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Review Article a Review on Olefin Metathesis Reactions As a Green Method for the Synthesis of Organic Compounds

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Review Article a Review on Olefin Metathesis Reactions As a Green Method for the Synthesis of Organic Compounds Hindawi Journal of Chemistry Volume 2021, Article ID 3590613, 14 pages https://doi.org/10.1155/2021/3590613 Review Article A Review on Olefin Metathesis Reactions as a Green Method for the Synthesis of Organic Compounds Atitegeb Abera Tsedalu Department of Chemistry, Arba Minch University, Arba Minch, Ethiopia Correspondence should be addressed to Atitegeb Abera Tsedalu; [email protected] Received 15 August 2020; Revised 4 February 2021; Accepted 9 July 2021; Published 6 September 2021 Academic Editor: Pasquale Longo Copyright © 2021 Atitegeb Abera Tsedalu. )is is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. Olefin metathesis is a metal-mediated C-C bond exchange by which the two fragments within the olefin precursor are redis- tributed as a result of breaking the double bond to obtain a new product. Currently, most of the synthetic organic compounds, polymers, drugs, plastics, and other synthetic materials are synthesized via the application of olefin metathesis reactions. In this review, different types of olefin metathesis reactions with their plausible mechanisms and their application in synthetic organic chemistry have been discussed. 1. Introduction )e aforementioned old methods have been proved in a synthesis framework of organic chemistry for C-C double )ere are many chemical transformation ways that are bond formation with their drawbacks. But because of the nonmetal processes that employ reactive functional groups, above overwhelming problems, the effective, environmen- like aldehydes and ketones, to form carbon-carbon bonds for tally friendly, and elegant method which is the olefin me- the synthesis of natural and synthetic organic compounds tathesis reaction has been viewed as a synthetic route for the applicable for different purposes. Once these reactive synthesis of target organic compounds. )is reaction con- functionalities are introduced, the subsequent cross-cou- sists of a metal-catalyzed carbon skeleton redistribution in pling reactions are very reliable double bond-forming which a mutual exchange of unsaturated carbon-carbon processes. In many cases, however, protective groups are bonds takes place, as illustrated in the catalyzed self-reaction required to mask these functional groups prior to their of propene leading to ethene and but-2-ene shown in conversion to olefins, such as carbonyl protective groups. Scheme 2 [4, 5]. Another drawback of these traditional methods is the use of harsh reagents, such as triflic anhydride and brominating 2. Olefin Metathesis reagents to prepare cross-coupling reagents. )e most ob- vious reactions for C-C bond formation which are the Wittig Olefin metathesis is a metal-catalyzed transformation, which and Grignard reactions require highly basic conditions that acts on carbon-carbon double bonds and rearranges them are incompatible with many substrates of interest. In the case via cleavage and reassembly [6–10]. )is type of reaction is of Wittig reactions, every mole of the desired carbon-carbon relatively simple and it often creates fewer undesired by- double bond comes along with an equivalent of triphenyl- products and hazardous wastes than alternative organic phosphine oxide, which is difficult to remove on a large scale reactions. Most of the olefin metathesis reactions are as a waste of raw materials [1–3]. transition metal alkylidene-catalysed reactions. )ese con- )e following reactions (Schemes 1(a) and 1(b)) are stitute a facile and efficient strategy for approching alkene examples of old methods to form C-C double bonds using precursors for the synthesis of various synthetic and natural different reaction routes. products through olefin metathesis reactions. Such reaction 2 Journal of Chemistry Suzuki–Miyaura coupling R BR R2 2 R2 R 2 + Br R R 2 R 1 1 O Wittig reaction 1 + R1 + H Br Ph3P Base MeO C MeO2C 2 + Heck coupling O R2 + Peterson olefnation R2 R SiR R 1 3 Base 1 SnR3 R Me 2 R2 Me R + TiO Stille coupling 1 R1 (a) (b) Scheme 1: (a) Metal-catalyzed alkene formation reactions. (b) Alkene formation reactions without metal catalyst. Catalyst + + + Scheme 2: Metathesis reaction of 1-propene to form trans and cis-2-butene. routes have been emerged in due time in different effortful According to this mechanism (Scheme 5), the coordi- research studies in different industries and academia nation of an olefin to a metal-carbene catalytic species leads [11, 12]. to the reversible formation of a metallacyclobutane inter- Olefin metathesis is one of the very few fundamentally mediate. )e metallacyclobutane can eliminate an olefin novel organic reactions which open up new industrial routes from either side of the ring, leading to degenerate metathesis, to important petrochemicals, polymers, oleochemicals, and in which the starting olefin and carbene are reformed specialty chemicals applicable for different purposes [13]. (nonproductive path), or productive metathesis, in which )is type of reaction is now being used in drug discovery for new olefins and carbenes are produced. As the catalytic cycle the synthesis of anticancer and other antibiotic organic continues, an equilibrium mixture of olefins is produced, compounds. Mazur et al. discovered a novel drug, the ansa- and the ultimate product ratio is determined by thermo- ferrocene-triazole-uracil conjugate, (±)-9 for the relief of dynamic parameters. For instance, if one of the olefins is breast cancer through metathesis reactions using 1,1′-dia- volatile, it can be removed from the system to drive the llylferrocene (1) as a starting material through ring-closing equilibrium towards the desired products [12]. metathesis and other consecutive reactions in the presence )ere are two major approaches that are commonly of Grubbs catalysts (Schemes 3(a)–3(c)) [14]. employed to drive the reaction towards the desired products. Development of metathesis catalysts (Figure 1) and One tactic is to rely on Le Chatelier’s principle by contin- improving different metathesis reactions for the synthesis of uously removing one of the products from the reaction useful polymers and novel materials have been of interest to system in order to shift the equilibrium in favor of the other many researchers. In fact, the availability of various me- product. )is method is especially effective in the case of tathesis catalysts together with research efforts focused on cross-metathesis (CM) reactions involving terminal olefins, the development of more active complexes helps to improve ring-closing metathesis (RCM), and acyclic diene metathesis the economical outcome of industrial processes including polymerization (ADMET) because the volatile gas by- those in the pharmaceutical industry [15]. product (like ethene and propene) formed in these processes On the other hand, a metal alkylidene catalyst-free can be easily removed [17–25]. metathesis reaction for the construction of the C-C double )e other approach capitalizes on the ring strain of cyclic bond is now taking view and interest in many organic olefins such as cyclooctenes and norbornenes. )e energy laboratories. Haung et al. (2016) synthesized tetrasubstituted released during the ring-opening reaction of these com- quinolinones using diazo compounds and para-quinone pounds is sufficient to drive reactions such as ring-opening methides via metathesis reactions using TiCl4 as the Lewis cross metathesis (ROCM) and ring-opening metathesis po- acid and dichloromethane as a solvent (Scheme 4) [16]. lymerization (ROMP) forward. In some instances, substrate concentration, which often distinguishes ADMET from RCM or the catalysts’ sensitivity to olefin substitution, can also be 2.1. General Reaction Mechanism of Transition Metal Alky- taken advantage of to influence product selectivity. All of lidene Olefin Metathesis. )ough the olefin metathesis re- these methods are currently successfully employed in the action was discovered in the mid-1950s, its accepted synthesis of a large variety of small, medium, and polymeric mechanism (Scheme 5) was proposed by Chauvin and molecules, as well as novel materials [6, 7, 24, 26–35]. Herisson in 1971 which indicated that the reaction is cat- Since all of these processes are fully reversible, only alyzed by metal carbenes [12]. statistical mixtures of starting materials as well as all of the Journal of Chemistry 3 a) b) c) Fe Fe Fe Fe O 1 O 2 (±)-3 (±)-4 (a) Fe Fe a) Fe b) Fe + O O O O O O O (±)-3 (±)-5 H H OH c) HO 6 Fe O (±)-3′ (b) a) c) Fe Fe b) Fe O Fe N O N N HO N3 N N O (±)-3′ (±)-7 (±)-8 H (±)-9 (c) Scheme ° 3: (a) Synthesis of the (±)-3and (±)-4 aldehydes: a) [Ru(�CHPh)Cl2(PCy3)2], CH2Cl2, reflux, 3 h; b) CH(OEt)3, AlCl3, toluene, 0 C ° to rt, 1 h or DMF, POCl3, CHCl3, rt, 20 h. (b) Resolution of (±)-3 into enantiomers: a) CH(OMe)3, p-TsOH, 80–90 C; b) (S)-(-)-1,2,4- ° ° ° butanetriol, p-TsOH, CHCl3, 60 C; then crystallization from hexanes and 2-propanol at 4 C; c) p-TsOH, CH2Cl2,H2O, 60 C. (c) Synthesis of ° (±)-9: a) NaBH4, MeOH, THF, rt, 24 h for 7a; 48 h for (±)-7; b) NaN3, CH3COOH, 50 C, 3 h; c) 3-propargyluracil, CuSO4 × 5H2O, sodium ascorbate, EtOH, rt 4 days for (±)-9. L P(Cy) L P(Cy) 3 3 Cl Cl Cl Cl Ru Ru Ru Ru Cl Cl Cl Cl O P(Cy) O P(Cy)3 3 G-I G- II; G- II' H- 4 H-II; H-II' L Cl L L Cl Ph Ru Cl Ru Cl Ru Cl O NO2 O Cl O P(Cy)3 MeO E-II; E-II' E-II; E-II' Ind-II; Ind-II' Figure 1: Selected modern ruthenium-based olefin metathesis catalysts. 4 Journal of Chemistry R1 HO R2 N2 R1 3 R O2C 3 R O2C O 4 R4 R1 R1 R N2 R2 R3 O R1 N R2 OH R1 R3 O R1 = tert-but Scheme 4: Synthesis of tetrasubstituted quinolinones using diazo compounds and para-quinone methides via metathesis reactions using ticl4 as the Lewis acid and dichloromethane as a solvent.
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