metal complex catalysis in organic and organometallic...

Chemistry for Sustainable Development 16 (2008) 621�632 621

Metal Complex Catalysis in Organicand Organometallic Synthesis

U. M. DZHEMILEV

Institute of Petrochemistry and Catalysis, Ufa Scientific Centre of the Russian Academy of Sciences,Pr. Oktyabrya 141, Ufa 450075 (Russia)

E-mail: [email protected]

Abstract

Some directions and results of scientific research in the field of metal complex catalysis initiated byAcademician G. A. Tolstikov as well as new directions successfully developed today by his followers areconsidered. The main attention is given to reactions, efficient reagents and promising preparatory methodsof metal complex catalysis in organic and organometallic synthesis.

Key words: catalysis, organic and organometallic synthesis, unsaturated compounds, scientific school ofAcademician G. A. Tolstikov

Contents

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 631 Hydroperoxide oxidation of organic compounds catalyzed by molybdenum complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 631Organic and organometallic synthesis with the participation of metal complex catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 634Catalytic ethylmagnesiation of olefins with non-activated double bond by means of RMgX and R2Mg . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 638Novel reactions of organometallic compounds of non-transition metals . . . . . . . . . . . 639Prospects of the further research development in the field of metal complex catalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 641Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 642

INTRODUCTION

January, 2008 marks the 75th anniversaryof Academician of the RAS G. A. Tolstikov,an outstanding organic chemist, the head ofa brilliant scientific school of chemists. Theachievements of this scientific school areknown far outside our country; it supports ahigh authority of Russia on the Internationalscientific Olympus.

The present review is devoted to theconsideration of some key directions of researchinitiated by Academician G. A. Tolstikov in thefield of metal complex catalysis with referenceto the problems of chemistry of unsaturatedcompounds. For the objective analysis of theachievements, as well as for distinct ranging

ideas put forward and realized by G. A. Tol-stikov�s scientific school the results obtained areexpounded according to a chronological sequencecovering both the Ufa period of AcademicianG. A. Tolstikov�s activity (1970�1994) and the nextyears of his work in the Vorozhtsov NovosibirskInstitute of Organic Chemistry, SB RAS.

HYDROPEROXIDE OXIDATION OF ORGANIC COMPOUNDS

CATALYZED BY MOLYBDENUM COMPLEXES

One could say with no exaggeration that theresearches in the field of hydroperoxide oxi-dation of organic compounds under the actionof transition metal complexes initiated by Pro-fessor G. A. Tolstikov in the beginning of

622 U. M. DZHEMILEV

by an activated hydroperoxide molecule to re-sults in the formation of difficult to obtainβ-oxides of ∆5-steroids [3].

The studies carried out have demonstratedthat the reaction of β-epoxidation of ∆5-ste-roids and other related natural compounds bymeans of hydroperoxides in the presence ofÌî-containing complex catalysts is of generalnature, and it offers new possibilities in thefield of the synthesis of stereochemically in-accessible derivatives from various classes oforganic compounds.

Moreover, in the next experiment concern-ing the epoxidation of diosgenine acetate by theexcess of tert-amyl hydroperoxide in the pres-ence of catalyst wherefore MoCl5 was used, theresearchers obtained acetate such as 5-oxa-6-ketodiosgenine with a high yield instead of theexpected α-oxide of corresponding ∆5-steroid [4].

We have not realized at once that we had dis-covered the reaction of one-stage oxyketonationof olefines with triply substituted double bond.The subsequent research concerning the marginsof application for the method mentioned by theexamples of oxyketonation of steroids, mono-,di- and triterpenes have demonstrated that thereaction is of general nature and it could be wide-ly used in synthetic practice.

Basing on the experimental results obtainedG. A. Tolstikov have proposed the most proba-ble scheme of the mechanism for the forma-tion of oxyketones:

1970ths at the Institute of Chemistry, Bash-kiria Branch of the USSR Academy of Sci-ences (nowadays the Institute of Organic Chem-istry, Ufa Scientific Centre of the RAS), aswell as the accumulated experimental opera-tional experience in this field have formed astrong basis for expanding fundamental andapplied works for the next years according tothe scientific direction �Metal complex cataly-sis in organic and organometallic synthesis� [1].

At the first stage we have engaged in thestudies on the stereochemistry of epoxidationof olefines (by the example of ∆5-steroids) bymeans of tert-amyl hydroperoxide, catalyzedby molybdenum complexes. It has been estab-lished that the operation with hydroperoxidesless hazardous than with such classical epoxi-dizing reagents as peracids widely used in syn-thetic practice.

It should be noted that by the moment ofbeginning the studies on the hydroperoxide ox-idation the works by V. Bril, M. Sheng andD. G. Zayachek concerning the epoxidation ofsimplest olefines by means of such hydroper-oxy species as tert-butyl, tert-amyl, ethylben-zene and cumene hydroperoxides, with the par-ticipation of Ti, V, W, Cr and Mo complexesas catalysts had been already published in theworld literature. The best results have been ob-tained with the complexes of molybdenum.

G. A. Tolstikov first has suggested to studythe stereochemistry of hydroperoxide-basedepoxidation basing on classical objects such asnatural steroids and terpenes [2]. The first ex-periments concerning the oxidation of ∆5-ste-roids have demonstrated that the stereochem-istry of hydroperoxide epoxidation fundamen-tally differs from stereoselectivity of other ep-oxidizing reagents described elsewhere. In eachexperiment mainly β-oxides were obtained,whereas other reagents resulted in the forma-tion of mostly α-oxides. These results indicatedthe attack of the double bond in ∆5-steroids bysuch a reactant as hydroperoxide- salt molyb-denum to proceed from the most shielded β-side.

A detailed investigation of the mentionedeffect has allowed the researchers to establishthat the this reagent is first of all coordinatedwith the heteroatom bound with Ñ3-β atom of∆5-steroids from the least shielded α-side. Fur-ther there proceeds a β-attack of double bond

METAL COMPLEX CATALYSIS IN ORGANIC AND ORGANOMETALLIC SYNTHESIS 623

It has been established, that the reagentmentioned exhibits a high stability, whereasas far as the oxidizing ability is concerned, it issimilar to that of meta-chloroperbenzoic acidwidely used abroad.

By analogy with the method for meta-carb-methoxyperbenzoioc acid we have for the firsttime obtained stable pentafluoroperbenzoic acid,which pentafluoroperbenzoic acid surpasses allthe peracids known up till now in reactivity [8].

So, after the oxidation of ald- and ketazinesof meta-chloroperbenzoic acid we obtained ox-ides of azines those thermally decomposed un-der the conditions chosen and converted intocorresponding esters of meta-carbmethoxyben-zoic acid according to the following scheme [9]:

The results obtained have led me to the ideathat peracid in this reaction could be replaceby a reagent such as hydroperoxide�molybde-num in order to obtain corresponding olefins.This idea has been successfully realized withketazines obtained from cyclic ketones

Homolytical transformations presented in thisscheme are based on the chemistry of alkylhy-droperoxides. However, these reactions havebeen considered without taking into account therole of intermediate molybdenum complexes.

Further this fertile scientific field was pro-foundly and carefully �ploughed� by Dutchchemist K. B. Sharpless who succeeded in estab-lishing a detailed mechanism for hydroperox-ide oxidation of olefins catalyzed by transitionmetal complexes as well as identifying the struc-tures of catalytically active complexes. For theseworks K. B. Sharpless has been rewarded withthe Nobel Prize in 2001.

After obtaining so bright results with respectto the hydroperoxide subject G. A. Tolstikov hascharged me with studies of the synthetic po-tentialities of such reagent as hydroperoxide �molybdenum salt in oxidation reactions for var-ious classes of organic compounds � amines (in-cluding nitrosoamines), nitrogen-containing het-erocyclic compounds, sulphides, sulphoxides,dehydropyridines, alcohols, and carbohydrates.

We have found that the reagent mentionedis not only competitive with classical oxidizingreagents in particular, peracids) for the efficien-cy, reaction selectivity and preparative value,but also surpasses them in the availability andthe simplicity of performing the reaction [5, 6].

In addition, another reaction which we havediscovered during these studies should be men-tioned. In the middle of 1975 Prof. A. M. Moi-seenkov (Zelinsky Institute of Organic Chem-istry, RAS, Moscow) and Prof. G. B. Bylina(Byelorussia) have suggested us to engage inthe studies on oxidizing capabilities such a newreagent as meta-carbmethoxyperbenzoic acidformed in the meta-carbmethoxybenzaldehyde(a waste from tetraphtalic acid manufacture)oxidation by ozon-oxygen mixture [7].

624 U. M. DZHEMILEV

Thus, we have succeeded in discovering an-other reaction that can allow researchers to con-vert cyclic ketones into olefins with a high yieldusing only one preparative stage [10].

By the middle of 1975 the studies in thefield of hydroperoxide oxidation were almostcompleted and a new stage began such as ametal complex period which proceeds to thisvery day as well. At the initial stage of theseresearches we have engaged in cyclooligomer-ization of conjugated dienes.

A primary goal formulated by G. A. Tolsti-kov consisted in mastering the reactions of iso-prene cyclodimerization and trimerization toproduce 1,5-dimethyl-cis,cis-cyclooctadiene and1,5,9-trimethyl-trans,trans,trans-cyclododecatri-ene, respectively [11].

To the point, the studies in this directionhave just begun with solving the mentionedproblem, and for the next years new problemsappeared and the first successes of G. A. Tol-stikov�s scientific school have exhibited in thefield of chemistry conjugated dienes with theparticipation of complex catalysts [12�14].

In several years these studies were alreadybeing performed according to the following pro-spective directions:

. Linear and cyclic oligomerization of conju-gated dienes and olefins including strained onesunder the action of metal complex catalysts.

. Heterocyclization of conjugated dienes withsmall molecules and atoms, as well as aliphat-ic, aromatic and heteroaromatic primary àìèíîâwith carbonyl compounds.

. Metal complex catalysis in the chemistryof organosulphur compounds.

. Catalytic telomerization of conjugated dieneswith compounds containing labile hydrogen atoms.

. Hydro- and carbometallation of olefins bymeans of Mg and Al alkyl and hydride deriva-tives with the participation of Ti, Zr, Hf andTa complexes.

This is an incomplete list of scientific re-search directions developed within the periodfrom 1972 to 1991.

Since 1992 the research in the field of or-ganic and organometallic synthesis with theparticipation of metal complex catalysts werecontinued at a newly organized Institute of Pet-rochemistry and Catalysis, RAS (Ufa), and thecollective of researchers engaged in the afore-mentioned work has concentrated the efforts onthe development of the following directions:

� Cyclometallation of olefins, acetylenes,allenes by means of Mg, Zn, Al, Jn, Ga, Balkyl derivatives catalyzed by Ti, Zr, Hf, Taand Co complexes.

� Chemistry small, medium and giant car-bo-, hetero- and metallocarbocycles on the ba-sis of non-transition metals (Mg, Al, B).

� Selective heterofunctialization of carbon clus-ters with the participation of complex catalysts.

� New organometallic reagents for the cyclo-propanation of acetylenes, allenes and olefins.

� Mechanisms of catalytic reactions with theparticipation of transition metal complexes.

� Multicomponental reactions, catalyzed bytransition metal complexes for the synthesis ofcyclic and acyclic heteroatomic compounds.

ORGANIC AND ORGANOMETALLIC SYNTHESIS

WITH THE PARTICIPATION OF METAL COMPLEX CATALYSTS

Already at the initial stage of coming-to-bethe research in the field of metal complex ca-talysis we postulated the potentiality of apply-ing homogeneous complex catalytic systems forthe synthesis of organosulphur compounds thoserepresent poisons for heterogeneous catalysts.

On short notice we succeeded in consider-able advancing these work and in developing anew research field such as one-stage catalyticsynthesis of cyclic and acyclic unsaturated or-ganosulphur compounds with the participationof homogeneous metal complex catalysts.

The realization of this work program hasallowed us to develop novel fundamental reac-tions, general principles and methods for het-erocyclization of conjugated dienes and acety-lenes with small molecules and atoms as wellas heteroolefins, with the obtaining of a wideclass of practically important sulphur-contain-ing compounds [13, 15].

Some novel reactions developed while per-forming the work program concerning the cre-


Scheme 2. Metal complex catalysis in the chemistry of sulphonic acids and carbon bisulphide.

Scheme 3. Metal complex catalysis in the chemistry of elemental sulphur (S8).

ation of prospective methods for the synthesisof organosulphur compounds, are presented inSchemes 1�3.

The aforementioned cycle of research has beencompleted with the development and manufac-turing application of efficient flocculating agents,hydrogen sulphide neutralizers, bactericides, in-hibitors of sulphate-reducing bacteria, efficientextracting agents and sorbents, pharmaceuticalpreparations for medicine and agriculture.

The representatives of G. A. Tolstikov�s sci-entific school have drawn an important contri-bution to the development of one of the mostprospective and promising directions of mod-ern chemistry such as catalytic activation ofsmall and low-stable molecules in the reactionswith conjugated dienes, and acetylenes.

Moreover, they have performed prioritystudies on the catalytic activation of carbondioxide, formaldehyde, carbon disulphide,water, ammonia with the obtaining of practi-

Scheme 1.

626 U. M. DZHEMILEV

Scheme 4. Metal complex catalysis in the chemistry of small molecules and atoms.

Scheme 5. Novel reactions in the synthesis of linear isoprenoids.

Scheme 6. Metal complex catalysis in the chemistry of compounds containing a labile hydrogen atom.


Basic research in the field of chemistry ofnitrogen-containing heterocycles have resultedin the development of general methods for thesynthesis of pyridines, quinolines, naphthyri-dines and phenantrolines prospective for prac-tical realization, based on multicomponent con-densation of aliphatic and aromatic amines withcarbonyl compounds as well as co-trimerizationof acetylenes with nitriles under the action ofmetal complex catalysts [16].

Together with our colleagues from the labo-ratory No. 5 of the Zelinsky Institute of Or-ganic Chemistry, RAS (head of the laborato-ry being Academician O. M. Nefedov) we havedeveloped a new strategy for single-stage cat-alytic synthesis of polycyclic compounds withunique structure. New general reactions werediscovered for obtaining strained polycyclic com-pounds constructed of three-, four- and five-membered cycles [17].

As a result, more than 1500 practically im-portant polycyclic hydrocarbons and their de-rivatives were synthesized, as well as physicaland chemical properties; stereochemistry andenergy characteristics have been studied for themost promising samples whose manufacture wasmastered on an experimental industrial scale.

cally important oxygen-, nitrogen- and sulphur-containing heterocycles, higher amines, alco-hols, carbonic acids and other valuable multi-functional compounds (Scheme 4) [13].

Novel reactions developed according to thisdirection were used for the synthesis of prac-tically important isoprenoids; in particular ci-tral, farnesol and other derivatives were ob-tained (Scheme 5).

The researchers G. A. Tolstikov�s scientificschool have accomplished one of the most large-scale programs concerning catalytic telomeriza-tion of conjugated dienes and trienes with al-iphatic, aromatic and heteroaromatic primaryand secondary amines, alcohols, carbonic andsulphinic acids. This work has resulted in thedevelopment of the methods for the synthesisof higher unsaturated amines, amino acids,aminoalcohols, esters of carbonic and sulphin-ic acids, as well as alcohols (Scheme 6) pro-spective for practical realization [13].

Due to the investigations carried out aimingat the studies on the mechanism of the forma-tion of metal complex catalysts with the par-ticipation of nickel complexes in the reactionsof homo- and co-oligomerization of conjugat-ed dienes, the researchers for the first timesucceeded in introducing into practice of ho-mogeneous metal complex such activatorligands (L) as the esters of ortho- and metabo-ric acids, siloxanes, silatranes, boratranes andsmall molecules (CO2, SO2). Basing on these re-sults, catalytic systems with the activity andselectivity earlier unachievable have been ob-tained both in Russia and abroad.

628 U. M. DZHEMILEV

acetylenes, allenes with the help of alkyl andhydride derivatives of non-transition metals(Mg, In, Al, Zn, Ga, B, etc.) with the partici-pation of Ti, Zr, Hf, Ta, Co and other transi-tion metal complexes as catalysts. As a result,fundamental reactions of carbomagnesiationand carboalumination of α-olefins by means ofRMgR′, Et2AlCl, AlEt3 with the participationof complex catalysts based on Ti and Zr com-pounds have been developed [18�22].

CATALYTIC ETHYLMAGNESIATION OF OLEFINS

WITH NON-ACTIVATED DOUBLE BOND

BY MEANS OF RMgX AND R2Mg

This reaction has received the name Dzhe-milev reaction in the world literature; it is wide-ly used in synthetic practice:

In this series of the studies the followingreactions were discovered:

� catalytic 1,2-carboalumination of α-ole-fins with Et2AlCl and AlEt3 under the actionof Ti and Zr complexes;

� β-alkylation of olefins by means of Et2AlClcatalyzed by (RO)nZrCl4 � n.

Alongside with these achievements, efficientmethods are developed for catalytic hydroalumi-nation of cyclic and acyclic olefins by means ofiso-Bu2AlH, iso-Bu2AlCl, iso-Bu3Al (Scheme 9).

The implementation of the methods of met-al complex catalysis in the chemistry of orga-nometallic compounds of non-transition metalshas allowed us to discover a phenomenon ofcatalytic substitution of transition metal atoms(Ti, Zr, Hf, Ta, Hb, Co) in metallocarbocycles

Scheme 7.

In order to realize this work program wehave created for the first time in the worldpractice a single reactor method for cyclopro-panation of olefins with no use of toxic andexplosive diazonium compounds.

Research performed in this direction allowedfixing the priority of the Russian scientists in thefield of synthesis and application of highlystrained polycyclic structures, as well as imple-menting the technologies for obtaining novel ma-terials and products with record characteristics.

Some novel reactions developed within theframework of the mentioned program are pre-sented in Schemes 7, 8.

For the last 10�15 years, priority directionshave been developed in the field of catalyticactivation of carbon�carbon, metal�carbon andmetal�hydrogen bonds, which allowed re-searchers to carry out chemo-, regio- and ste-reoselective reactions of catalytic hydro-, car-bo- and cyclometallation of olefins, dienes,

Scheme 8. Novel single-reactor method for catalytic cy-clopropanation of olefins without preliminary diazo-methane obtaining.


Scheme 9.

Scheme 11. Cycloalumination of acetylenes.

by non-transition metal atoms (Mg, Zn, Al, Ga,In, B) as well as to develop novel reagents andfundamental reactions of catalytic cycloalumi-nation, cyclomagnesiation and cycloboration ofolefins, acetylenes and allenes.

These studies marked the beginning of thedevelopment of a new research field such asthe chemistry of small, medium and macro-metallocycles containing non-transition metals.

NOVEL REACTIONS OF ORGANOMETALLIC COMPOUNDS

OF NON-TRANSITION METALS

The mentioned above research direction isliterally �sparkling� with novel reactions andnon- trivial transformations of Al- and Mg-or-ganic compounds under the action of metalcomplex catalysts (Schemes 10, 11).

Catalytic cyclomagnesiation of olefins andacetylenes with the help of RMgX and Et2Mg,catalyzed by Zr complexes allows researchersto obtain magnesacyclopentanes, magnesacy-clopentenes and magnesacyclopentadienes witha high yield (Scheme 12).

Catalytic cycloboration of acetylenes bymeans of such a reagent as PhBCl2 in the pres-ence of a halogenide ion acceptor (metallic Mg)as well as such a catalyst as Cp2ZrCl2.

Scheme 10. Cycloalumination of cyclic and acyclic olefins.

630 U. M. DZHEMILEV

and organometallic reactions those are widelyused nowadays in the preparative chemistry.

Some of the single-stage synthetic methodsdeveloped are presented below:

In the series of these studies an efficientreagent such as AlR3�CH2I2 has been developedwhose use resulted in performing for the firsttime a direct cyclopropanation of disubstitut-ed acetylenes with the obtaining of alumini-um-containing cyclopropanes (Scheme 13).

One could consider research concerning thedevelopment of general catalytic methods forselective functionalization of carbon clusterswith the use of hydroamination by primaryand secondary amines, small molecules (H2O,NH3, H2S), as well as [3 + 2]-cycloaddition cyclicand acyclic amines, phosphines, sulphides,sulphoxides to the molecule of fullerene Ñ60 tobe an important achievement.

Scheme 12.

As the result of research performed in thefield of catalytic cyclometallation of acetylenesand allenes within the recent two or three years,universal single-reactor methods were developedfor designing giant organometallic macrocyclesof a universal purpose.

The fundamental and applied research in thefield of chemistry of non-transition metal or-ganometallic compounds with the use of com-plex catalysts based on transition metals haveallowed us to develop novel classes of organic

Scheme 13. Direct cyclopropanation of distributed acetylenes.


Basing on the developments performed with-in the framework of the research directionsmentioned above, the manufacture of the fol-lowing chemical products is mastered at the in-dustrial enterprises of Russia: 4-vinylcyclohex-ene, trans-trans-trans-1,5,9-cyclododecatriene,chloronorbornene, norbornadiene, special prod-ucts with record characteristics, novel efficientneutralizers of hydrogen sulphide, inhibitorsfor hydrosulphuric corrosion, extracting agentsfor the regeneration of spent catalysts, phe-nolic antioxidants, lubricants and lubricoolantliquids, immunostimulants for plants, antifun-gal preparations for plants and animals.

PROSPECTS OF THE FURTHER RESEARCH DEVELOPMENT

IN THE FIELD OF METAL COMPLEX CATALYSIS

For the nearest 5�10 years it is planned tocontinue the studies on the general mechanism forthe action of Ziegler�Natta catalysts by the exam-ple of model reactions of hydro-, carbo- and cy-cloalumination, as well as di-, oligo- and polymer-ization of olefins under the action of complex cat-alysts based on zirconium salts and complexes.

Much consideration will be devoted to thestudies on the influence of electronic structureof the catalyst�s central atom, its ligand sur-rounding, the stereochemistry of intermediatecomplexes, as well as to the identification oftheir structure and to the measurement of ki-netic parameters with respect to activity, se-lectivity and structural selectivity of the afore-

mentioned reactions with the use of catalystsbased on zirconium compounds.

There is no doubt that an important role inthese studies will be played by quantum chem-ical calculations of energy profile for these re-actions, the construction of a kinetic model.

The investigations of the catalytic cycloalu-mination and cyclomagnesiation reaction discov-ered will be continued with the purpose of ex-tending this method over acyclic, cyclic andheterocyclic olefins, including strained hete-roolefins, acetylenes, allenes, cumulenes andnatural compounds.

Our efforts will be directed at the furtherdevelopment of the discovered phenomenon ofcatalytic substitution of transition metal atomsin metallocarbocycles by non-transition metalatoms in order to extend this method over met-allocarbocycles of other non-transition metals(B, Ge, Ga, Zn, Sn).

Among important and prospective researchdirections for the nearest 5�10 years one couldconsider the investigation and development ofmulticomponent conjugated reactions under theaction metal complex catalysts (including het-erogenized ones) those would allow researchersto perform a directed self-assembling of com-plicated cyclic, acyclic and heteroatomic com-pounds proceeding from simple molecules.

Taking into account the world tendency forthe development of chemistry and chemicaltechnologies it is planned to realize novel reac-tions promising for the creation of modern com-petitive technologies based on the use of re-newable raw materials (H2O, CO2, C (carbonraw material), CH2O, N2, S8) with the partici-pation of homogeneous and heterogeneousmetal complex catalysts.

Research work concerning the developmentof promising methods for practical applicationof selective functionalization of carbon clusters,unsaturated macrocycles, skeletal and polycy-clic compounds will be continued and expanded.

An outstanding place among the studiesplanned will belong to the works connected withthe development of essentially new, single-re-actor methods of for designing metallo-, car-bo- and heterocyclic macrocycles based on theapplication of the reactions of catalytic cy-cloalumination and cyclomagnesiation of α,ω-

632 U. M. DZHEMILEV

diacetylenes, α,ω-diallenes, cyclic mono- anddiacetylenes, as well as of cyclocotrimeriza-tion of cyclic Ñ8�Ñ12 acetylenes with acetoni-trile under the action of cobalt-containing com-plex catalysts, homocyclotrimerization and tet-ramerization of cyclic acetylenes with the sub-sequent oxidative scission of double bonds inthe unsaturated polycycles formed.

The strategically important directions ofresearch for the nearest 5�10 years also includethe development of scientific research aimedat the development of radically new types ofchiral complex catalysts on the basis of transi-tion metal ions bound with natural biopolymerssuch as fibres, nucleic acids, carbohydrates,obtaining and studies on the properties of self-organizing catalytic systems those simulate nat-ural enzymatic systems. The latter is intendedfor using in order to realize asymmetric reac-tions of oxidation, reduction, condensation,cycloaddition, hydro-, carbo- and cyclometal-lation of unsaturated compounds for synthe-sizing a wide assortment of optically pure sub-stances and materials.

CONCLUSION

This review is devoted to the presentationof the most important results obtained by thedisciples and followers of G. A. Tolstikov forthe last 30 years within the framework of thedirection �Metal complex catalysis in the chem-istry of unsaturated and organometallic com-pounds�. The contribution of the disciples ofAcademician G. A. Tolstikov to the developmentof one of the most prospective and promisingfields of modern organic and organometallicchemistry is demonstrated.

REFERENCES

1 G. A. Tolstikov, Reaktsii Gidroperekisnogo Okisleniya,Nauka, Moscow, 1976.

2 G. A. Tolstikov, U. M. Dzhemilev, V. P. Yurjev, Zh.Org. Khim., 8, 10 (1972) 2204.

3 G. A. Tolstikov, U. M. Dzhemilev, V. P. Yurjev,S. R. Rafikov, Dokl. AN SSSR, 208, 2 (1973) 376.

4 U. M. Dzhemilev, V. P. Uyriev, G. A. Tolstikov et al.,Ibid., 196, 3 (1971) 588.

5 G. A. Tolstikov, U. M. Dzhemilev, N. P. Yurjev et al.,Tetrahedron Lett., 30 (1971) 2807.

6 G. A. Tolstikov, U. M. Dzhemilev, V. P. Yurjev, Usp.Khim., 44, 4 (1975) 645.

7 G. S. Bylina, U. M. Dzhemilev, N. S. Vostrikov et al.,Izv. AN SSSR. Ser. Khim., 2 (1978) 447.

8 U. M. Dzhemilev, N. S. Vostrikov, A. M. Moiseenkov,G. A. Tolstikov, Ibid., 4 (1979) 913.

9 N. S. Vostrikov, U. M. Dzhemilev, G. S. Bylina et al.,Ibid., 10 (1978) 2337.

10 U. M. Dzhemilev, N. S. Vostrikov, G. A. Tolstikov,S. R. Rafikov, Dokl. AN SSSR, 244, 2 (1979) 369.

11 U. M. Dzhemilev, G. E. Ivanov, G. A. Tolstikov, Zh. Org.Khim., 11, 5 (1975) 1636.

12 G. A. Tolstikov, U. M. Dzhemilev, Khim. Geterogen.Soyed., 2 (1980) 147.

13 G. A. Tolstikov, Soviet Scientific Reviews: Section B.Chemistry Reviews. Organic Chemistry, in N. K. Ko-chetkov and M. E. Volpin (Eds.), vol. 7, GmbH Harwood,Chur etc., 1985.

14 U. M. Dzhemilev, O. S. Vostrikova, G. A. Tolstikov, Usp.Khim., 59, 12 (1990) 1972.

15 U. M. Dzhemilev, R. V. Kunakova, J. Org. Chem., 450,1�2 (1993) 24.

16 F. A. Selimov, U. M. Dzhemilev, O. A. Ptashko,Metallokompleksny Katalizm v Sinteze PiridinovykhOsnovaniy, Khimiya, Moscow, 2003.

17 G. A. Tolstikov, Organic Synthesis: Modern Trends,Proc. 6th IUPAC Int. Symp., in O. Chizhov (Ed.),Blackwell, Oxford etc., 1987.

18 U. M. Dzhemilev, Mendeleev Commun., 18, 1 (2008) 1.19 U. M. Dzhemilev, A. G. Ibragimov, in: Modern Reduction

Methods, in P. Andersson and J. Munslow (Eds.), Wiley-VCH Verlag GmbH, Wienheim, 2008, pp. 437�479.

20 U. M. Dzhemilev, A. G. Ibragimov, Usp. Khim., 74, 9(2005) 886.

21 U. M. Dzhemilev, A. G. Ibragimov, Ibid., 69, 2 (2000) 134.22 U. M. Dzhemilev, Tetrahedron, 51 (1995) 4333.

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