Alkene and olefin functionalization via addition reactions.
Abstract
Alkene and olefin functionalization via addition of electro‐ or nucleophilic reagents is one of the convenient synthetic methods for the insertion of heteroatoms into organic molecules. The use of organometallic reagents in these reactions in combination with the specific catalysts provides high substrate conversion and process selectivity. The introduction of this approach into the chemistry of organoaluminum compounds leads to the development of chemo‐, regio‐ and stereoselective catalytic methods of alkene and olefin functionalization. The chapter focuses on the modern concepts of the alkene hydro‐, carbo‐ and cycloalumination mechanisms, that is, the experimental and theoretical data on the intermediate structures involved in the product formation, the effects of the catalyst and organoaluminum compound structure, reaction conditions on the activity and selectivity of the bimetallic systems. The prospects of the development of enantioselective methods using these catalytic systems for the alkene and olefin transformations are considered.
Keywords
- hydrometalation
- carbometalation
- cyclometalation
- zirconocenes
- organoaluminum compounds
- reaction mechanism
- asymmetric catalysis
1. Introduction
Insertion of various functional groups into the molecules is one of the central problems of organic chemistry. In this regard, alkene and olefin double bonds are often considered as possible reactive centers for the construction of C‐heteroatom fragments. The classic functionalization methods are based on the addition reaction of electro‐ or nucleophilic reagents toward the unsaturated substrates, for example, halogenation, oxidation, hydrohalogenation, hydroboration, hydroamination, hydrosilylation, hydro‐ and carbometalation, etc. (Table 1).
Each type of functionalization goes under specific conditions and involves various reagents and catalysts, which obviously affects the mechanisms of the processes and product structure. Thus, this chapter is focused on the reactions of alkenes with organometallic compounds as the effective routes for the synthesis of numerous classes of organic compounds.
Reactions of alkenes with organometallic reagents run with high substrate conversion and selectivity due to the generation of active intermediates with C‐metal bonds (Table 1), further modification of which provides a wide range of products. The organoaluminum compounds (OACs) occupied a strong position in the chemistry of alkenes and olefins [1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11]. The acyclic and cyclic products bearing organoaluminum moiety obtained as a result of hydro‐, carbo‐ and cycloalumination require no further separation and could be readily modified to alcohols, halides, heterocycles, carbocycles and others [9, 12, 13, 14, 15, 16, 17, 18]. For example, the well‐known Ziegler‐Alfol process for the synthesis of higher and linear primary alcohols from ethylene [12] has been realized in the industrial scale.
The application of transition metal complexes as catalysts enables the reactions of OAC and alkenes to proceed under mild conditions with chemo‐ and stereoselectivity control. Among the complexes Group IV transition metals played a significant role in the development of alkene functionalization methods using OAC. Structural types of catalysts can be varied from metal salts to metallocenes and postmetallocenes (Scheme 1). The special milestone in this research is the discovery of metallocene catalysis, which serves as an effective tool for the stereochemistry regulation via η5‐ligand structure variation and provides an opportunity to a comprehensive study of the reaction mechanisms.
The future development of these methods needs understanding the reaction mechanisms: how the OAC nature, reaction conditions, catalyst and alkene structure regulate the substrate conversion, chemo‐ and enantioselectivity; what kinds of intermediates define the process pathways. Among the mechanistic studies much attention has been paid to the catalytic systems based on zirconocenes due to several reasons. First, a broad range of catalytic reactions can be implemented in these systems, from hydro‐, carbo‐ and cyclometalation to polymerization of unsaturated compounds. Second, these systems are convenient for fundamental investigations, since η5‐ligands bound to zirconium atoms act like magnetic probes indicating the electronic state of the transition metal atom and reflecting the molecule symmetry. Third, the reaction times and intermediate lifetimes appear to be convenient for nuclear magnetic resonance (NMR) monitoring, which is the most informative method for the studies of homogeneous catalytic reactions. Moreover, the systems are substantially free of paramagnetic species, which, for example, in the case of titanium complexes, preclude observation of the genesis of intermediates due to pronounced NMR signal broadening.
Thus, the chapter presents the results on the experimental and theoretical studies of the mechanisms of alkene hydro‐, carbo‐ and cyclometalation by organoaluminum compounds (AlR3 and XAlBui2), catalyzed with zirconium η5‐complexes. The factors that determine the intermediate reactivity and, consequently, the activity of the catalytic systems, reaction pathway and enantioselectivity are considered. The prospects of the development of stereoselective methods using these catalytic systems for the alkene and olefin transformations are discussed.
2. Mechanisms of alkene functionalization, catalyzed by zirconium η5‐complexes
2.1. Mechanism of zirconocene catalysis in alkene hydroalumination
The catalytic alkene hydroalumination has found wide application as an efficient regio‐ and stereoselective method for the double and triple bond reduction providing important synthons for organic and organometallic chemistry [4, 13, 14, 15]. Various transition metal complexes can be used as the catalysts of the reaction, however, the compounds based on the metals with no vacant d orbital show much less activity in the reaction (e.g., Cu, Zn vs. Ti, Zr, Co, Ni) [16, 17, 18, 19, 20, 21]. Moreover, the significant effect of the OAC nature and ligand structure on the hydrometalation product yield has been shown [22, 23].
Studies on the catalytic activity of the systems L2ZrCl2‐XAlBui2 (L = C5H5, C5H4Me, Ind, C5Me5; L2 =
The reaction mechanism (e.g., see [16, 17, 18, 19, 20, 21]) implies the generation of transition metal hydride LnMH formed upon σ‐ligand exchange; then this species coordinates alkene to give an alkyl derivative. In the last step, as a result of the transmetalation of alkyl fragment from M to Al, the organoaluminum product is formed and the transition metal hydride is recovered (Scheme 2).
Furthermore, a large number of various bimetallic hydride complexes were identified in reactions of metal chlorides, hydrides and alkyl derivatives with OAC (see, e.g., reviews [24, 25]) that gave an idea on the involvement of such a type of complexes as key intermediates in the hydrometalation reaction. The structural types of the hydride Zr, Al‐complexes, which could be observed in the reactions of zirconocenes with aluminum hydrides or alkylaluminums, are presented in Scheme 3.
Our studies on the olefin hydroalumination by XAlBui2 (X = H, Cl, Bui), catalyzed with Zr η5‐complexes, using the quantum chemical methods [31, 32], chemical kinetics [33] and NMR [22, 23], showed that the reaction is a complex multi‐step process (Scheme 4). The use of zirconocenes with less electron‐donating and sterically hindered ligands provides the stable Zr, Al‐hydride clusters L2Zr(μ‐H)3(AlBui2)2(μ‐Cl) (
Reaction of Cp2ZrCl2with AlBui3 goes via alkyl chloride exchange and isobutylene elimination, which give the intermediates Cp2Zr(μ‐H)3(AlBui2)(AlBui3) and Cp2Zr(μ‐H)3(AlBui2)2(μ‐Cl).The absence of fast exchange between these hydride clusters increases the lifetime of the active sites with free Zr─H bond, and this is responsible for the high activity of the Cp2ZrCl2‐AlBui3catalytic system toward alkene [23].
High yields of hydroalumination products in the reactions of alkenes with HAlBui2, catalyzed by Zr complexes with bulky ligands (L = CpMe5,
Thus, the L2ZrCl2‐XAlBui2systems provide Zr, Al‐hydride complexes with Zr─H─Zr and Zr─H─Al‐bridged bonds in which intra‐ and intermolecular hydride exchange between Zr and Al, controlled by the steric factor of the η5‐ligand, OAC nature and by the reaction conditions (reactant ratio), plays the key role in the catalytic process. The energy of cleavage of these bridging bonds and the ability of the complex to have initially a free Zr─H bond are the factors determining the activity of Zr, Al‐hydride intermediates in the alkene hydroalumination.
2.2. Mechanisms of zirconocene catalysis in alkene carbo‐ and cycloalumination
Catalytic alkene and acetylene carbo‐ and cycloalumination are convenient one‐pot synthetic routes to the acyclic and cyclic OACs that could be converted into alcohols, halides, heterocycles, carbocycles and others [2, 3, 4, 5, 6, 7, 8, 9, 10, 11]. The using of enantiomerically pure complexes as the catalysts affords the asymmetric induction in the reactions. Thus, the method of Zr‐catalyzed asymmetric carboalumination of alkenes‐ZACA‐reaction has been developed [7, 8, 9, 10, 11, 34], which was applied to the synthesis of a number of biologically active compounds. The involvement of methylaluminoxane (MAO) [35, 36, 37, 38] or other Lewis acidic cocatalysts [39] substantially increases the activity of the catalytic systems providing alkene dimers, oligomers and polymers.
Summarizing the information on the study of the reaction of alkenes with alkylaluminums (R = Me, Et) in the presence of metalcomplexes [40, 41, 42, 43, 44, 45, 46], it should be noted that the process can give various products depending on the reagent nature, catalyst structure and reaction conditions (Scheme 5): saturated and unsaturated alkylated products (
L2ZrCl2 | Solvent | Hexene‐1 conversion, % | Product yield, % | |||
---|---|---|---|---|---|---|
15 | 16 | 17 | 18 | |||
Cp2ZrCl2 | CH2Cl2 | 92 | 3 | 14 | 7 | 68 |
C6H5CH3 | 69 | 3 | 21 | 7 | 38 | |
(CpMe)2ZrCl2 | CH2Cl2 | 84 | 11 | 14 | 7 | 52 |
C6H5CH3 | 39 | 9 | 9 | 9 | 12 | |
(CpMe5)2ZrCl2 | CH2Cl2 | 68 | 53 | 8 | 7 | ‐ |
C6H5CH3 | 44 | 15 | 14 | 14 | 1 | |
Ind2ZrCl2 | CH2Cl2 | 87 | 28 | 18 | 8 | 33 |
C6H5CH3 | 70 | 38 | 14 | 10 | 8 |
L2ZrCl2 | Solvent | Hexene‐1 conversion, % | Product yield, % | ||||
---|---|---|---|---|---|---|---|
15 | 16 | 17 | 18 | 19 | |||
Cp2ZrCl2 | CH2Cl2 | 96 | 16 | 16 | 13 | <1 | 51 |
C6H6 | 91 | 24 | 2 | 2 | – | 63 | |
(CpMe)2ZrCl2 | CH2Cl2 | 98 | 16 | 9 | 10 | – | 62 |
C6H6 | 97 | 6 | 10 | 12 | – | 69 | |
(CpMe5)2ZrCl2 | CH2Cl2 | 99 | 48 | 13 | 10 | 7 | 21 |
C6H6 | 96 | 15 | 2 | 5 | – | 74 | |
Ind2ZrCl2 | CH2Cl2 | 93 | 36 | 3 | 7 | 2 | 45 |
C6H6 | 99 | 25 | – | <1 | <1 | 74 |
Obviously, the reaction pathways are determined by the catalytically active sites of a definite type. Thus, bimetallic Zr, Al‐alkyl complexes L2ZrR(μ‐Cl)AlRnCl3‐
Further transformations of the neutral alkyl bimetallic complexes via α‐C‐H (Ti) or β‐C‐H (Zr) activation gives the stable structures with M‐CH2‐Al, M‐CH2CHR‐Al or M‐CH2CH2‐M bridges. Five‐membered bimetallic complex L2ZrCH2CH2(μ‐Cl)AlEt2was found to be the intermediate that is responsible for the cycloalumination pathway [50, 56, 57].
The Me‐group exchange between Zr and Al atoms in the complexes L2ZrMe(μ‐Cl)AlMe3 has been observed by the means of dynamic 2D NMR spectroscopy [58, 59] (Figure 3a). Moreover, the exchange between the magnetically nonequivalent hydrogens, which belong to the opposite parts of
On the basis of these investigations, we proposed the mechanism, where the alkyl chloride bimetallic complex associated with the AlR3 molecule is the starting point of the several catalytic cycles, carbo‐, cyclometalation, hydrometalation and dimerization (Scheme 7). The zirconocenes with more electron‐deficient η5‐ligands in combination with chlorinated solvents provide a greater concentration of a key intermediate, which speeds up all the pathways, ensuring the high conversion of a substrate. The sterical hindrances in η5‐ligand and solvation by chlorine containing solvents delay the processes of C─H activation in the methylalkyl substituted intermediate increasing the cabometalation product yield.
As shown in Figure 4, dynamic processes are also characteristic to the five‐membered bimetallic complex L2ZrCH2CH2(μ‐Cl)AlEt2. Thus, we found intermolecular exchange by hydrogens in the pairs H1‐H4 and H2‐H3of
Another evidence of the zirconacyclopropane generation in the systems L2ZrCl2‐AlEt3 could be the observation of diastereomeric five‐membered bimetallic complexes CpCp′ZrCH2CH2(μ‐H)AlEt2(Cp′= η5‐(1‐neomenthyl‐4,5,6,7‐tetrahydroindenyl)) [60], the formation is possible due to realization of two parallel stages—two types of β‐C‐H activation in L2ZrEt2 (Scheme 7): (i) elimination of ethane to give zirconacyclopropane and (ii) formation of Et2AlH from Et3Al and L2ZrHEt with loss of ethylene.
Moreover, our density functional theory (DFT) calculations showed that equilibrium between zirconacyclopropane (
3. Asymmetric alkene carbo‐ and cycloalumination, catalyzed by enantiomerically pure Group IV metallocenes
The development of stereoselective catalytic methods for the synthesis of cyclic and acyclic OAC using chiral transition metal η5
Thus, in the reaction of alkenes with organoaluminum compounds C2‐ and C1‐symmetric conformationally labile (
Study on the olefin carboalumination with AlMe3 in the presence of conformationally rigid
Thus, the chemo‐ and enantioselectivity of these reactions are substantially affected by the catalyst and alkene structures, OAC nature and reaction conditions (temperature, reactant ratio and solvent). Presumably, the key factor determining the dependence of enantioselectivity on the solvent nature and OAC structure is the conformational behavior of the η5
In this connection, further optimization of the ligand environment, namely the search for appropriate conformers that could be formed via either introduction of suitable substituents into the indenyl ligand or upon binding of ligands could advance these studies toward the design of more efficient catalysts for alkene functionalization by organomagnesium and ‐aluminum reagents.
4. Conclusions
Thus, the catalytic alkene hydro‐, carbo‐ and cycloalumination are complex multi‐step processes, in which a large number of intermediate bimetallic Zr, Al‐complexes are involved. Studies of the reaction mechanisms allow to understand the chemistry of the processes on a deeper level and to narrow the search for new catalytic systems.
Finally, the next remarks should be sound. First, the initial OACs exist as self‐associated structures in the solutions, where the exchange between hydride atoms or alkyl groups could run via dissociation on monomers, which represents the Lewis acids and which effective concentration influences on the stages of key intermediates formation. Second, since the catalyst (IV group transition metals) is a Lewis acid too due to a free nonbonding orbital, then it disturbs the above balance, making the system more dynamic. Thus, one of the important roles of the catalyst besides the formation of active species is to accelerate the exchange through the dissociation with the release of the active OAC monomer. Third, the interaction of alkyl or hydride complex with the monomer gives active species—bimetallic intermediates, which reactivity depends on the availability of the free nonbonding orbital (Scheme 9). The active species should be coordinatively unsaturated, where at least one of the bridge bond is broken. In the case of bimetallic hydride complexes, there is the tendency to form inactive bridge bonds, whereas bimetallic alkyl substituted intermediates are inclined to the dissociation. Therefore, the activity of intermediates depends on the living time of active species, in which the electrophilicity of the metal center could be increased via η5‐ligand, thereby accelerating the process of alkene introduction. However, there is a danger of another process—C─H activation in the products, which could be prevented by using more bulky ligands or more polar solvents. Fourth, the activity of catalytic systems and the degree of asymmetric induction in catalytic alkene functionalization by OACs is substantially affected by the intramolecular ligand mobility and conformational composition of the bimetallic intermediates.
Thus, the regulation of activity, chemo‐ and stereoselectivity of the studied systems is the problem of fine tuning of the catalytically active center, in which should be a balance between electronic and steric factors of the catalyst, OAC and the substrate.
Acknowledgments
The authors thank the Russian Foundation of Basic Research for financial support.
References
- 1.
Woodward S, Dagorne S, editors. Modern Organoaluminum Reagents. Preparation, Structure, Reactivity and Use. Berlin Heidelberg: Springer‐Verlag; 2013. p. 312. DOI: 10.1007/978‐3‐642‐33672‐0 - 2.
Tolstikov GA, Dzhemilev UM, Tolstikov AG. Aluminiyorganicheskie soedineniya v organicheskom sinteze (Organoaluminum compounds in organic synthesis). Novosibirsk: Akad. izd. GEO; 2009. p. 645. ISBN 978‐5‐9747‐0147‐4 - 3.
Ibragimov AG, Dzhemilev UM. Metal complex catalysis in the synthesis of organoaluminium compounds. Russian Chemical Reviews. 2000; 69 (2):121-135. DOI: 10.1070/RC2000v069n02ABEH000519 - 4.
Dzhemilev UM, Ibragimov AG. Hydrometallation of unsaturated compounds. In: Andersson PG, Munslow IJ, editors. Modern Reduction Methods. Weinheim: Wiley‐VCH Verlag GmbH & Co. KGaA; 2008. pp. 447‐490. Chapter 18. DOI: 10.1002/9783527622115.ch18 - 5.
Dzhemilev UM, Ibragimov AG. Catalytic cyclometalation reaction of unsaturated compounds in synthesis of magnesa‐ and aluminacarbocycles. Journal of Organometallic Chemistry. 2010; 695 (8):1085-1110. DOI: 10.1016/j.jorganchem.2010.01.002 - 6.
D’yakonov VA. Dzhemilev Reaction in Organic and Organometallic Synthesis. Chemistry Research and Applications Series. New York: Nova Science Publishers; 2010. p. 96. ISBN: 978‐1‐60876‐683‐3 - 7.
Negishi E. Asymmetric carbometallations. In: Ojima I, editor. Catalytic Asymmetric Synthesis. 2nd ed. New York, USA: John Wiley & Sons, Inc.; 2005. pp. 165‐190. Chapter 4. DOI: 10.1002/0471721506.ch5 - 8.
Negishi E, Huo S. Zirconium‐catalyzed enantioselective carboalumination of “unactivated” alkenes as a new synthetic tool for asymmetric carboncarbon bond formation. Pure and Applied Chemistry. 2002; 74 (1):151-157. DOI: 10.1351/pac200274010151 - 9.
Negishi E. Transition metal‐catalyzed organometallic reactions that have revolutionized organic synthesis. Bulletin of the Chemical Society of Japan. 2007; 80 (2):233-257. DOI: 10.1246/bcsj.80.233 - 10.
Negishi E. Bimetallic catalytic systems containing Ti, Zr, Ni, and Pd. Their applications to selective organic syntheses. Pure and Applied Chemistry. 1981; 53 (12):2333-2356. DOI: 10.1351/pac198153122333 - 11.
Xu S, Negishi E. Zirconium‐catalyzed asymmetric carboalumination of unactivated terminal alkenes. Accounts of Chemical Research. 2016; 49 (10):2158-2168. DOI: 10.1021/acs.accounts.6b00338 - 12.
Ziegler K, Krupp F, Zosel K. Eine einfache synthese primärer Alkohole aus Olefinen. Angewandte Chemie. 1955; 67 :425-426. DOI: 10.1002/ange.19550671609 - 13.
Guiry PJ, Coyne AG, Carroll AM. 10.19 – C–E bond formation through hydroboration and hydroalumination. In: Crabtree RH, Mingos DMP, editors. Comprehensive Organometallic Chemistry III. Elsevier Ltd.; Oxford. 2007. pp. 839-869. DOI: 10.1016/B0‐08‐045047‐4/00141‐2 - 14.
Zaidlewicz M, Wolan A, Budny M. 8.24 Hydrometallation of C=C and C=C bonds. Group 3. In: Knochel P, Molander GA, editors. Comprehensive Organic Synthesis II. 2nd ed. Elsevier Ltd.; Amsterdam. 2014. pp. 877-963. DOI: 10.1016/B978‐0‐08‐097742‐300826‐0 - 15.
Joseph J, Jaroschik F, Harakat D, Radhakrishnan KV, Vasse JL, Szymoniak J. Titanium‐catalyzed hydroalumination of conjugated dienes: Access to fulvene‐derived allylaluminium reagents and their diastereoselective reactions with carbonyl compounds. Chemistry—A European Journal. 2014; 20 (18):5433-5438. DOI: 10.1002/chem.201304775 - 16.
Sato F, Sato S, Sato M. Addition of lithium aluminium hydride to olefins catalyzed by zirconium tetrachloride: A convenient route to alkanes and 1‐haloalkanes from 1‐alkenes. Journal of Organometallic Chemistry. 1976; 122 (2):C25‐C27. DOI: 10.1016/S0022‐328X(00)80622‐1 - 17.
Sato F, Sato S, Kodama H, Sato M. Reactions of lithium aluminum hydride or alane with olefins catalyzed by titanium tetrachloride or zirconium tetrachloride. A convenient route to alkanes, 1‐haloalkanes and terminal alcohols from alkenes. Journal of Organometallic Chemistry. 1977; 142 (1):71-79. DOI: 10.1016/S0022‐328X(00)91817‐5 - 18.
Ashby EC, Noding SA. Hydrometalation. 3. Hydroalumination of alkenes and dienes catalyzed by transition metal halides. Journal of Organic Chemistry. 1979; 44 (24):4364-4371. DOI: 10.1021/jo01338a025 - 19.
Ashby EC, Noding SA. Hydrometalation. 5. Hydroalumination of alkenes and alkynes with complex metal hydrides of aluminum in the presence of bis(cyclopentadienyl)dichlorotitanium. Journal of Organic Chemistry. 1980; 45 (6):1035-1041. DOI: 10.1021/jo01294a023 - 20.
Negishi E, Yoshida T. A novel zirconium‐catalyzed hydroalumination of olefins. Tetrahedron Letters. 1980; 21 (16):1501-1504. DOI: 10.1016/S0040‐4039(00)92757‐6 - 21.
Weliange NM, McGuinness DS, Gardinera MG, Patel J. Cobalt‐bis(imino)pyridine complexes as catalysts for hydroalumination–isomerisation of internal olefins. Dalton Transactions. 2016; 45 :10842-10849. DOI: 10.1039/c6dt01113f - 22.
Parfenova LV, Pechatkina SV, Khalilov LM, Dzhemilev UM. Mechanism of Cр2ZrCl2‐catalyzed olefin hydroalumination by alkylalanes. Russian Chemical Bulletin, International Edition. 2005; 54 :316-327. DOI: 10.1007/s11172‐005‐0254‐z - 23.
Parfenova LV, Kovyazin PV, Nifant’ev IE, Khalilov LM, Dzhemilev UM. Role of Zr, Al‐hydride intermediate structure and dynamics in alkene hydroalumination by XAlBui2 (X= H, Cl, Bui), catalyzed with Zr η5‐Complexes. Organometallics. 2015; 34 (14):3559-3570. DOI: 10.1021/acs.organomet.5b003 - 24.
Parfenova LV, Khalilov LM, Dzhemilev UM. Mechanisms of reactions of organoaluminium compounds with alkenes and alkynes catalyzed by Zr complexes. Russian Chemical Reviews. 2012; 81 (6):524-548. DOI: 10.1070/RC2012v081n06ABEH004225 - 25.
Butler MJ, Crimmin MR. Magnesium, zinc, aluminium and gallium hydride complexes of the transition metals. Chemical Communications. 2017; 53 :1348-1365. DOI: 10.1039/c6cc05702k - 26.
Wailes PC, Weigold H, Bell AP. Reaction of dicyclopentadieny zirconium dihydride with trimethyaluminum. Formation of a novel hydride containing both Zr‐H‐Zr and Zr‐H‐Al. Journal of Organometallic Chemistry. 1972; 43 :С29‐С31. DOI: 10.1016/S0022‐328X(00)81589‐2 - 27.
Shoer LI., Gell KI, Schwartz G. Mixed‐metal hydride complexes containing Zr‐H‐Al bridges. Synthesis and relation to transition‐metal‐catalyzed reactions of aluminum hydrides. Journal of Organometallic Chemistry. 1977; 136 :c19‐c22. DOI: 10.1016/S0022‐328X(00)82126‐9 - 28.
Baldwin SM, Bercaw JE, Brintzinger HH. Alkylaluminum‐complexed zirconocene hydrides: Identification of hydride‐bridged species by NMR Spectroscopy. Journal of the American Chemical Society. 2008; 130 :17423-17433. DOI: 10.1021/ja8054723 - 29.
Parfenova LV, Vildanova RF, Pechatkina SV, Khalilov LM, Dzhemilev UM. New effective reagent [Cp2ZrH2·ClAlEt2]2 for alkene hydrometallation. Journal of Organometallic Chemistry. 2007; 692 :3424-3429. DOI: 10.1016/j.jorganchem.2007.04.007 - 30.
Weliange NM, McGuinness DS, Gardinera MG, Patel J. Insertion and isomerisation of internal olefins at alkylaluminium hydride: Catalysis with zirconocene dichloride. Dalton Transactions. 2015; 44 :20098-20107. DOI: 10.1039/c5dt03257a - 31.
Pankratyev EY, Tyumkina TV, Parfenova LV, Khalilov LM, Khursan SL, Dzhemilev UM. DFT study on mechanism of olefin hydroalumination by XAlBui2 in the presence of Cp2ZrCl2 catalyst. I. Simulation of intermediate formation in reaction of HAlBui2 with Cp2ZrCl2. Organometallics. 2009; 28 :968-977. DOI: 10.1021/om800393j - 32.
Pankratyev EY, Tyumkina TV, Parfenova LV, Khalilov LM, Khursan SL, Dzhemilev UM. DFT and ab initio study on mechanism of olefin hydroalumination by XAlBui2, in the presence Cp2ZrCl2 catalyst. II. Olefin interaction with catalytically active centers. Organometallics. 2011; 30 :6078-6089. DOI: 10.1021/om200518h - 33.
Parfenova LV, Balaev AV, Gubaidullin IM, Pechatkina SV, Abzalilova LR, Spivak SI, Khalilov LM, Dzhemilev UM. Kinetic model of olefin hydroalumination by HAlBui2 and AlBui3 in presence of Cp2ZrCl2 catalyst. International Journal of Chemical Kinetics. 2007; 39 (6):333-339. DOI: 10.1002/kin.20238 - 34.
Negishi E. Discovery of ZACA reaction − Zr‐catalyzed asymmetric carboalumination of alkenes. Archive for Organic Chemistry. 2011;(8):34-53. DOI: 10.3998/ark.5550190.0012.803 - 35.
Sinn H, Kaminsky W, Vollmer HJ, Woldt R. Lebende Polymere bei Ziegler‐Katalysatoren extremer Produktivität. Angewandte Chemie. 1980; 92 (5):396-402. DOI: 10.1002/ange.19800920517 - 36.
Sinn H, Kaminsky W, Vollmer HJ, Woldt R. “Living polymers” on polymerization with extremely productive ziegler catalysts. Angewandte Chemie International Edition. 1980; 19 (5):390-392. DOI: 10.1002/anie.198003901 - 37.
Sinn H, Kaminsky W. Ziegler‐Natta catalysis. Advances in Organometallic Chemistry. 1980; 18 :99-149. DOI: 10.1016/S0065‐3055(08)60307‐X - 38.
Kaminsky W, editor. Polyolefins: 50 years after Ziegler and Natta II. Polyolefins by Metallocenes and Other Single‐Site Catalysts. Berlin Heidelberg: Springer‐Verlag; 2013. p. 366. DOI: 10.1007/978‐3‐642‐40805‐2 - 39.
Chen EY‐X, Marks TJ. Cocatalysts for metal‐catalyzed olefin polymerization: Activators, activation processes, and structure−activity relationships. Chemical Reviews. 2000; 100 (4):1391-1434. DOI: 10.1021/cr980462j - 40.
Dzhemilev UM, Vostrikova OS, Tolstikov GA, Ibragimov AG. New method for inserting ethyl group in β‐position of higher α‐olefins using diethylaluminum chloride. Russian Chemical Bulletin. 1979; 28 :2441-2442. DOI: 10.1007/BF00951739 - 41.
Dzhemilev UM, Ibragimov AG, Vostrikova OS, Tolstikov GA,Zelenova LM. New method of β‐alkylation of α‐olefins using dialkylaluminum chlorides with catalytic amounts of Ti, Zr, and Hf complexes. Russian Chemical Bulletin. 1981; 30 :281-284. DOI: 10.1007/BF00953581 - 42.
Dzhemilev UM, Ibragimov AG, Vostrikova OS., Tolstikov GA. Carbalumination of higher α‐olefins catalyzed by titanium and zirconium complexes. Russian Chemical Bulletin. 1985; 34 :196-197. DOI: 10.1007/BF01157356 - 43.
Kondakov DY, Negishi E. Zirconium‐catalyzed enantioselective methylalumination of monosubstituted alkenes. Journal of the American Chemical Society. 1995; 117 :10771-10772. DOI: 10.1021/ja00148a031 - 44.
Kondakov DY, Negishi E. Zirconium‐catalyzed enantioselective alkylalumination of monosubstituted alkenes proceeding via noncyclic mechanism. Journal of the American Chemical Society. 1996; 118 :1577-1578. DOI: 10.1021/ja953655m - 45.
Christoffers J, Bergman RG. Zirconocene‐alumoxane (1:1) – a catalyst for the selective dimerization of α‐olefins. Inorganica Chimica Acta. 1998; 270 :20-27. DOI: 10.1016/S0020‐1693(97)05819‐2 - 46.
Parfenova LV, Gabdrakhmanov VZ, Khalilov LM, Dzhemilev UM. On study of chemoselectivity of reaction of trialkylalanes with alkenes, catalyzed with Zr π‐complexes. Journal of Organometallic Chemistry. 2009; 694 :3725-3731. DOI: 10.1016/j.jorganchem.2009.07.037 - 47.
Kaminsky W, Sinn H. Mehrfach durch Metalle Substituierte Athane. Liebigs Annalen der Chemie. 1975;(3):424-437. DOI: 10.1002/jlac.197519750307 - 48.
Kaminsky W, Vollmer HJ. Kernresonanzspektropishe Untersuchungen an den Systemen Dicyclopentadienyl zircon (IV) und Organoaluminium. Liebigs Annalen der Chemie. 1975;(3):438-448. DOI: 10.1002/jlac.197519750308 - 49.
Yoshida T, Negishi E. Mechanism of the zirconium‐catalyzed carboalumination of alkynes. Evidence for direct carboalumination. Journal of the American Chemical Society. 1981; 103 :4985-4987. DOI: 10.1021/ja00406a071 - 50.
Negishi E., Kondakov DY, Choueiri D, Kasai K, Takahashi T. Multiple mechanistic pathways for zirconium‐catalyzed carboalumination of alkynes. Requirements for cyclic carbometallation processes involving C‐H activation. Journal of the American Chemical Society. 1996; 118 :9577-9588. DOI: 10.1021/ja9538039 - 51.
Beck S, Brintzinger HH. Alkyl exchange between aluminium trialkyls and zirconocene dichloride complexes—a measure of electron densities at the Zr center. Inorganica Chimica Acta. 1998; 270 :376-381. DOI: 10.1016/S0020‐1693(97)05871‐4 - 52.
Tritto I, Zucchi D, Destro M, Sacchi MC, Dall’Occo T, Galimberti M. NMR investigations of the reactivity between zirconocenes and β‐alkyl‐substituted aluminoxanes. Journal of Molecular Catalysis A Chemical. 2000; 160 :107-114. DOI: 10.1016/S1381‐1169(00)00237‐5 - 53.
Tebbe FN, Parshall GW, Reddy GS. Olefin homologation with titanium methylene compounds. Journal of the American Chemical Society. 1978; 100 :3611-3613. DOI: 10.1021/ja00479a061 - 54.
Bochmann M, Lancaster SJ. Cationic group IV metal alkyl complexes and their role as olefin polymerization catalysts: The formation of ethyl‐bridged dinuclear and heterodinuclear zirconium and hafnium complexes. Journal of Organometallic Chemistry. 1995; 497 :55-59. DOI: 10.1016/0022‐328X(95)00109‐4 - 55.
Rocchigiani L, Busico V, Pastore A, Macchioni A. Comparative NMR study on the reactions of Hf(IV) organometallic complexes with Al/Zn alkyls. Organometallics. 2016; 35 :1241-1250. DOI: 10.1021/acs.organomet.6b00088 - 56.
Khalilov LM, Parfenova LV, Rusakov SV, Ibragimov AG, Dzhemilev UM. Synthesis and conversions of metallocycles. 22. NMR studies of the mechanism of Cp2ZrCl2‐catalyzed cycloalumination of olefins with triethylaluminum to form aluminacyclopentanes. Russian Chemical Bulletin. 2000; 49 :2051-2058. DOI: 10.1023/A:1009536328369 - 57.
Balaev AV, Parfenova LV, Gubaidullin IM, Rusakov SV, Spivak SI, Khalilov LM, Dzhemilev UM. The mechanism of Cp2ZrCl2‐Catalyzed alkene cycloalumination with triethylaluminum to give alumacyclopentanes. Doklady Physical Chemistry. 2001; 381 :279-282. DOI: 10.1023/A:1012900227841 - 58.
Gabdrakhmanov VZ. Mechanism of catalytic olefin carboalumination by trialkylalanes in the presence of Zr n5‐complexes [dissertation]. Ufa; 2010. p. 112 - 59.
Kovyazin PV, Permyakov VK, Parfenova LV, Nifant’ev IE, Khalilov LM, Dzhemilev UM. Zirconium ansa‐complexes as catalysts in reactions of trialkylalanes with alkenes. In: Book of Abstracts of International Symposium «Modern trends in Organometallic Chemistry and Catalysis» (devoted to 90th Anniversary of Academician M.E. Volpin); June 3-7; Moscow. 2013. p. P48 - 60.
Parfenova LV, Berestova TV, Molchankina IV, Khalilov LM, Whitby RJ, Dzhemilev UM. Stereocontrolled monoalkylation of mixed‐ring complex CpCp’ZrCl2 (Cp’ = 1‐neomenthyl‐4,5,6,7‐tetrahydroindenyl) by lithium, magnesium and aluminum alkyls. Journal of Organometallic Chemistry. 2013; 726 :37-45. DOI: 10.1016/j.jorganchem.2012.12.004 - 61.
Tyumkina TV, Islamov DN, Parfenova LV, Whitby RJ, Khalilov LM, Dzhemilev UM. Mechanistic aspects of chemo‐ and regioselectivity in Cp2ZrCl2‐catalyzed alkene cycloalumination by AlEt3. Journal of Organometallic Chemistry. 2016; 822 :135-143. DOI: 10.1016/j.jorganchem.2016.08.019 - 62.
Dzhemilev UM, Ibragimov AG. Regio‐ and stereoselective synthesis for a novel class of organoaluminium compounds — substituted aluminacyclopentanes and aluminacyclopentenes assis. Journal of Organometallic Chemistry. 1994; 466 :1-4. DOI: 10.1016/0022‐328X(94)88022‐0 - 63.
Dzhemilev UM. Catalytic replacement of transition metal atoms in metallacarbocycles by the atoms of nontransition metals. Mendeleev Communications. 2008; 18 :1-5. DOI: 10.1016/j.mencom.2008.01.001 - 64.
Hoveyda AH, Morken JP. Enantioselective C‐C and C‐H bond formation mediated or catalyzed by chiral ebthi complexes of titanium and zirconium. Angewandte Chemie International Edition. 1996; 35 :1263-1284. DOI: 10.1002/anie.199612621 - 65.
Hoveyda AH. Chiral zirconium catalysts for enantioselective synthesis. In: Marek I, editor. Titanium and Zirconium in Organic Synthesis. Weinheim, Germany: Wiley‐VCH Verlag GmbH & Co. KgaA; 2002. pp. 180-229.Chapter 6. DOI: 10.1002/3527600671.ch6 - 66.
Parfenova LV, Berestova TV, Tyumkina TV, Kovyazin PV, Khalilov LM, Whitby RJ, Dzhemilev UM. Enantioselectivity of chiral zirconocenes as catalysts in alkene hydro‐, carbo‐ and cycloalumination reactions. Tetrahedron Asymmetry. 2010; 21 :299-310. DOI: 10.1016/j.tetasy.2010.01.001 - 67.
Parfenova LV, Kovyazin PV, Tyumkina TV, Makrushina AV, Khalilov LM, Dzhemilev UM. Catalytic enantioselective ethylalumination of terminal alkenes: Substrate effect and absolute configuration assignment. Tetrahedron Asymmetry. 2015; 26 :124-135. DOI: 10.1016/j.tetasy.2014.11.019 - 68.
Parfenova LV, Zakirova IV, Kovyazin PV, Karchevsky SG, Istomina GP, Khalilov LM, Dzhemilev UM. Intramolecular mobility of η5‐ligands in chiral zirconocene complexes and enantioselectivity of alkene functionalization by organoaluminum compounds. Dalton Transactions. 2016; 45 :12814-12826. DOI: 10.1039/c6dt01366j - 69.
Parfenova LV, Kovyazin PV, Tyumkina TV, Berestova TV, Khalilov LM, Dzhemilev UM. Asymmetric alkene cycloalumination by AlEt3, catalyzed with neomenthylindenyl zirconium η5‐complexes. Journal of Organometallic Chemistry. 2013; 723 :19-25. DOI: 10.1016/j.jorganchem.2012.10.021 - 70.
Parfenova LV, Berestova TV, Kovyazin PV, Yakupov AR, Mesheryakova ES, Khalilov LM, Dzhemilev UM. Catalytic cyclometallation of allylbenzenes by EtAlCl2 and Mg as new route to synthesis of dibenzyl butane lignans. Journal of Organometallic Chemistry. 2014; 772-773 :292-298. DOI: 10.1016/j.jorganchem.2014.09.033 - 71.
Bell L, Whitby RJ, Jones RVH, Standen MCH. Catalytic asymmetric carbomagnesiation of unactivated alkenes. A new, effective, active, cheap and recoverable chiral zirconocene. Tetrahedron Letters. 1996; 37 :7139-7142. DOI: 10.1016/0040‐4039(96)01561‐4 - 72.
Bell L, Brookings DC, Dawson GJ, Whitby RJ, Jones RVH, Standen MCH. Asymmetric ethylmagnesiation of alkenes using a novel zirconium catalyst. Tetrahedron. 1998; 54 :14617-14634. DOI: 10.1016/S0040‐4020(98)00920‐X - 73.
Shaughnessy H, Waymouth RM. Enantio– and diastereoselective catalytic carboalumination of 1‐Alkenes and α, ω‐dienes with cationic zirconocenes: Scope and mechanism. Organometallics. 1998; 17 :5728-5745. DOI: 10.1021/om9807811 - 74.
Wipf P, Ribe S. Water/MAO acceleration of the zirconocene–catalyzed asymmetric methylalumination of α‐olefins. Organic Letters. 2000; 2 :1713-1716. DOI: 10.1021/ol005865w - 75.
Wipf P, Ribe S. Water–accelerated tandem Claisen rearrangement–catalytic asymmetric carboalumination. Organic Letters. 2001; 3 :1503-1505. DOI: 10.1021/ol015816z - 76.
Millward DB, Cole AP, Waymouth RM. Catalytic carboalumination of olefins with cyclopentadienyl amidotitanium dichloride complexes. Organometallics. 2000; 19 :1870-1878. DOI: 10.1021/om990707y - 77.
Petros RA, Camara JM, Norton JR. Enantioselective methylalumination of α‐olefins. Journal of Organometallic Chemistry. 2007; 692 :4768-4773. DOI: 0.1016/j.jorganchem.2007.06.028 - 78.
Ota Y, Murayama T, Nozaki K. One‐step catalytic asymmetric synthesis of all‐syn deoxypropionate motif from propylene: Total synthesis of (2R,4R,6R,8R)‐2,4,6,8‐tetramethyldecanoic acid. Proceedings of the National Academy of Sciences. 2016; 113 :2857-2861. DOI: 10.1073/pnas.1518898113