal alkynes were elaborated and it was found out that Pd(0) complex with the simplest phosphine ligand PPh3 afforded corresponding alkenes, the products of a-phosphonylation of the triple bond in high yields (Scheme 1). These compounds were further

Pd,(dbaVPPh,

Ar

Ar

H2 Ru-catalyst Ar

AC-CH t HP(0)<0Et), P^ba)3CHCI3/PP^ =< H;, Ru-Calalyst or -X *" l+ÎÎSCt.

HCOONH4. Pd/C-catalyst ^ 6-MeO^-Nf R = H. Et

77-86% ee

Ar

O R = Et

phosphine ligands I pph2 Me0

MeOv

PPh2 MeO ,PPh2 MeO

(S)-BINAP (R)-MeO-BIPHEP (R)-2-furyl-MeO-BIPHEP (R,R)-Me-DuPHOS Scheme 1. Pd(0) catalysis in C-P bond formation; Ru(II) catalysis in asymmetric hydrogénation.

converted into highly demanded chiral a-arylphosphonates by hydrogenation in the presence of RuBr2 complexes with various chiral diphosphines like BINAP, MeO-BIPHEP, 2-furyl-MeO-BIPHEP and Me-DuPHOS. Enantioselec-tivity of the process reached 86 % (Scheme 1).[1,2]

The diphenyl phoshine addition to the triple bond was investigated in the partnership with Prof. Dixneuf (University of Rennes). It was demonstrated that the catalytic addition of Ph2PH to phenylacetylene regioselectively led to the Ph2P-CH=CHPh isomer in the presence of Pd(PPh3)4 in acetonitrile and to the Ph2P-C(Ph)=CH2 isomer when using Ni(acac)2/(EtO)2P(O)H in benzene. Very high regioselectivity was also observed in the catalytic addition of Ph2PH to tert-butylacetylene and tolane (Scheme 2).[3] In all cases near to quantitative yields of the addition products were obtained.

Next step in the application of transition metal catalyzed reactions was a thorough investigation of the C-N bond formation via Pd-catalyzed amination of aryl halides. The process found independently in mid 1990s by Buchwald, Hartwig and Beletskaya,[4-6] was applied to the aryla-tion of diamines and polyamines. This aspect of the catalytic amination became the domain of Prof. Beletskaya for two decades to come. A fruitful and long-run cooperation with Prof. Guilard (University of Burgundy, Dijon) began from the investigation of the conditions for selective mono-, di-and exhaustive arylation of di- and polyamines (Scheme 3). It was established that the application of PdCl2(dppf) complex with additional amount of dppf in boiling dioxane was helpful for selective monoarylation of diamines and poly-amines with various aryl bromides provided polyamines

Ph-

Ph Ni(acac)2/(EtO)2P(Q)H " + Pd(PPh3>4 ,

Ph/ benzene, 80°C ph*pH MeCN, 130°C

90%

Ph — Ph + ph,PH

Ni(acac)2 benzene, 80°C ph p'

Ph^_PPh2

95%

Ph Ph

98%

Scheme 2. Pd(0) vs Ni(II) catalysis in the triple bond phosphorylation.

H

up to 95%-* PdCI2(dppf)/dppf

Hal = Br, CI up to 95%

Pd(dba)2/dppf or BINAP

H Pd(dba)2/dppf

T>ai

h2N^X^NH2 = H2N^nh* H2N"^"NH2 H2N

h2n

"nh2 h2n'

H H

up to 92%

Pd(dba)2/BINAP Ak

N X N i i Ar Ar

up to 95%

,Ar

Scheme 3. Studies of the Pd(0)-catalyzed amination of linear di- and polyamines. Макрогетер0циmbl/Macroheterocycles 2018 11 (2) 126-134

were taken in excess. In all reactions sodium tert-butoxide was used as a base. This protocol allowed up to 95 % yields of the target products.[7] The main feature of this approach was selective arylation of only primary amino group in the presence of secondary amino groups. This exciting finding was further successfully applied in numerous reactions employing different polyamines. In the case of active aryl bromides Pd(dba)2/dppf catalytic system could be used for the A,A'-diarylation while in other reactions Pd(dba)2 with a more efficient BINAP ligand should have been used. The same catalyst but in greater amounts was shown to be efficient for polyarylation of diamines also providing excellent yields of the desired products.[8]

The possibility to selectively substitute one halogen atom in the presence of another in dihalobenzenes was shown also using Pd(dba)2/dppf catalytic system, and the priority of the substitution in the range I>Br>Cl was firmly established.^10 Key role of Dr. A. Bessmertnykh-Lemeune in the elaboration of this fruitful approach to versatile poly-amines modifications leading to linear and macrocyclic derivatives as well as in their further use in the chemistry

of chemosensors and organo-inorganic materials is to be underlined.

The scope of Pd(0)-catalyzed arylation of di- and polyamines was elucidated and appropriate catalytic systems were selected for further proliferation of this method which was applied in the synthesis of novel series of N-and O-containing macrocycles in the course of a close cooperation between the group of Prof. Beletskaya and French colleagues from Dijon (Scheme 4).

The protocol for Pd(0)-catalyzed macrocyclization implies the reaction of dihaloarenes or dihaloheteroarenes (preferably dibromides) with polyamines taken in equi-molar amounts. Enough diluted solutions (0.01-0.04 M) in dioxane should be used to suppress competing formation of cyclic and linear oligomers. The most universal catalytic system Pd(dba)2/BINAP was shown to be appropriate in the majority of cases. The first attempts to introduce the simplest 1,2-dibromobenzene in the macrocyclization failed, however, 2-bromo-1,3-dichlorobenzene successfully reacted with a variety of polyamines and oxadiamines to give corresponding macrocycles in yields up to 47 %.[11]

n

n\r~\

HN X NH

Scheme 4. Pd(0)-Catalyzed amination in the synthesis of polyazamacrocycles.

This approach was extended to the derivatives of 1,3-disub-stituted benzene and in this case the highest yield was 56 % what can be regarded as a big success.[12] Further investigations were carried out by exploiting different aryl dihalides as building blocks for the new macrocycles. It was shown that 2,7-dibromonaphthalene could be successfully transformed into naphthalene-containing macrocycles by (1+1) cycloaddition reactions.[13] The possibility to form so-called cyclic dimers comprising two naphthalene and two poly-amine fragments was investigated via two alternative two-step processes.[14] In the reactions with 2,7-dibromonaphtha-lene another catalytic system, Pd(dba)2/DavePhos, in some cases demonstrated its utility. Similar protocols were applied to the synthesis of biphenyl-containing macrocycles which were synthesized in yields up to 44 %.[15-17] It should be noted that in every case the dependence of the reaction outcome on the structure of polyamines was investigated.

An interesting investigation was conducted with 1,8- and 1,5-dichloroanthracenes and anthraquinones.[18-20] The macrocyclization was quite successful with dichlorides, moreover, in the case of dichloroanthraquinones cesium carbonate instead of sodium tert-butoxide was employed as starting compounds did not tolerate this stronger base. Further development of this approach led to the application of chiral phosphine ligands like (R)-BINAP or ferrocene-based ligands of Josiphos series for enantioselective synthesis of planar-chiral macrocycles based on 1,5-disubstituted anthracene and anthraquinone. The best enantiomeric excess reached 60 %.[21] Another research direction was the synthesis of colo-rimetric detectors for metal cations using cyclic and non-cyclic polyamino derivatives of anthraquinone, this became possible due to intensive absorption of such compounds in visible region (ca 520-530 nm). The decoration of the compounds with amidophosphonate arms in order to provide solubility in water resulted in the creation of several selective molecular sensors for Cu(II) and Pb(II) cations (Figure 1).[2223]

The importance of the introduction of heteroaro-matic moieties as endocyclic fragments is obvious as they can profoundly modify binding properties of macrocycles and contribute useful optical and physicochemical properties. Thus the elaboration of the synthesis of pyridine-based macrocycles was conducted using 2,6- and 3,5-dihalopyri-dines and a wide range of polyamines.[24-27] Corresponding macrocycles were obtained in yields ranging from near trace to 42 % depending on the polyamine used, and cyclic dimers with larger cavity sizes were also synthesized. This

investigation was helpful for the further synthesis of valuable macrocycles based on 6,6'-diamino-2,2'-bipyridine. [28] One of the products, the macrocycle with trioxadiamine chain, was tested as a colorimetric and fluorescent detector of some metal cations. Later on the synthetic procedures leading to 1,10-phenanthroline-based and quinoline-based macrocycles were worked out, in these reactions the standard Pd(dba)2/BINAP was found to be less efficient, thus the ligands DavePhos and Josiphos were applied in order to increase the yields up to 32-35 %.[2930] In the case of phenanthroline-based macrocycle with trioxadiamine chain its Ru(II) complex with additional bipyridyl ligands was synthesized which was tested as an efficient fluorimetric sensor for Cu(II) cations. Quinoline-based macrocycles were equally shown to be applicable as fluorimetric detectors of the same metal. Thus the Pd(0)-catalyzed amination for macrocycles construction contributes to the solution of the problem of heavy and toxic metals detection.

The methodology of Pd(0)-catalyzed macrocycliza-tion was tried in the synthesis of ¿ismacrocyclic compounds in view of producing polytopic macrocyclic receptors for metal cations. In order to achieve this goal the aryla-tion of the secondary amino groups should have been carried out. In this connection the formation of ¿is(cyclen) and ¿is(cyclam) derivatives with rn-phenylene spacer was thoroughly investigated,[31] and a meticulous adjustment of the reaction conditions allowed to synthesize target molecules in yields up to 32 % overcoming almost inevitable catalytic reduction of the second bromine atom (Scheme 5). For this purpose the application of N,N',N''-trimethylsubstituted tetraazamacrocycles was important. The introduction of two tetraazamacrocycles or two azac-rown ethers to positions 1 and 8 of the anthracene moiety helped to synthesize compounds with face-to-face arranged macrocycles. However, the amination process was accompanied by the reduction of the second chlorine atom and the yields of the target ¿ismacrocycles were enough

humble.[32]

The difficulty of the diamination of dihaloarenes with compounds bearing secondary amino groups was partially overcome in the syntheses of trimacrocycles when N,N'-¿is(bromobenzyl) derivatives of cyclen, cyclam and diazac-rown ethers were employed in the reactions with azacrown ethers (Scheme 4). The catalytic system Pd(dba)2/DavePhos was helpful and corresponding trimacrocycles were isolated in better yields reaching 45-46 %.[3334]

(EtO^OJP^N^O

o

O HN

colorimetric sensor for Cu(ll)

(Et0)2(0)P^N^0 O

A N^

(EtO^P^N^--""

(EtOMOJp-^N-^S O HN

PO(OEt)2 NH

(EtO)2OP\ O^S PO(OEt)2

"V VNH

° L J0

NH O HN

colorimetric sensor for Cu(il) and Pb(ll)

colorimetric sensor for Pb(ll)

Figure 1. Colorimetric chemosensors derived from polyamine-substituted anthraquinones. Макрогетер0циmbl/Macroheterocycles 2018 11 (2) 126-134

Me

.Me

с ) П

Ме'^ме M/U- BrÜB

up to 25% -

N N Me' "Me

ч /—л f \ ,Me

, "N JíJ^Í N"\ >^nJ 4V>

w Me Me ^ up to 32%

Pd(dba)2/DavePhos, fBuONa,

С

dioxane

Г

N

MeN ГЛ ,H

cN

N N Me \_I Me

Г

С °

-N N

Br n = 0, 1

m-Br, p-Br

Pd(dba)2/DavePhos fBuONa, dioxane

Me

I/

rN Ni r^OrO

Pd(dba)2/BINAP NaOfBu, dioxane ,

-л

10%

V b с^ЦсА,

/ H о \ JN0 J

11%

с

л.

NH NC N HN'

M

'Br

С

л

NH N N HN

Br

О mim-^

о о

w

m = 1, 2 2 equiv.

Br

n = 0,1 m-Br, p-Br

Pd(dba)2/DavePhos iBuONa, dioxane

H ^

ry 4°

о O-

up to 45%

up to 46%

Scheme 5. Pd(0)-Catalyzed amination in the synthesis of polymacrocyclic compounds.

The approach to cryptand-type macrobicycles implies the introduction of two bromobenzyl moieties in the structure of the first macrocycle followed by the Pd(0)-catalyzed macrocyclization. Above mentioned macrocycles based on 2,7-disubstituted naphthalene and 3,3'-disubstituted biphenyl moieties were modified with two bromobenzyl fragments followed by macrocyclization with various polyamines and oxadiamines to provide corresponding cryptands in yields up to 30-35 %.[3536] Much more versatile cryptands were synthesized on the basis of trans-N, N'-di(bromobenzyl) substituted cyclen and cyclam. At first the scope and limitations of this approach were determined to demonstrate the possibility of the synthesis of the cryptands in yields up to 45 %, the formation of interesting by-products, cylindri-cally shaped macrotricycles, was noted in many cases.[37] The possibility to synthesize macrobicycles with pyridine-containing spacers was also shown though the maximal yields were lower.[38] Important cryptands bearing two naphthalene spacers were obtained by the similar approach,[14] and later on the family of macrobicycles and macrotricyles was extended to compounds with tetrabenzyl- and dibenzyldipyrimidinyl substituted cyclen or cyclam central moieties.[39,40] Unusual bicyclic conjugates of tetraazamacrocycles with 1,3-disub-stituted adamantane were described,[41] and the investigation of the synthesis of planar-chiral macrobicycles derived from tetrasubstituted cyclam with short diamine linkers unable to rotate around the cyclam moiety was carried out using a panel of chiral diphosphine ligands.[42] Quite different architecture of macrotricylic compounds, i.e. spherically shaped cryptands, was developed by a stepwise accomplishment of the catalytic macrocyclization reactions.[43] The possibility

to obtain another representatives of heteroditopic cylindrical cryptands was achieved by the combination of tetraazamac-rocycels with end-capping diazacrown ether moieties.[33]

Thus, a great variety of various macropolycycles differing by the number of nitrogen and oxygen atoms and cavity sizes can be obtained using the described general approach. Now these compounds are being further modified to create fluorescent chemosensors for metal cations and small organic molecules. More detailed information on the Pd(0)-catalyzed amination aimed at the synthesis of linear (hetero)aryl derivatives of polyamines can be found in ref.[44] while the syntheses of macrocycles and polymacro-cycles are collected in the following reviews.[45-47]

The interests of Prof. Beletskaya cover the chemistry of porphyrins as well. During last decade she boosted the research of the catalytic transformations of these important molecules. As the porphyrins have been always very important research domain at the University of Burgundy, two joint reviews were published. One is a chapter in a profound Handbook of Porphyrin Science dedicated to catalytic transformations of porphyrins[48] while another one is a deep review of the supramolecular chemistry of metalloporphyrins in Chemical Reviews.[49]

Different aspects of catalysis were also the ground for the collaboration with F. Lamaty (University of Montpellier). One was the studies of the amination reactions run in poly(ethylene) glycols under microwave irradiation catalyzed by copper and amino acids as ligands. The best results were achieved with CuO/Z-histidine in PEG-400. Also the N-arylation of amino acids without additional ligands in PEGs catalyzed by Cu2O was studied (Scheme 6).[50]

up to 35%

h-n n-h

n = 1, up to 29% n = 2, up to 13%

up to 31%

fVi^

k ) >-NH > HN f

fW f

Ar = m-C6H4 n = 0, up to 45% Ar = p-C6H4'n = 0, up to 47% Ar = m-C6H4 n = 1, up tp 34% Ar = p-C6H4i'n = 1, up to 28% Ar = 3-Py, n = 0, up to 32% Ar = 3-Py, n = 1, up to 19% Ar = 2-Py, n = 0, up to 23% Ar = 2-Py, n = 1, up to 11%

NH HN

NH HN

Ph—\

N N. ' n

H

up to 35%

n = 1, m-NH, up to 31% n = 1, p-NH, up to 20% n = 2, m-NH, up to 24% n = 2, p-NH, up to 18%

<rrifV*-

n = 1, up to 32% n = 2, up to 14%

n = 1, m-NH, up to 15% n = 1, p-NH, up to 18% n = 2, m-NH, up to 10% n = 2, p-NH, up to 19%

Q „ ^^ a—n ^rO^x^vQ

N > c© CVC ^) " H )

C. J

NH

,n n;

o

H

n = 1, m-NH, up to 19% n = 1, p-NH, up to 31%

n = 1, m-NH, up to 31% n = 1, p-NH, up to 17%

Boo.

c

N N

N N

Boo

H

__^N N-

O HN

HN-

-O 24%

f „ oJ

30%

Figure 2. Versatile architecture of polymacrocyclic compounds obtained by Pd(0)-catalyzed amination.

Mutual investigations also dealt with the Cu(I)-catalyzed amination of diamines and oxadiamines for the synthesis of polyoxadiamino derivatives of azacrown ethers, this research was essential for establishing the scope and limitations of the copper catalysis in the modifications of macrocycles in order to replace much more expensive palladium.™

Prof. Beletskaya has been deeply interested in the synthesis of immobilized catalysts for their repeated use. The synthetic approach to chiral Bransted acids like 3,3'- or 6,6'-disubstituted (^)-BINOL phosphoric acids (BINOL=l,l'-binaphthyl-2,2'-diol) bearing either triple bonds or azide groups was developed. Their immobilization using Cu(I)-catalyzed alkyne-azide cycloaddition (CuAAC, "click"-reaction) with azide or propargyl derivative of PEG-5000 was carried out. In the first case the synthetic procedure included 6 steps, in the second

case - 5 steps. As a result, two immobilized (R)-BINOL phosphoric acids with triazolyl cycles in positions 3 and 3' were obtained (Figure 3). The substituents in ortho-position to the acid catalytic center are necessary to achieve higher enantiomeric excess compared to unsubstituted (R)-BINOL phosphoric acids. Both immobilized acids showed catalytic activity in the Pudovik reaction and in the imines reductions using Hantzsch ester. Products yields were good and did not decrease in 3 cycles, however, enanti-oselectivity was 23 % ee in the Pudovik reaction and 26 % ee in the reduction reaction. To note, the introduction of the substituents in positions 3 and 3' led to a twofold increase in enantioselecivity.[52]

Another aspect is the preparation of hybrid organo-inorganic materials for catalysis and detection. The approach to the precursors of interesting building blocks, cyclopropane-based diphosphonic esters, was elaborated, a key step

Ú

ArX 2 equiv.

G

N CuO/L-His (10/20 mol%) ^

H PEG-400, Cs2C03 (2 equiv.), MW, 150°C Ar

r PhHIg (Hlg = I, Br) ^

HjN^COOH cu20 (10 mol%), Cs2C03 (3 equiv.) ^^ COOH

PEG-400, MW

^NpCOOH Ph.NXCOQH PluNXCOOH

H H

Ia Phl V

COOH ^N tOOH Ph^NACOOH H H H

Scheme 6. Copper-catalyzed amination conducted in PEGs.

Figure 3. PEG-supported chiral BINOL-phosphoric acids.

=<

NHCHO

P(0)(0Me)2

X = Br

-N2

XHQ>-CHN2

X = P(0)(0Et)2

- HC(0)NH2

(Et0)2(0)P-

NHCHO Pd-catalysis

<

P(0)(0Me)2

NHCHO

P(0)(0Me)2

R = P(0)(0Et)2, 4-(Et0)2P(0)-C6H4, frans-(Et0)2P(0)-CH=CH

P(0)(0Me)2

Scheme 7. Formation of cyclopropane-based diphosphonic esters.

being the introduction of the second phosphorus in the molecules by means of Pd catalysis (Scheme 7).[53]

The first step of the research dealing with immobilized copper catalysts was the synthesis of mono- and diphos-phorylated 1,10-phenanthrolines. For this purpose a general protocol for the coupling of mono- and dihalo-1,10-phenan-throlines with diethyl phosphite was elaborated featuring the Pd(OAc)2/dppf catalytic system and triethylamine taken as a base.[54] Further on two series of copper(I) complexes with diethoxyphosphoryl substituted 1,10-phenanthroline ligands were synthesized and characterized in the solid state and in solution. The first comprised mixed-ligand CuI complexes with phenanthroline and triphenylphosphine,

the second series included ¿«chelates with two phenanthroline ligands, both were studied using NMR and X-Ray technique.[55] Diethoxyphosphoryl substituted 1,10-phen-anthroline copper(I) complexes were tested as catalysts in the Sonogashira-type reaction, a-arylation of phos-phoryl-stabilized C-H acids, C-N, C-P bond forming reactions (substitution reactions) and in the reaction of phenyl-acetylene and 6/'s(pinacolato)diboron (addition reaction). The complexes demonstrated fairly high catalytic activity and in some cases their efficiency was superior to that of the parent Cu(phen)(PPh3)Br (phen = phenanthroline).[56] Such fruitful collaboration with the chemists from Dijon resulted in the synthesis of the immobilized copper

TiO,

/=</-^P(0)(OSiMe3)2 Srft~590 m2/g ' J CH2CI2

Cu(MeCN)4BF4 CH2OI2

TiO,

Ti02(Cu(3-Pphen))

+ = // w 5mol% \

■=/ 16 h, Cs2C03, PPh3 toluene, 110 °C

O

99%, 5 cycles without loss of activity

f\

Ti02(Cu(3-Pphen)) N

1 mol%

THF, Et3N, 50°C

99%, 10 cycles without loss of activity

Scheme 8. Grafted copper complexes with phenanthroline and their use in the catalysis.

catalyst. Different strategies for the immobilization of copper complexes with 1,10-phenanthroline (phen) using the phos-phonate anchoring group were investigated to prepare robust and porous heterogeneous catalysts. Homoleptic and heteroleptic copper(I) complexes with phenanthro-line bearing the 6/'s(trimethylsiloxy)phosphoryl anchoring group (Pphen-Si) at different positions of the phenanthro-line backbone were prepared and covalently incorporated into titania (TiO2) xerogels by using the sol-gel process or grafted onto the surface of mesoporous TiO2 (SBET = 590 m2/g). Copper(I) £/'s(Pphen-Si) complexes were the only complexes that were successfully anchored onto the TiO2 surface because the heterogenization was often accompanied by the undesirable dissociation of copper complexes. Hybrid materials based on copper(I) chelates with one phenanthroline ligand were obtained following a two-step procedure involving the immobilization of Pphen-Si chela-tors and their successive complexation with copper(I) ions. Porous material was synthesized according to this approach and excellent catalytic performance of this reusable immobilized complex in the Sonogashira-type coupling and the Huisgen 1,3-dipolar cycloaddition was also demonstrated (Scheme 8).[57] The catalyst can be recycled 5 times without loss of activity.

Acknowledgements. The research was carried out in the frames of the ARCUS Burgundy-Russia Project (2007-2010) and LIA LAMREM Joint Laboratory (2011-2019), it was supported by the following grants: INTAS 97-1874, PICS 2105, RFBR 03-03-32627, 03-0322001, 06-03-32376, 08-03-92505, 09-03-00735, 12-0393107. The financial support of the French Embassy and French Government is highly appreciated.

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Received 06.02.2018 Accepted 22.02.2018