Novel ruthenium complexes, methods for their synthesis, intermediate compounds used in the methods, methods for their synthesis, and use of novel ruthenium complexes in olefin metathesis reactions

Abstract

The subject of the present invention is a novel ruthenium complex of the general formula Ru-1, in which all variable substituents have the meanings defined herein. The subject of the present invention is also a process for obtaining the ruthenium complex, a ligand precursor intermediate compound used in the preparation of the ruthenium complex CAAC-1, and the use of this ruthenium complex as a (pre)catalyst in olefin metathesis reactions.

Description

[Technical Field]

[0001] The subject of the present invention is novel ruthenium complexes bearing CAAC-type ligands (cyclic alkylaminocarbenes), which have found widespread use as catalysts and / or (pre)catalysts for olefin metathesis reactions, and their use in olefin metathesis reactions. The subject of the present invention also includes intermediate compounds used to synthesize the novel ruthenium complexes bearing CAAC ligands, as well as methods for synthesizing the novel ruthenium complexes bearing CAAC ligands. The present invention finds use as a desirable tool in widely understood organic synthesis, particularly in cross-metathesis reactions with ethylene, the selective synthesis of olefins bearing C=C bonds in ethenolysis. [Background technology]

[0002] In recent years, significant progress has been made in the use of olefin metathesis in organic synthesis [RH Grubbs (editors), AG Wenzel (editors), DJ O'Leary (editors), E. Khosravi (editors), Handbook of Olefin Metathesis, 2nd edition, Vol. 3, 2015, Wiley-VCH Verlag GmbH & Co. KGaA, p. 1608]. The state-of-the-art technology includes a number of homogeneous ruthenium-based olefin metathesis catalysts that not only exhibit high activity in various types of metathesis reactions but also high tolerance toward functional groups present in the substrates / products. This combination of features makes metathesis catalysts extremely important in modern organic synthesis and industry. The ruthenium complexes most prevalent in the literature and most widely used in olefin metathesis reactions include the Grubbs-type ruthenium complexes (Gru-I, Gru-II, and Gru-III), the Hoveyda-Grubbs complexes (Hov-I and Hov-II), and the first-, second-, and third-generation indenylidene complexes (Ind-I, Ind-II, and Ind-III) [Grubbs et al., Chem. Rev. 2010, 110, 1746-1787; Nolan et al. Chem. Commun. 2014, 50, 10355-10375]. In other cases, the majority of olefin metathesis catalyst structures are derived from the aforementioned ruthenium complexes.

[0003] Recently, NHC ligands in ruthenium catalyst structures have been replaced with cyclic(alkyl)(amino)carbene ligands (CAAC), and the resulting complexes have become important in modern organic synthesis due to their use in cross-metathesis reactions and ring-closing metathesis [Grubbs et al., Chem. Rev, 2010, 110, 1746-1787; WO 2017 / 055945].

[0004] [ka]

[0005] In modern organic synthesis, in an era of increasing scarcity of resources, including fossil fuels, and a risk of shortage of raw materials for the synthesis of polymers, for example, based on products obtained from crude oil, it is crucial to develop new techniques and reactions that enable the synthesis of target compounds. Such processes include ethenolysis reactions, particularly the ethenolysis of methyl / ethyl derivatives of long-chain fatty acids. Ruthenium complexes bearing CAAC ligands in the ruthenium coordination sphere are particularly used for this purpose. The first literature report of a ruthenium catalyst for olefin metathesis bearing a CAAC ligand dates back to 2005 [Bertrandt et al., Angew. Chern. Int Ed., 2005, 44, 5705-5709]. In this scientific publication, Bertrandt described for the first time the CAAC ligand and its use in organic synthesis. In a subsequent publication from 2007 [Bertrandt et al., Angew. Chem. Int Ed., 2007, 46, 7262-7265], Bertrandt described the first methods for the synthesis of ruthenium complexes bearing the CAAC ligand. In both cases, the ligand contained 2,6-diisopropylbenzene at the nitrogen atom and either two methyl (Ru5) or cyclohexyl (Ru10) substituents at carbon atom C2. Next, Professor Bertrand's team, in collaboration with Professor Grubbs' team, synthesized and tested 17 catalysts for their activity in the ethenolysis reaction of methyl oleate, in which the CAAC ligands contained symmetric substituents at the nitrogen atom, i.e., mesityl, 2,6-diisopropylbenzene, 2,6-diethylbenzene, as well as unsymmetric substituents, i.e., 2-ethyl-6-methylbenzene, 2-isopropyl-6-methylbenzene, 2-methyl-6-tertbutylbenzene, while the C2 carbon atom contained two of the following substituents: methyl, ethyl, n-propyl, cyclohexyl, adamantyl, or phenyl [Bertrandt et al., Angew. Chern. Int Ed., 2015, 54, 1919-1923].These catalysts showed high activity towards the C-C double bond of methyl oleate in the presence of ethylene overpressure, which led to the formation of 1-decene and 9-decenoic acid methyl esters, which are valuable industrial products in olefin metathesis reactions.

[0006] [ka]

[0007] In 2017, Gawin et al. first published a method for the synthesis of indenylidene-type complexes bearing two CAAC ligands [Gawin et al., Angew. Chem. Int Ed. 2017, 56, 981-986; EP 3356379]. This publication presents a method for the preparation of indenylidene complexes bearing two CAAC ligands and tests the activity of the complexes in selected reactions, including macrocyclization, ethenolysis, and α-olefin cross-metathesis. This document also discloses a novel approach to the synthesis of Hoveyda-Grubbs catalysts bearing CAAC ligands, involving thermal dissociation of one CAAC ligand in the indenylidene complex followed by reaction of the intermediate with the relevant styrene.

[0008] [ka]

[0009] In 2017, Gawin et al. published a method for synthesizing a para-nitro Hoveyda-Grubbs analogue using a bis-CAAC complex as a substrate [Gawin et al., ACS Catal. 2017, 7, 5443-5449]. The complex proved effective in macrocyclization and cross-metathesis reactions with acrylonitrile.

[0010] [ka]

[0011] The European patent [EP 3356379] discloses the structure Ru35-Ru37 with modified benzylidene fragments.

[0012] [ka]

[0013] Subsequent modifications of ruthenium catalysts included Hoveyda-Grubbs-type complexes, in which the hydrogen atoms of the styrene moiety were replaced with EWG or EDG groups. Mignagni et al. investigated the reactivity of Ru38 and Ru39 catalysts by adjusting the nature of the styrene ether ligands (FR 2947189; FR 2934178). The presence of electron-donating amino groups was shown to have a negative effect on catalytic activity. On the other hand, modification of Ru40 with electron-accepting SO2NMe2 groups (Zhan-type catalysts) enabled the synthesis of highly active catalysts for the ethenolysis of fatty acids (EP 1905777; US 2011 / 0306815).

[0014] [ka]

[0015] Verpoort et al. investigated the effects of labile chelating groups, namely benzyl ether, benzyl thioether, and benzyl amine [WO 2017 / 185324]. All catalysts converted methyl oleate with high selectivity and high TON values ​​(180,000–210,000) [turnover number—number of catalytic cycles, calculated number of moles of substrate reacted per mole of catalyst]. The reaction with ethylene in the presence of Ru43 chelated with benzyl amine and an activator (HSiCl3) (99.995%) yielded the highest TON value (390,000) ever recorded.

[0016] [ka]

[0017] Lemcoff et al. demonstrated that an analogue of the Hoveyda-Grubbs catalyst exists with the cis / trans pair Ru44-Ru47, chelated by sulfur in the benzylidene moiety. The activity of the complex was investigated, namely in the polymerization of norbornene derivatives [Rozenberg, I. et al., ACS CataL 2018, 8, 8182-8191].

[0018] [ka]

[0019] The limited availability of a wide range of structurally diverse aldehydes used as substrates in the synthesis of CAAC ligands is a significant problem known to the state of the art. Their use is primarily limited to simple aldehydes, including isobutanal or 2-phenylpropanal. The high cost and limited availability of other aldehyde derivatives, especially those containing heterocycles, which provide the expected products in low yields, as well as the long and complex synthetic routes to these and other derivatives, significantly limit the possibilities for designing novel ruthenium catalysts containing modified CAAC ligands. These characteristics pose significant limitations to the further development of ruthenium-based organometallic catalysts bearing novel CAAC ligands. In particular, obtaining novel catalysts for olefin metathesis using a wide variety of aldehyde-based ligands with the desired properties has become difficult to implement in chemical synthesis, making industrial scale-up economically unjustifiable.

[0020] In the search for novel ruthenium complexes with high catalytic activity and improved stability and selectivity, allowing for the attainment of high TON values, it is important that convenient synthetic routes based on readily available and inexpensive substrates lead to these compounds. From the perspective of industrial scale-up, it is also important that the planned synthesis is efficient at every stage and that the reaction products can be purified in a simple manner using techniques such as crystallization or distillation. It is also important to expand the library of ligands, including alternative and / or improved sources of ruthenium complex structures for use as catalysts in the ethenolysis of ester derivatives of fatty acids.

[0021] From an industrial perspective, it is crucial that the activity of novel ruthenium complexes makes it possible to carry out the ethenolysis process on crude vegetable oils through the laborious multi-step procedure of purifying the raw material from compounds that deactivate the active catalyst molecules, such as oxygen, water, amines, sulfur compounds, halides, and peroxides. From an industrial perspective, it is equally important to be able to carry out the metathesis process using ethylene available in industrial facilities, rather than simply using commercially available high-purity ethylene (ethylene 3.0 = 99.9% purity or ethylene 4.5 = 99.995% purity). It is worth emphasizing that the procedures performed in a glove box under an argon atmosphere, as described by numerous prominent scientists in reputable academic journals, cannot be reproduced and applied under industrial conditions. Therefore, it is essential to investigate novel ruthenium catalysts that are robust under reaction conditions and, at the same time, active and efficient for carrying out the metathesis process.

[0022] Equally important is the ease and possibility of transporting and storing the catalyst under normal atmospheric conditions, without the use of inert gases and low temperatures. The properties of these catalysts anticipated by industry allow for their easy use on a large industrial scale, without the need for complex equipment.

[0023] Surprisingly, it has been discovered that complexes containing CAAC ligands with heteroaromatic substituents exhibit properties desired and sought after by industry. Surprisingly, it has been found that the ethenolysis process catalyzed by the novel ruthenium complexes tolerates the presence of oxygen, allowing the device to be assembled in air and allowing the use of lower purity ethylene than processes known in the literature, as well as derivatives of fatty acid esters (plant-derived oils) without the need for lengthy purification processes to achieve high purity of the raw material. Summary of the Invention

[0024] The subject of the present invention is a compound of formula CAAC-1 [ka] During the ceremony, X is a halogen anion, BF4 - , PF6 - , ClO4 - , CF3SO2O - represents an anion selected from the group comprising: R 1 , R 2 , R 3 , R 4 , and R 5 are independently hydrogen atoms, C1-C 12 Alkyl groups, C3-C 12 Cycloalkyl groups, C5-C 20 Aryl group or C5-C 20 Heteroaryl groups, C5-C 25 Aralkyl groups, which are hydrogen atoms, halogen atoms, C1-C 12 Alkyl groups, C1-C 12 Perfluoroalkyl groups, C5-C 20 Aryl groups, C5-C 20 Perfluoroaryl groups, C5-C 20 Heteroaryl groups, C1-C 12 Alkoxy groups, C5-C 24 Aryloxy group, C5-C 20Each of the R groups may be independently substituted by one or more substituents selected from the group consisting of a heteroaryloxy group, a sulfide group (-SR"), an amino group (-NR"), and the R groups may be independently selected from the group consisting of a hydrogen atom, a C1-C5 alkyl, a C6-C 24 Aryl, C7-C 24 Indicates aralkyl or Alternatively, R 1 , R 2 , R 3 , R 4 , and R 5 are joined together, C5-C 25 Forming a ring; Each substituent R 6 , R 7 , and R 8 is a hydrogen atom, halogen atom, C1-C 12 Alkyl group or C5-C 20 aryl groups, which are hydrogen atoms, C1-C 12 Alkyl groups, C1-C 12 Perfluoroalkyl groups, C5-C 20 Aryl groups, C5-C 20 Perfluoroaryl groups, C5-C 20 Heteroaryl groups, C1-C 12 Alkoxy groups, C5-C 24 Aryloxy group, C5-C 20 and / or a group including a heteroaryloxy group or a halogen atom, a sulfide group (-SR"), an amino group (-NR"), wherein the R" group is selected from the group consisting of a hydrogen atom, a C1-C5 alkyl, a C6-C 24 Aryl, C7-C 24 Aralkyl independently indicated; Substituent R 9 represents a substituted or unsubstituted heterocyclic group or an organometallic complex group such as ferrocene, which may be a hydrogen atom, a C1-C 12 Alkyl groups, C1-C 12 Perfluoroalkyl groups, C5-C 20 Aryl groups, C5-C 20 Perfluoroaryl groups, C5-C 20 Heteroaryl groups, C1-C12 Alkoxy groups, C5-C 24 Aryloxy group, C5-C 20 and R′ groups may be independently substituted by one and / or more substituents selected from the group including heteroaryloxy groups, sulfide groups (—SR′′), amino groups (—NR′′), and R′ groups may be independently substituted by one or more substituents selected from the group including hydrogen atoms, C1-C5 alkyl, C6-C 24 Aryl, C7-C 24 Aralkyl can be independently represented, Alternatively, R 6 and R 7 and / or R 8 and R 9 are joined together, C5-C 25 Forming a ring; It is a precursor of cyclic alkylamine carbene (CAAC) represented by the formula:

[0025] Preferably, the substituent R 9 represents a substituted or unsubstituted heterocyclic group selected from the group consisting of thiophene, benzothiophene, furan, benzofuran, pyrrole, benzopyrrole, aziridine, oxirane, thiirane, azetidine, oxetane, thietane, pyrrolidine, tetrahydrofuran, tetrahydrothiophene, piperidine, tetrahydropyran, thiane, pyridine, azepane, oxepane, thiepane, azepine, oxepine, thiepine, oxazole, imidazole, thiazole, isoxazole, pyrazole, isothiazole, triazine, pyrrolidine, pyridine, pyrimidine, hydantoin, quinoline, isoquinoline, chromonyl, coumarin, indole, indolizine, indazole, purine, quinolizine, isoquinol, quinol, phthalazine, naphthyridine, carbazole, and β-carboline, or the substituent R 9 represents a substituted or unsubstituted organometallic complex group comprising a cyclopentyl ring and a metal atom selected from iron, cobalt, nickel, chromium, titanium, zirconium (metallocene).

[0026] Preferably, the substituent R 9represents a substituted or unsubstituted heterocyclic group selected from thiophene, benzothiophene, furan, benzofuran, or ferrocene.

[0027] Preferably, the precursor defined above has a structure represented by formula L1, L2, L3, L4, L5, L6, L7, L8, L9, L10, L11, L12, L13, L14, L15, L16, L17, L18, L19, L20, L21, or L22: [ka]

[0028] The subject of the present invention is also a compound of formula 1-Ru [ka] During the ceremony, X 1 and X 2 are, independently of each other, halogen anions, -CN, -SCN, -OR a , -SR a , -O(C=O)R a , -O(SO2)R a , and -OSi(R a )3 groups, and R a is C1-C 12 Alkyl, C3-C 12 Cycloalkyl, C2-C 12 Alkenyl, or C5-C 20 aryl, which have at least one C-C 12 Alkyl, C1-C 12 Perfluoroalkyl, C1-C 12 Alkoxyl, C5-C 24 Aryloxyl, C5-C 20 optionally substituted with heteroaryloxyl or halogen atoms; R 1 , R 2 , R 3 , R 4 , and R 5 are independently hydrogen atoms, C1-C12 Alkyl groups, C3-C 12 Cycloalkyl groups, C5-C 20 Aryl group or C5-C 20 Heteroaryl groups, C5-C 25 Aralkyl groups, which are hydrogen atoms, halogen atoms, C1-C 12 Alkyl groups, C1-C 12 Perfluoroalkyl groups, C5-C 20 Aryl groups, C5-C 20 Perfluoroaryl groups, C5-C 20 Heteroaryl groups, C1-C 12 Alkoxy groups, C5-C 24 Aryloxy group, C5-C 20 and optionally substituted independently by one and / or more substituents selected from the group comprising a heteroaryloxy group, a sulfide group (—SR″), an amino group (—NR″2), wherein the R″ group is selected from the group consisting of a hydrogen atom, a C1-C5 alkyl, a C6-C 24 Aryl, C7-C 24 Aralkyl may be independently designated or, alternatively, R 1 , R 2 , R 3 , R 4 , and R 5 are joined together, C5-C 25 Forming a ring; Each substituent R 6 , R 7 , and R 8 is a hydrogen atom, halogen atom, C1-C 12 Alkyl group or C5-C 20 aryl groups, which are hydrogen atoms, C1-C 12 Alkyl groups, C1-C 12 Perfluoroalkyl groups, C5-C 20 Aryl groups, C5-C 20 Perfluoroaryl groups, C5-C 20 Heteroaryl groups, C1-C 12 Alkoxy groups, C5-C 24 Aryloxy group, C5-C 20and optionally substituted independently by one and / or more substituents selected from the group comprising a heteroaryloxy group or a halogen atom, a sulfide group (—SR″), an amino group (—NR″2), wherein the R″ group is selected from the group consisting of a hydrogen atom, a C1-C5 alkyl, a C6-C 24 Aryl, C7-C 24 Aralkyl stands for Aralkyl; Substituent R 9 represents a substituted or unsubstituted heterocyclic group and / or organometallic complex group, which may be a hydrogen atom, a halogen atom, a C1-C 12 Alkyl groups, C1-C 12 Perfluoroalkyl groups, C5-C 20 Aryl groups, C5-C 20 Perfluoroaryl groups, C5-C 20 Heteroaryl groups, C1-C 12 Alkoxy groups, C5-C 24 Aryloxy group, C5-C 20 and optionally substituted independently by one and / or more substituents selected from the group comprising a heteroaryloxy group, a sulfide group (—SR″), an amino group (—NR″2), wherein the R″ group is selected from the group consisting of a hydrogen atom, a C1-C5 alkyl, a C6-C 24 Aryl, C7-C 24 Aralkyl can be independently represented, Alternatively, R 6 and R 7 and / or R 8 and R 9 are joined together, C5-C 25 Forming a ring; R 16 and R 17 are independently hydrogen atoms, halogen atoms, C1-C 25 Alkyl, C3-C 12 Cycloalkyl, C1-C 12 Perfluoroalkyl, C2-C 25 Alkenes, C2-C 25 Alkenyl, C3-C 25 Cycloalkenyl, C2-C 25 Alkynyl, C3-C 25 Cycloalkynyl, C1-C 25 Alkoxy, C5-C25 Aryl, C5-C 25 Aryloxyl, C6-C 25 Aryl alkyl, C5-C 25 Heteroaryl, C5-C 25 Heteroaryloxyl, C5-C 25 perfluoroaryl, a 3- to 12-membered heterocycle containing a sulfur, oxygen, nitrogen, selenium, or phosphorus atom; Substituent R 16 and R 17 can be combined to form C3-C 25 Cycloalkyl, C3-C 25 Cycloalkenyl, C3-C 25 Cycloalkynyl, C5-C 25 Aryl, C5-C 25 Heteroaryl, C5-C 25 forming a ring selected from the group consisting of perfluoroaryl, sulfur, oxygen, nitrogen, selenium, or phosphorus atom-containing 3- to 12-membered heterocycles, which may be hydrogen atoms, halogen atoms, C1-C 25 Alkyl, C3-C 25 Cycloalkyl, C1-C 12 Perfluoroalkyl, C2-C 25 Alkenes, C2-C 25 Alkenyl, C3-C 25 Cycloalkenyl, C2-C 25 Alkynyl, C3-C 25 Cycloalkynyl, C1-C 25 Alkoxyl, C5-C 25 Aryl, C5-C 25 Aryloxyl, C6-C 25 Aryl alkyl, C5-C 25 Heteroaryl, C5-C 25 Heteroaryloxyl, C5-C 25 optionally independently substituted with one or more substituents selected from the group including perfluoroaryl, 3- to 12-membered heterocycle; G is selected from the following: -Ligand of formula CAAC-1 [ka] In the formula, X and the substituent R 1 ~R 9 has the meaning defined above, or - 1 heteroatom selected from the group containing oxygen, sulfur, or selenium atoms, and 25 Alkyl, C1-C 25 Perfluoroalkyl, C3-C 25 Cycloalkyl, C5-C 20 Alkoxyl, C5-C 20 Aryl, C5-C 20 Perfluoroaryl, C7-C 20 Aralkyl, C5-C 24 Aryloxyl, C2-C 12 Alkenyl, C6-C 20 Heteroaryl or heteroaryloxyl C5-C 24 , 3- to 12-membered heterocycles, and the like, and optionally substituted by an acyl group (-COR'), a cyano group (-CN), a carboxyl group (-COOH), an ester group (-COOR'), an ester group (-CHCOOR'), an ester group (-CHR'COOR'), an ester group (-C(R')COOR'), an amide group (-CONR'2), a Weinreb amide (-CON(R')(OR')), a sulfone group (-SOR'), a formyl group (-CHO), a sulfonamide group (-SOiNR'2), a ketone group (-COR'), a thioamide group (-CSNR'2), a thioketone (-CSR'), a thionoester group (-CSOR'), a thioester group (-COSR'), or a dithioester group (-CS2R'), and the R' groups are independently C1-C 25 Alkyl, C1-C 25 Perfluoroalkyl, C3-C 25 Cycloalkyl, C5-C 20 Alkoxyl, C5-C 20 Aryl, C5-C 20 Perfluoroaryl, C7-C 20 Aralkyl, C5-C 24 Aryloxyl, C2-C 12 Alkenyl, C6-C20 Heteroaryl, C5-C 24 The dashed line indicates the heteroatom and the substituent R 17 a direct bond between, or a methylene bridge, -CH2-, -CHR'-, or -CR'2-, the substituent R 17 and the heteroatom, and the substituent R 14 But C5-C 15 aryl, optionally containing a hydrogen atom, a halogen atom, a C-C 25 Alkyl, C3-C 25 Cycloalkyl, C2-C 25 Alkenyl, C3-C 25 Cycloalkenyl, C2-C 25 Alkynyl, C3-C 25 Cycloalkynyl, C1-C 25 Perfluoroalkyl, C5-C 20 Alkoxyl, C5-C 20 Aryl, C5-C 20 Perfluoroaryl, C7-C 20 Aralkyl, C5-C 24 Aryloxyl, C6-C 20 Heteroaryl or C5-C 24 Heteroaryloxyl, 3- to 12-membered heterocycle, alkoxyl group (-OR''), sulfide group (-SR''), sulfoxide group (-S(O)R''), sulfonium group (-S + R''2), sulfone group (-SO2R''), sulfonamide group (-SO2NR''2), amino group (-NR''2), ammonium group (-N + R''3), nitro group (-NO2), cyano group (-CN), phosphine group (-P(O)(OR'')2), phosphinic acid group (-P(O)R''(OR'')), phosphonine group (-P(OR'')2), phosphine group (-PR''2), phosphine oxide group (-P(O)R''2), phosphonium group (-P +R''3), carboxyl group (-COOH), ester group (-COOR''), amide group (-CONR''2), amide group (-NR''C(O)R''), formyl group (-CHO), ketone group (-COR''), thioamide group (-CSNR''2), thioketone group (-CSR''), thionoester group (-CSOR''), thioester group (-COSR''), dithioester group (-CS2R''), and the R'' group is substituted by 1 to 4 substituents independently selected from the group consisting of C1-C5 alkyl, C1-C5 perfluoroalkyl, C6-C 24 Aryl, C7-C 24 Aralkyl, C5-C 24 denotes a perfluoroaryl, or -2 heteroatoms selected from the group containing nitrogen or phosphorus atoms, substituted by groups selected from hydrogen atoms, methylidene, etc., and optionally, substituents R', C1-C 25 Alkyl, C1-C 25 Perfluoroalkyl, C3-C 25 Cycloalkyl, C5-C 20 Alkoxyl, C5-C 20 Aryl, C5-C 20 Perfluoroaryl, C7-C 20 Aralkyl, C5-C 24 Aryloxyl, C2-C 12 Alkenyl, C6-C 20 Heteroaryl or C5-C 24 Heteroaryloxyl, 3- to 12-membered heterocycle, acyl group (-COR'), ester group (-COOR'), tert-butyloxycarbonyl group (t-Boc) or 9-fluorenylmethoxycarbonyl group (Fmoc), carbamine group (-CONR'2), sulfone group (-SOR'), formyl group (-CHO), and R' group is C1-C 25 Alkyl, C1-C 25 Perfluoroalkyl, C3-C 25 Cycloalkyl, C5-C 20 Alkoxyl, C5-C 20 Aryl, C5-C 20 Perfluoroaryl, C7-C 20Aralkyl, C5-C 24 Aryloxyl, C2-C 12 Alkenyl, C6-C 20 Heteroaryl or C5-C 24 represents a heteroaryloxyl group, optionally substituted with an acyl group (-COR'), a cyano group (-CN), a carboxyl group (-COOH), an ester group (-COOR'), an ester group (-CHCOOR'), an ester group (-CHR'COOR'), an ester group (-C(R')COOR'), an amide group (-CONR'2), a sulfone group (-SOR'), a formyl group (-CHO), a sulfonamide group (-SOR'2), a ketone group (-COR'), a thioamide group (-CSNR'2), a thioketone group (-CSR'), a thionoester group (-CSOR'), a thioester group (-COSR'), or a dithioester group (-CS2R'), wherein the R' group is a C1-C 25 Alkyl, C1-C 25 Perfluoroalkyl, C3-C 25 Cycloalkyl, C5-C 20 Alkoxyl, C5-C 20 Aryl, C5-C 20 Perfluoroaryl, C7-C 20 Aralkyl, C5-C 24 Aryloxyl, C2-C 12 Alkenyl, C6-C10 heteroaryl, or C5-C 24 The dashed line indicates the heteroatom and the substituent R 14 a direct bond between, or a methylene bridge, (CH2)-, -(CHR')-, or -(CR'2)-, 17 and the heteroatom, and the substituent R 17 But C5-C 15 aryl, optionally containing a hydrogen atom, a halogen atom, a C-C 25 Alkyl, C3-C 25 Cycloalkyl, C2-C 25 Alkenyl, C3-C 25 Cycloalkenyl, C2-C 25 Alkynyl, C3-C 25 Cycloalkynyl, C1-C 25Perfluoroalkyl, C5-C 20 Alkoxyl, C5-C 20 Aryl, C5-C 20 Perfluoroaryl, C7-C 20 Aralkyl, C5-C 24 Aryloxyl, C6-C 20 Heteroaryl or C5-C 24 Heteroaryloxyl, 3- to 12-membered heterocycle, alkoxyl group (-OR''), sulfide group (-SR''), sulfoxide group (-S(O)R''), sulfonium group (-S + R''2), sulfone group (-SO2R''), sulfonamide group (-SO2NR''2), amino group (-NR''2), ammonium group (-N + R''3), nitro group (-NO2), cyano group (-CN), phosphine group (-P(O)(OR'')2), phosphinic acid group (-P(O)R''(OR'')), phosphonine group (-P(OR'')2), phosphine group (-PR''2), phosphine oxide group (-P(O)R''2), phosphonium group (-P + R"3), carboxyl group (-COOH), ester group (-COOR"), amide group (-CONR"), amide group (-NR"C(O)R"), formyl group (-CHO), ketone group (-COR"), thioamide group (-CSNR"), thioketone group (-CSR"), thionoester group (-CSOR"), thioester group (-COSR"), dithioester group (-CS2R"), and the group R" is substituted with 1 to 4 substituents independently selected from the group consisting of C1-C5 alkyl, C1-C5 perfluoroalkyl, C6-C 24 Aryl, C7-C 24 Aralkyl, C5-C 24 denotes a perfluoroaryl, or -3 heteroatoms halogen atoms, and the dashed line indicates the heteroatom and R 17 R indicates a direct bond between the substituents 17 The substituents are C5-C 15 Aryl, or C5-C 25 polyaryl, optionally containing hydrogen atoms, halogen atoms, C-C25 Alkyl, C3-C 25 Cycloalkyl, C2-C 25 Alkenyl, C3-C 25 Cycloalkenyl, C2-C 25 Alkynyl, C3-C 25 Cycloalkynyl, C1-C 25 Perfluoroalkyl, C5-C 20 Alkoxyl, C5-C 20 Aryl, C5-C 20 Perfluoroaryl, C7-C 20 Aralkyl, C5-C 24 Aryloxyl, C6-C 20 Heteroaryl or C5-C 24 Heteroaryloxyl, 3- to 12-membered heterocycle, alkoxy group (-OR''), sulfide group (-SR'), sulfoxide group (-S(O)R''), sulfonium group (-S + R''2), sulfone group (-SO2R''), sulfonamide group (-SO2NR''2), amino group (-NR''2), ammonium group (-N + R''3), nitro group (-NO2), cyano group (-CN), phosphonic acid group (-P(O)(OR'')2), phosphinic acid group (-P(O)R''(OR'')), phosphonine group (-P(OR'')2), phosphine group (-PR''2), phosphine oxide group (-P(O)R''2), phosphonium group (-P + R''3), carboxyl group (-COOH), ester group (-COOR''), amide group (-CONR''2), amide group (-NR''C(O)R''), formyl group (-CHO), ketone group (-COR''), thioamide group (-CSNR''2), thioketone group (-CSR''), thionoester group (-CSOR''), thioester group (-COSR''), dithioester group (-CS2R''), and the R'' group is substituted with 1 to 4 substituents independently selected from the group consisting of C1-C5 alkyl, C1-C5 perfluoroalkyl, C6-C 24 Aryl, C7-C 24 Aralkyl, C5-C 24 Indicates perfluoroaryl; It is a ruthenium complex represented by the formula:

[0029] The ruthenium complex is preferably of the formula 1a-Ru [ka] In the formula, X 1 and X 2 , and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 The substituents have the meanings defined above; "n" means 1 or 0; Z is selected from the group comprising a halogen atom, an O atom, a S atom, a Se atom, or an NR''' group, and R''' is methylidene, C1-C 25 Alkyl, C1-C 25 Perfluoroalkyl, C3-C 25 Cycloalkyl, C5-C 20 Alkoxyl, C5-C 20 Aryl, C5-C 20 Perfluoroaryl, C7-C 20 Aralkyl, C5-C 24 Aryloxyl, C2-C 12 Alkenyl, C6-C 20 Heteroaryl or C5-C 24 Heteroaryloxyl, 3- to 12-membered heterocycle, acyl group (-COR'), ester group (-COOR'), tert-butylcarboxycarbonyl group (t-Boc) or 9-fluorenylmethoxycarbonyl group (Fmoc), carbamine group (-CONR'2), sulfone group (-SOR'), formyl group (-CHO), and R' group is C1-C 25 Alkyl, C1-C 25 Perfluoroalkyl, C3-C 25 Cycloalkyl, C5-C 20 Alkoxyl, C5-C 20 Aryl, C5-C 20 Perfluoroaryl, C7-C 20Aralkyl, C5-C 24 Aryloxyl, C2-C 12 Alkenyl, C6-C 20 Heteroaryl or C5-C 24 represents heteroaryloxyl; or a halogen atom, and when Z represents a halogen atom, R 18 does not exist; R 18 are independently hydrogen atoms, C1-C 25 Alkyl, C1-C 25 Cycloalkyl, C5-C 20 Alkoxyl, C5-C 20 Aryl, C5-C 24 aryloxyl, -COOR''', -CHCOOR''', -CONR''', -CHCONR''', -COR''', -CHCOR''', -CON(OR''')(R'''), -CHCON(OR''')(R''') or halogen atom, wherein R''' is C1-C 12 Alkyl, C3-C 12 Cycloalkyl, C2-C 12 Alkenyl, C6-C 20 aryl, which optionally includes at least one C-C 12 Alkyl, C1-C 12 Perfluoroalkyl, C1-C 12 Alkoxyl, C6-C 24 substituted with aryloxyl or halogen atoms; R 19 , R 20 , R 21 , and R 22 are independently hydrogen atoms, halogen atoms, C1-C 25 Alkyl groups, C2-C 25 Alkenyl groups, C5-C 25 Aryl group, alkoxy group (-OR''), sulfide group (-SR''), sulfoxide (-S(O)R''), sulfonium group (-S + R''2), sulfone group (-SO2R''), sulfonamide group (-SO2NR''2), amino group (-NR''2), ammonium group (-N +R''3), nitro group (-NO2), cyano group (-CN), phosphonic acid group (-P(O)(OR'')2), phosphinic acid group (-P(O)R''(OR'')), phosphonine group (-P(OR'')2), phosphine group (-PR''2), phosphine oxide group (-P(O)R''2), phosphonium group (-P + R''3), carboxyl group (-COOH), ester group (-COOR''), amide group (-CONR''2), amide group (-NR''C(O)R'), formyl group (-CHO), ketone group (-COR''), thioamide group (-CSNR''2), thioketone group (-CSR''), thionoester group (-CSOR''), thioester group (-COSR''), dithioester group (-CS2R''), where R'' group is C1-C5 alkyl, C1-C5 perfluoroalkyl, C6-C 24 Aryl, C7-C 24 Aralkyl, C5-C 24 indicates perfluoroaryl, and R 16 , R 17 , R 18 , and R 19 The substituents may be bonded, thus forming a substituted or unsubstituted C4-C 10 Cyclic or C4-C 12 Forming polycyclic ring systems; It is expressed as:

[0030] The ruthenium complex is preferably of the formula 1b-Ru [ka] In the formula, X 1 and X 2 , and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 The substituents have the meanings defined above; R 16 and R 17 are independently a hydrogen atom, a halogen atom, or an optionally substituted C-C25 Alkyl, optionally substituted C-C 25 Cycloalkyl, optionally substituted C-C 12 Perfluoroalkyl, optionally substituted C-C 25 Alkenes, optionally substituted C2-C 25 Alkenyl, optionally substituted C-C 25 Cycloalkenyl, optionally substituted C-C 25 Alkynyl, optionally substituted C-C 25 Cycloalkynyl, optionally substituted C-C 25 Alkoxyl, optionally substituted C5-C 25 Aryl, optionally substituted C5-C 25 Aryloxyl, optionally substituted C6-C 25 Arylalkyl, optionally substituted C5-C 25 Heteroaryl, optionally substituted C5-C 25 Heteroaryloxyl, optionally substituted C5-C 25 perfluoroaryl, an optionally substituted 3- to 12-membered heterocycle containing a sulfur, oxygen, nitrogen, selenium, or phosphorus atom; R 16 and R 17 The substituents may be bonded to C3-C 25 Cycloalkyl, C3-C 25 Cycloalkenyl, C3-C 25 Cycloalkynyl, C5-C 25 Aryl, C5-C 25 Heteroaryl, C5-C 25 forming a ring selected from the group consisting of perfluoroaryl, sulfur, oxygen, nitrogen, selenium, or phosphorus atom-containing 3- to 12-membered heterocycles, which may be hydrogen atoms, halogen atoms, C1-C 25 Alkyl, C3-C 25 Cycloalkyl, C1-C 12 Perfluoroalkyl, C2-C 25 Alkenes, C2-C 25 Alkenyl, C3-C 25 Cycloalkenyl, C2-C 25 Alkynyl, C3-C 25 Cycloalkynyl, C1-C25 Alkoxyl, C5-C 25 Aryl, C5-C 25 Aryloxyl, C6-C 25 Aryl alkyl, C5-C 25 Heteroaryl, C5-C 25 Heteroaryloxyl, C5-C 25 may be independently substituted with one or more substituents selected from the group including perfluoroaryl, 3- to 12-membered heterocycle; It is expressed as:

[0031] The ruthenium complexes are preferably represented by the formula Ru1a, Ru2a, Ru3a, Ru4a, Ru5a, Ru6a, Ru7a, Ru8a, Ru9a, Ru10a, Ru11a, Ru11a, Ru12a, Ru13a, Ru14a, Ru15a, Ru16a, Ru17a, Ru18a, Ru19a, Ru20a, Ru21a, Ru22a: [ka] TIFF2025531833000016.tif120160

[0032] The subject of the present invention is also a method for obtaining a ruthenium complex of formula 1a-Ru as defined above, comprising the steps of: [ka] Here, the method is as follows: [ka] During the ceremony, L 1 represents a neutral ligand selected from the group consisting of pyridine or substituted pyridine, P(R')3, P(OR')3, O(R')2, N(R')3, and each R' is independently C1-C 12 Alkyl, C3-C 12 Cycloalkyl, C5-C 20 Aryl, C7-C 24 Aralkyl, C5-C 24perfluoroaryl, 5- to 12-membered heteroaryl; N, Z, X 1 , X 2 , and the substituent R 18 , R1', R 20 , R 21 , and R 22 has the meaning defined above, The alkylidene ruthenium complex represented by the formula 8 [ka] In the formula, the substituent R 1 ~R 9 has the meaning defined above, This is a method in which the carbene reacts with the carboxyl group.

[0033] The subject of the present invention also relates to the use of compounds of formula 1-Ru as defined above as precatalysts and / or catalysts in olefin metathesis reactions, in particular in ring-closing metathesis (RCM), cross-metathesis (CM), homometathesis (cross-metathesis between two molecules of the same olefin), ethenolysis, isomerization, diastereoselective ring rearrangement metathesis (DRRM) reactions, "alkene-alkyne" (ene-yne) metathesis or ROMP or ADMET polymerization reactions.

[0034] The reaction is preferably carried out in an organic solvent such as toluene, mesitylene, hexane, cyclohexane, ethyl acetate, methyl acetate, methyl carbonate, ethyl carbonate, tert-butyl methyl ether, cyclopentyl methyl ether, diethyl ether, THF, 2-Me-THF, 4-Me-THP, dioxane, DME, PAO, PEG, paraffin, esters of saturated fatty acids, and the like.

[0035] The reaction is preferably carried out in a solvent-free system.

[0036] The reaction is preferably carried out at a temperature of from 20°C to 200°C.

[0037] The reaction is preferably carried out for a period of from 5 minutes to 48 hours.

[0038] The 1-Ru compound is preferably used in an amount of 10 mol % or less.

[0039] The 1-Ru compound is preferably used in an amount of 0.1 mol % or less.

[0040] The 1-Ru compound is preferably added to the reaction mixture in aliquots as a solid and / or as a solution in an organic solvent continuously using a pump.

[0041] The gaseous by-products of the reaction, selected from ethylene, propylene, butylene, are preferably vigorously removed from the reaction mixture using inert gas barbotage or under reduced pressure. [Brief explanation of the drawings]

[0042] The subject matter of the present invention is illustrated in the embodiments of the drawings.

[0043] [Figure 1] The structure of the Ru17a compound obtained based on X-ray structural analysis is shown below. [Figure 2] 1 provides an overview of commercially available olefin metathesis pre-catalysts and catalysts and novel pre-catalysts and catalysts according to the present invention. [Figure 3] (A) Photographs showing the set-up and sealed reaction system—autoclave, and (B) the reaction system (autoclave) that is opened prior to the ethenolysis reaction, eliminating the need for a glovebox at any stage of the reaction process. DETAILED DESCRIPTION OF THE INVENTION

[0044] In the description of this specification, the terms used have the following meanings:

[0045] Terms not defined herein have the meanings provided and understood by a person skilled in the art given the best available knowledge, this disclosure, and the contents of this patent application description.

[0046] Unless otherwise specified, the following chemical terminology notations are used in the description herein and have the meanings set forth in the definitions below.

[0047] As used in the present description, the term "halogen atom" means an element selected from F, Cl, Br, I.

[0048] The term "carbene" refers to an electrically inert molecule in which a carbon atom has two non-bonding electrons occurring in a single or triplet state and is linked to two groups by a single covalent bond or to one group by a double covalent bond. The term "carbene" also includes carbene analogs in which the carbene carbon atom is replaced by another chemical element, such as boron, silicon, germanium, tin, lead, nitrogen, phosphorus, sulfur, selenium, or tellurium.

[0049] The term "alkyl" refers to a saturated, straight- or branched-chain hydrocarbon substituent having the specified number of carbon atoms. Examples of alkyl substituents include -methyl, -ethyl, -n-propyl, -n-butyl, -n-pentyl, -n-hexyl, -n-heptyl, -n-octyl, -n-nonyl, and -n-decyl. Representative branched-(C1-C10) alkyls include -isopropyl, -sec-butyl, -isobutyl, -tert-butyl, -isopentyl, -neopentyl, -1-methylbutyl, -2-methylbutyl, -3-methylbutyl, -1,1-dimethylpropyl, -1,2-dimethylpropyl, -1-methylpentyl, -2-methylpentyl, -3-methylpentyl, -4-methylpentyl, -1-ethylbutyl, -2-ethylbutyl, -1,1-dimethylbutyl, -1,2-dimethylbutyl, -1 ,3-dimethylbutyl, -2,2-dimethylbutyl, -2,3-dimethylbutyl, -3,3-dimethylbutyl, -1-methylhexyl, -2-methylhexyl, -3-methylhexyl, -4-methylhexyl, -1,2-dimethylpentyl, -1,3-dimethylpentyl, -5-methylhexyl, -1,2-dimethylhexyl, -1,3-dimethylhexyl, -3,3-dimethylhexyl, -1,2-dimethylheptyl, -1,3-dimethylheptyl, -3,3-dimethylheptyl, and the like.

[0050] The term "alkoxyl" refers to an alkyl substituent, as defined above, attached through an oxygen atom.

[0051] The term "perfluoroalkyl" refers to an alkyl group as defined above in which all hydrogen atoms have been replaced with the same or different halogen atoms.

[0052] The term "cycloalkyl" refers to a saturated, monocyclic or polycyclic hydrocarbon substituent having the specified number of carbon atoms. Examples of cycloalkyl substituents include -cyclopropyl, -cyclobutyl, -cyclopentyl, -cyclohexyl, -cycloheptyl, -cyclooctyl, -cyclononyl, -cyclodecyl, and the like.

[0053] The term "alkenyl" refers to an unsaturated, straight-chain or branched-chain, acyclic hydrocarbon substituent having a specified number of hydrogen atoms and containing at least one carbon-carbon double bond. Examples of alkenyl substituents include vinyl, allyl, 1-butenyl, 2-butenyl, isobutenyl, 1-pentenyl, 2-pentenyl, 3-methyl-1-butenyl, 2-methyl-2-butenyl, 2,3-dimethyl-2-butenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 1-heptenyl, 2-heptenyl, 3-heptenyl, 1-octenyl, 2-octenyl, 3-octenyl, 1-nonenyl, 2-nonenyl, 3-nonenyl, 1-decenyl, 2-decenyl, 3-decenyl, and the like.

[0054] The term "cycloalkenyl" refers to an unsaturated, cyclic or branched, cyclic hydrocarbon substituent having a specified number of hydrogen atoms and containing at least one carbon-carbon double bond. Examples of cycloalkenyl substituents include -cyclopropene, -cyclobutene, -cyclopentene, -cyclohexene, -cycloheptene, -cyclooctene, -cyclononene, -cyclodecene, -methylcyclopropene, -ethylcyclobutene, -isopropylcyclopentene, -methylcyclohexene, and the like.

[0055] The term "aryl" refers to an aromatic, monocyclic or polycyclic hydrocarbon substituent having the specified number of carbon atoms. Examples of aryl substituents include -phenyl, -tolyl, -xylyl, -naphthyl, -2,4,6-trimethylphenyl, -2-fluorophenyl, -4-fluorophenyl, -2,4,6-trifluorophenyl, -2,6-difluorophenyl, -4-nitrophenyl, and the like.

[0056] The term "aralkyl" refers to an alkyl substituent, as defined above, substituted with at least one aryl, as defined above. Examples of aralkyl substituents include -benzyl, -diphenylmethyl, -triphenylmethyl, and the like.

[0057] The term "heteroaryl" refers to an aromatic monocyclic or polycyclic hydrocarbon substituent having the specified number of carbon atoms, in which at least one carbon atom is replaced with a heteroatom selected from O, N, and S atoms. Examples of heteroaryl substituents include -furyl, -thienyl, -imidazolyl, -oxazolyl, -thiazolyl, -isoxazolyl, -triazolyl, -oxadiazolyl, -thiadiazolyl, -tetrazolyl, -pyridyl, -pyrimidyl, -triazinyl, -indolyl, -benzo[b]furyl, -benzo[b]thienyl, -indazolyl, -benzimidazolyl, -azaindolyl, -quinolyl, -isoquinolyl, -carbazolyl, and the like.

[0058] The term "heterocycle" refers to a saturated, unsaturated, or partially unsaturated hydrocarbon substituent having a specified number of carbon atoms, in which at least one carbon atom is replaced with a heteroatom selected from O, N, and S atoms. Examples of heterocyclic substituents include -furyl, -thiophenyl, -pyrrolyl, -oxazolyl, -imidazolyl, -thiazolyl, -isoxazolyl, -pyrazolyl, -isothiazolyl, -triazinyl, -pyrrolidinonyl, -pyrrolidinyl, -hydantoinyl, -oxiranyl, -oxetanyl, -tetrahydrofuranyl, -tetrahydrothiophenyl, -quinolinyl, -isoquinolinyl, -chromonyl, -coumarinyl, -indolyl, -indolizine, -benzo[b]furanyl, -benzo[b]thiophenyl, -indazolyl, -purinyl, -4H-quinolizine, -isoquinolyl, -quinolyl, -phthalazinyl, -naphthyridinyl, -carbazolyl, -β-carbolinyl, and the like.

[0059] The term "neutral ligand" refers to an uncharged substituent that can coordinate with a metal center (transition metal atom). Examples of such ligands can include N-heterocyclic carbenes (NHCs), cyclic (alkyl) (amino) carbenes (CAACs), amines, phosphines and their oxides, alkyl and aryl phosphites and phosphates, arsines and their oxides, ethers, alkyl and aryl sulfides, coordinatively unsaturated or aromatic hydrocarbons, alkyl and aryl halides, nitriles, isonitriles, sulfides, sulfoxides, sulfones, thioketones, thioamides, thioesters, thionoesters, and dithioesters.

[0060] The term "anionic ligand" refers to a substituent capable of coordinating with a charged metal center (transition metal atom) and capable of partially or completely compensating for the charge of the charged metal center. Examples of such ligands may include anions of fluoride, chloride, bromide, iodide, cyanide, cyanate, and thiocyanate, carboxylate, alcohol, phenol, thiol, and thiophenol, anions of hydrocarbons with delocalized charge (e.g., cyclopentadiene anion), anions of (organic) sulfates and (organic) phosphates and their esters (e.g., anions of alkyl and aryl sulfonates, anions of alkyl and aryl phosphates, anions of alkyl and aryl esters of sulfate, anions of alkyl and aryl esters of phosphate, anions of alkyl and aryl esters of alkyl and aryl phosphate, etc.).

[0061] The term "heteroatom" means an atom selected from the group including oxygen, sulfur, nitrogen, phosphorus, boron, silicon, arsenic, selenium, and tellurium.

[0062] The term "PAO" stands for Poly-Alpha-Olefins, an abbreviation used in the present case for low molecular weight polyolefins used as high-boiling solvents. It also refers to a class of solvents and / or lubricants that are products of the polymerization of ethylene derivatives, leading to the formation of branched, saturated hydrocarbons, used as heat-resistant, non-polar, high-boiling solvents.

[0063] Embodiments of the invention The following examples are included solely to illustrate and clarify certain aspects of the invention, and are not intended to limit the invention or to equate with the full scope of the invention as defined in the appended claims. In the following examples, unless otherwise indicated, standard materials and methods used in the art were used, or manufacturer's recommendations for particular reactants and methods were followed.

[0064] Where necessary, model compounds for metathesis reactions were purified by fractional distillation and then stored under an inert gas atmosphere over activated neutral aluminum oxide. Tetrahydrofuran was purified by sodium-potassium alloy distillation in the presence of benzophenone and then stored over 4 Å molecular sieves. Where necessary, selected reactions were carried out under an argon atmosphere using a reaction vessel heated to 130 °C. Aluminum oxide (Al2O3, neutral, Brockman Grade I) was activated by heating at 150 °C under reduced pressure for 16 hours.

[0065] The starting compounds for the synthesis of the aldehyde derivatives were commercially available.

[0066] Example I Synthesis of new aldehydes, precursors of CAAC ligands Scheme 9 below illustrates the first three steps in the synthesis of CAAC ligand precursors for the synthesis of ruthenium catalysts for olefin metathesis (general formulas Ru1a to Ru21a, Scheme 9), the subject of this invention. [ka]

[0067] Reactions R1 to R5 shown in Scheme 9 were carried out using commercially available substrates based on literature procedures with modifications developed by the authors of the present invention. Unless otherwise stated, commercially available solvents were used in the reactions described, and no care was taken in the presence of oxygen and / or moisture.

[0068] Reaction R1 In step R1 (Scheme 9), the synthesis of epoxides of general formula BX is carried out. For this purpose, ketones of general formula AX and trimethylsulfonyl salts, preferably either trimethylsulfonyl bromide (MeSBr) or iodide (MeSI), are used. The conversion is carried out in an organic solvent, preferably acetonitrile (MeCN) or another organic solvent, using stoichiometric amounts of sulfonium salt and metal hydroxide, preferably potassium hydroxide (KOH). The reaction mixture is carried out at elevated temperature, preferably 60 °C, for 2 to 16 hours. The product is isolated from the reaction mixture by filtration and distillation of the solvent.

[0069] R1 embodiment [ka]

[0070] A reaction vessel equipped with a stir bar was charged with 2-acetylthiophene (7.01 g, 6.00 mL, 55.0 mmol, 1.0 equiv.), Me3SI (14.9 g, 71.5 mmol, 1.3 equiv.), KOH (9.44 g, 0.14 mmol, 2.6 equiv.), distilled water (0.25 mL), and MeCN (55 mL) under an argon atmosphere. The contents of the vessel were stirred at 60 °C for 16 h. After the reaction was complete, 15 mL of diethyl ether (Et2O) was added, the precipitate was filtered, washed again with diethyl ether (40 mL), and the solvent was evaporated under reduced pressure. The remaining dark pink oil was washed with diethyl ether (40 mL), evaporated, washed with n-hexane (40 mL), and the solvent was evaporated under reduced pressure to give the expected product as a yellow oil in 91% yield (6.98 g, 49.8 mmol). 1 H NMR(400 MHz, CDCl3)δ ppm:7.21 (dd, j = 5.1, 1.2 Hz, 1H), 7.04 (dd, J = 3.7, 1.3 Hz, 1H), 6.96 (dd, J = 5.1, 3.6 Hz, 1H), 3.07 - 3.03 (m, 2H), 1.78 - 1.78 (m, 3H); 13 C NMR(101 MHz, CDCl3)δ ppm:145.9, 127.2, 125.0, 124.8, 58.7, 55.2, 22.2;

[0071] Reaction R2 In step R2 (Scheme 9), the synthesis of aldehydes of the general formula CX is carried out. For this purpose, an epoxide of the general formula BX and a Lewis acid, preferably SiO2, chloroform, ZnCl2 or ZnBr2, are used. The conversion is carried out in an organic solvent, preferably ethyl acetate (EtOAc), chloroform or toluene (PhMe). The reaction mixture is carried out at room temperature until complete conversion of the substrate (2.5-48 h). The product is purified by distillation of the solvent and is then used in the next step without further purification.

[0072] Embodiments for carrying out reaction R2 [ka]

[0073] 2-Methyl-2-(thiophen-2-yl)epoxide (6.6 g, 47.0 mmol, 1.0 equiv.), silicon dioxide (3.76 g), and ethyl acetate (90 mL) were placed in a reaction vessel equipped with a stirrer. The reaction was carried out at room temperature for 2.5 hours. The silicon dioxide was filtered, and the solvent was distilled off under reduced pressure to give the expected product as a yellow oil in 69% yield (2.60 g, 18.5 mmol).

[0074] Alternative Embodiments for Carrying Out Reaction R2 [ka]

[0075] 2-Methyl-2-(thiophen-2-yl)epoxide (6.6 g, 47.0 mmol, 1.0 equiv.) and chloroform (60 mL) were placed in a reaction vessel equipped with a stirrer. The reaction was carried out at room temperature for 2 hours. The solvent was distilled off under reduced pressure to give the expected product as a yellow oil in >99% yield (6.59 g, 47.0 mmol).

[0076] Alternative Embodiments for Carrying Out Reaction R2 [ka]

[0077] 2-Methyl-2-(benzothiophen-2-yl)epoxide (5.32 g, 28.0 mmol, 1 equiv.), zinc chloride (3.81 g, 28.0 mmol, 1 equiv.), and toluene (119 mL) were placed in a reaction vessel equipped with a stirrer. The reaction was carried out at room temperature for 2 h. The reaction mixture was filtered through a Schott funnel, the solvent was distilled off under reduced pressure, and the crude product was sublimed under reduced pressure using a Kugelrohr glass oven to give the expected product as a colorless solid in 97% yield (5.17 g, 27.2 mmol).

[0078] Reaction R3 In step R3 (Scheme 9), the synthesis of aldehydes of the general formula FX is carried out. For this purpose, aldehydes of the general formula CX and alkenyl halides, preferably chlorides, metal hydroxides, preferably NaOH, and quaternary ammonium salts, preferably tetra-N-butylammonium bromide, are used. The conversion is carried out in an organic solvent, preferably toluene. The reaction mixture is carried out at elevated temperature, preferably 40-60°C, for 30 minutes to 5 hours. The product is isolated from the reaction mixture by extraction. It is then dried over a drying agent, preferably sodium sulfate or magnesium sulfate, the solid is filtered, and the solvent is distilled off under reduced pressure. The product is used in the next step without further purification.

[0079] Embodiments for carrying out reaction R3 [ka]

[0080] A reaction vessel equipped with a stirrer was charged with thiophen-2-ylpropanal (6.4 g, 46.0 mmol, 1.00 equiv.), 3-chloro-2-methylpropene (5.1 g, 55.0 mmol, 1.20 equiv.), potassium hydroxide (2.7 g, 69.0 mmol, 1.50 equiv.), tetrabutylammonium bromide (0.6 g, 1.8 mmol, 0.04 equiv.), toluene (60 mL), and water (3 mL). The reaction was carried out at 60 °C for 3 h. The mixture was cooled to room temperature, 15 mL of water was added, and the mixture was extracted with toluene (4 × 25 mL) and dried over sodium sulfate. The drying agent was filtered, and the solvent was distilled off under reduced pressure to give the expected product as a yellow oil in 68% yield (7.3 g, 31.0 mmol).

[0081] [Table 1] TIFF2025531833000027.tif251160 TIFF2025531833000028.tif62160

[0082] Reaction R4 In step R4 (Scheme 9), the synthesis of enol ethers of general formula EX is carried out. For this purpose, DX ketone and an appropriate Wittig reagent, preferably a chloride, a strong base, preferably potassium tert-butoxide, are used. The transformation is carried out in an anhydrous organic solvent, preferably tetrahydrofuran. The reaction mixture is carried out at a temperature ranging from -78 °C to room temperature (RT) for 16 hours. Then, n-heptane is added to precipitate the phosphine oxide. After filtering the solid and distilling off the solvent, the product is isolated by column chromatography.

[0083] Alternative Embodiments for Carrying Out Reaction R4 [ka]

[0084] Wittig reagent (13.2 g, 385 mmol, 1.35 equiv.), potassium tert-butoxide (20.4 g, 38.5 mmol, 1.35 equiv.), and anhydrous tetrahydrofuran (57 mL) were placed in a reaction vessel equipped with a stirrer under an argon atmosphere. The reaction was carried out at -78 °C for 1 hour. The mixture was then warmed to room temperature and vigorously stirred for 30 minutes. The mixture was again cooled to -78 °C, and then a solution of acetylferrocene (6.50 g, 285 mmol, 1 equiv.) in anhydrous tetrahydrofuran (10 mL) was added dropwise. After 30 minutes, the mixture was warmed to room temperature and the reaction was carried out at this temperature for 16 hours. The solvent was then evaporated under reduced pressure, and n-heptane (250 mL) was added to the residue to precipitate the phosphine oxide, which was then filtered. The solvent was distilled off under reduced pressure, and the crude product was purified by column chromatography (AlO × 5% HO) using an eluent of 0–20% ethyl acetate in n-hexane to collect fractions. The expected product was obtained as a red-orange oil in 96% yield (6.98 g, 27.2 mmol). 1H NMR(400 MHz, CDCl3)δ ppm:6.22 - 6.20 (m, 0.53×1 H), 5.96 - 5.94 (m, 0.47×1 H), 4.60 - 4.56 (m, 0.47×2H), 4.25 - 4.22 (m, 0.53×2H), 4.19 - 4.16 (m, 0.47×2H), 4.16 - 4.14 (m, 0.53×2H), 4.12 (s, 0.53×5H), 4.08 (s, 0.47×5H), 3.65 (s, 0.47×3H), 3.64 (s, O.53×3H), 1.93 (d, j = 1.4 Hz, O.53×3H), 1.84 (d, j = 1.4 Hz, 0.47×3H). 13 C NMR(101 MHz, CDCl3)δ ppm:142.8, 141.5, 11.0, 109.3, 87.8, 83.6, 69.1, 68.9, 67.9, 67.7, 67.6, 64.2, 59.9, 59.8, 17.5, 12.8.

[0085] Reaction R5 In step R5 (Scheme 9), the synthesis of aldehydes of general formula CX is carried out. For this purpose, enol ether EX and a suitable inorganic acid, preferably hydrobromic acid, are used. The conversion is carried out in a mixture of organic solvent and water, preferably acetone and water (4-1 v / v). The acid is added dropwise at a temperature below -50 °C using a dry ice-acetone cooling bath, and the mixture is heated to 45 °C and vigorously stirred for another 2 h until complete conversion of the substrate is achieved. Next, a weak base, preferably sodium bicarbonate, is added until a pH of 8 is obtained, and the product is extracted with an organic solvent, preferably methylene chloride, and then dried over a drying agent, preferably sodium sulfate or magnesium sulfate. The solid is filtered and the product is obtained after evaporation of the solvent under reduced pressure.

[0086] Embodiments for carrying out reaction R5 [ka]

[0087] A reaction vessel equipped with a stir bar was charged with ether (2.60 g, 10.2 mmol, 1 eq.), acetone (12 mL), and water (3 mL). The mixture was cooled to below -50 °C, and HBr (48% aqueous solution, 2.30 mL, 2 eq.) was added dropwise under an argon atmosphere. The reaction was then carried out at 45 °C for 2 h. Aqueous NaHCO3 solution was added to the reaction mixture until a pH of 8 was reached. The product was extracted with methylene chloride, dried over magnesium sulfate, and then filtered. The solvent was distilled off under reduced pressure to give the expected product as a maroon oil in 93% yield (2.30 g, 9.50 mmol). 1 H NMR(400 MHz, CDCl3)δ ppm:9.72 (d, j = 2.2 Hz, 1H), 4.21 - 4.19 (m, 2H), 4.16 (s, 4H), 4.12 - 4.09 (m, 2H), 3.26 (qd, J = 7.0, 2.3 Hz, 1H), 1.36 (d, J = 7.0 Hz, 3H). 13 C NMR(101 MHz, CDCl3)δ ppm:201.0, 85.0, 68.8, 68.3, 68.3, 67.1, 67.0, 45.7, 14.7.

[0088] Example II Synthesis of CAAC ligands Scheme 15 below illustrates the synthesis of CAAC ligands that allow the preparation of ruthenium catalysts for olefin metathesis (general formulas Ru1a to Ru21a, Scheme 18), the subject of this invention.

[0089] The R6 and R8 reactions shown in Scheme 15 were carried out using commercially available compounds based on literature procedures with modifications developed by the authors. Unless otherwise noted, commercially available solvents were used in the reactions described, and no precautions were taken against the presence of oxygen and / or moisture.

[0090] [ka]

[0091] In step R6 (Scheme 15), the synthesis of imines HX is carried out. For this purpose, an appropriate aniline and an aldehyde of general formula FX are used in the presence of an acid, preferably p-toluenesulfonic acid (PTSA). The reaction is preferably carried out in toluene or another organic solvent. The reaction mixture is carried out at the boiling point of the solvent. The product is isolated by filtration through neutral Al2O3 and distillation of the solvent. The product is used in the next step without further purification.

[0092] In step R7 (Scheme 15), the synthesis of CAAC ligands of general formula LX is carried out, for which purpose the imines of general formula HX from steps R6 or R9 are used in the presence of an acid, preferably 4N hydrochloric acid in dioxane. The reaction is carried out in anhydrous toluene at 85°C under an argon atmosphere. The chloride ions are then preferably exchanged for tetrafluoroborate ions, and the crude product is precipitated from a mixture of organic solvents, preferably methanol:diethyl ether.

[0093] In step R8 (Scheme 15), the synthesis of imines GX is carried out. For this purpose, an appropriate aniline and an aldehyde of the general formula CX are used in the presence of a Lewis acid, preferably titanium(IV) isopropanolate. The reaction is carried out in an anhydrous organic solvent, preferably methanol or another organic solvent, at a temperature ranging from 25 to 45 °C. The product is isolated by precipitation and filtration through neutral Celite and evaporation of the solvent. The product is used in the next step without further purification.

[0094] In step R9 (Scheme 15), the synthesis of imine HX is carried out using imine GX, an alkyl halide, preferably chloride, a base, preferably n-BuLi, and an organic solvent, preferably tetrahydrofuran (THF) or another organic solvent. The reaction is carried out at -78°C to RT for 10 minutes, cooled to -20°C, an alkyl halide is added, and then warmed to room temperature and the reaction is carried out for 16 hours. The product is isolated by filtration through neutral Celite and distillation of the solvent. The product is used in the next step without further purification.

[0095] [ka]

[0096] A round-bottom flask equipped with a stir bar was charged with 2,4-dimethyl-2-thiophenylpent-4-enal (2.11 g, 9.00 mmol, 1.00 equiv.), aniline (1.87 g, 9.00 mmol, 1.00 equiv.), and PTSA (17 mg, 0.09 mmol, 1 mol%) dissolved in PhMe (C = 0.30 M). The reaction was carried out at the boiling point of toluene until complete conversion of the substrate (water was collected using a Dean-Stark apparatus). The solvent was evaporated under reduced pressure, and the crude reaction mixture was dissolved in n-hexane, filtered through neutral alumina (Al2O3, neutral, Brockman Grade I), washed with a mixture of n-hexane:ethyl acetate (98:2, v / v), and dried under reduced pressure to give the imine in 44% yield (1.50 g, 3.94 mmol), which was used in the next step without further purification.

[0097] The imine from the previous step, 4 M HCl (solution in dioxane, 2.53 g, 2.46 mL, 9.83 mmol, 2.5 equiv.), and anhydrous PhMe (C = 0.50 M) were placed in a round-bottom flask under an argon atmosphere. The reaction was carried out at 85 °C for 16 h. The solvent was evaporated under reduced pressure. The crude product was dissolved in a mixture of methylene chloride and water, and NaBF (0.86 g, 7.86 mmol, 2.0 equiv.) was added, and ion exchange was carried out for 2 h. The organic fraction was collected, washed with water, and dried over sodium sulfate. The product was precipitated from a MeOH:EtO mixture to give the final product as colorless crystals in 39% yield (0.72 g, 133 mmol). 1 H NMR(400MHz, CDCl3):9.62 - 9.55 (m, 1H), 8.94 (s, 1H), 7.68 - 7.62 (m, 1H), 7.56 - 7.47 (m, 3H), 7.39 - 7.31 (m, 5H), 7.29 - 7.27 (m, 1H), 7.16 - 7.07 (m, 2H), 6.71 - 6.61 (m, 1H), 3.08 = 23.3, 13.9 Hz, 2H), 2.72 = 54.9, 14.0 Hz, 2H), 2.16 (s, 3H), 1.95 (s, 3H), 1.85 (s, 3H), 1.57 - 132 (m, 5H), 1.45 (s, 4H), 1.34 (s, 5H), 1.27 (s, 4H), 1.17 (s, 5H). 13 C NMR (101 MHz, CDCl3):δ 184.9, 184.5, 151.0, 150.5, 142.2, 142.0, 142.0, 141.2, 132.1, 131.0, 130.7, 130.6, 129.2, 128.9, 128.6, 127.0, 126.6, 126.3, 125.5, 125.5, 123.1, 82.5, 823, 81.9, 81.9, 52.6, 52.4, 503, 49.2, 37.7, 37.1, 34.7, 34.5, 33.8, 33.7, 31.0, 30.9, 30.7, 29.4, 29.0, 28.9, 27.2, 26.6.

[0098] Embodiments for carrying out reaction R8-R9-R7 [ka]

[0099] In a round-bottom flask under an argon atmosphere, 2-ferrocenylpropanal (5.45 g, 22.5 mmol, 1.00 equiv.) and anhydrous methanol (150 mL) were placed, followed by titanium(IV) isopropanolate (13.3 mL, 45 mmol, 2.00 equiv.). 2,6-Diethylaniline (4.27 mL, 25.8 mmol, 1.15 equiv.) was added dropwise to the reaction mixture thus prepared. The reaction was carried out at 45 °C for 16 hours. The solvent was evaporated under reduced pressure. The crude product was dissolved in n-pentane and then filtered through neutral Celite. The solvent was evaporated to give the crude product as a maroon oily liquid in 73% yield (6.15 g, 16.5 mmol).

[0100] The imine (6.36 g, 17.1 mmol, 1.00 equiv.) and anhydrous tetrahydrofuran (835 mL) were placed in a round-bottom flask preheated under reduced pressure under an argon atmosphere. The mixture was then cooled to −78° C. in a dry ice-acetone cooling bath. n-BuLi solution (2.35 M solution in n-hexane, 8.72 mL, 20.5 mmol, 1.20 equiv.) was then added dropwise with vigorous stirring and then allowed to warm to room temperature. After 1 hour, the reaction mixture was again cooled to −78° C. in a dry ice-acetone cooling bath, and 3-chloro-2-methylpropene (2.50 mL, 25.6 mmol, 1.50 equiv.) was added dropwise. The reaction was carried out at room temperature for 16 hours. The solvent was evaporated under reduced pressure. The crude product was purified by distillation to give a maroon oily liquid in 100% yield (7.30 g, 17.1 mmol).

[0101] The imine from the previous step (7.30 g, 17.1 mmol, 1 equiv.) was dissolved in anhydrous PhMe (C = 500 mM) and placed in a round-bottom flask under an argon atmosphere. The mixture was cooled to -78 °C in a dry ice-acetone cooling bath. HCl solution (4 M solution in dioxane, 12.8 mL, 51.2 mmol, 3 equiv.) was then added dropwise, and the reaction was carried out at 85 °C for 16 h with vigorous stirring. The solvent was evaporated under reduced pressure. The crude product was dissolved in methylene chloride (approximately 10 mL), and a saturated aqueous solution of NaBF (3.75 g, 34.1 mmol, 2 equiv.) was added. The ion exchange was carried out for 2 h with vigorous stirring. The mixture was extracted three times with methylene chloride, dried over anhydrous magnesium sulfate, and filtered through neutral Celite. The solvent was then evaporated under reduced pressure. The product was precipitated from a DCM:Et2O mixture to give red crystals in 47% yield (4.14 g, 8.05 mmol).

[0102] [Table 2] TIFF2025531833000035.tif233151 TIFF2025531833000036.tif248153 TIFF2025531833000037.tif240151 TIFF2025531833000038.tif248153 TIFF2025531833000039.tif228151 TIFF2025531833000040.tif248154 TIFF2025531833000041.tif46151

[0103] [ka]

[0104] Example III Synthesis of complexes Ru1a-Ru20a by using CAAC ligands Embodiments of the present invention [ka]

[0105] Under an argon atmosphere, CAAC×BF4 ligand (430 mg, 916 μmol, 2.20 equiv.), first-generation Hoveyda-Grubbs complex (250 mg, 416 μmol, 1.00 equiv.), anhydrous THF (C CAAC =0.1 M) was placed in a heated Schlenk vessel and stirred for 1 min. LiHMDS (153 mg, 916 μmol, 2.20 equiv.) was then added and stirred until complete conversion was achieved (20 min). The crude mixture was filtered through neutral alumina (Al2O3, neutral, Brockman Grade I) using methylene chloride as the eluent. The green fraction was collected and evaporated under reduced pressure. A small amount of n-pentane was then added, and the mixture was placed in an ultrasonic bath. The product was filtered and washed with cold n-pentane. This process was repeated twice and then three times using diethyl ether. After drying under vacuum, a green crystalline solid was obtained in 91% yield (267 mg, 380 μmol).

[0106] Using the methodology set forth in Example III, a series of complexes, Ru1a through Ru21a, were obtained, the structures of which are shown below.

[0107] All complexes in the table below were characterized by nuclear magnetic resonance spectroscopy. Table 3 shows the 1 The shifts of the benzylidene protons of each complex in the H NMR spectrum are summarized.

[0108] [Table 3] TIFF2025531833000045.tif248155 TIFF2025531833000046.tif248155 TIFF2025531833000047.tif248155 JPEG2025531833000048.jpg213155

[0109] Example V Studies on the activity of complexes in the ethenolysis of methyl oleate Methyl oleate was degassed by stirring under reduced pressure (oil pump) for a minimum of 30 minutes. During this time, a sealed Schlenk vessel was prepared and weighed to determine its weight. The oil was then filtered through a syringe filter into the Schlenk vessel, and the vessel was weighed along with the oil to determine its weight. The vessel with the substrate was then subjected to reduced pressure. In a separate vessel, a catalyst solution (~3 mg in 2 mL of degassed toluene) was prepared. A preheated glass insert for the Amar reactor equipped with a stir bar was placed inside the Amar reactor, which was immersed in a preheated oil bath. The reactor was sealed, and the internal gas was evacuated using an oil pump. A portion of the catalyst (10 ppm, 3 ppm, or 500 ppb) was added to the Schlenk vessel containing the oil, and the mixture was immediately transferred to the reactor using Teflon tubing. The reactor was filled with ethylene to a dynamic pressure of 10 bar, after which stirring was initiated and the reaction was carried out for 3 or 6 hours. No glove box or inert gas atmosphere (argon) was used during the reaction.

[0110] The pressure was then normalized and the autoclave was dismantled. SnatchCat metal scavenger solution was immediately added and the contents of the vessel were stirred for several minutes. A sample was then taken, diluted with toluene, and subjected to GC analysis.

[0111] [ka]

[0112] The model reaction results are shown in Table 2.

[0113] [Table 4] TIFF2025531833000051.tif248155 TIFF2025531833000052.tif232155 TIFF2025531833000053.tif201155

[0114] Example 1: 99.9% ethylene, <30 min, 40°C, 10 bar pressure Example 2: 4 hours, 40°C, 10 bar pressure Examples 3 and 4: 99.95% ethylene, 3 hours, 40°C, 10 bar pressure Examples 5 and 6: 99.99% ethylene, 4 hours, 40°C, 10 bar pressure Examples 7-17: Reaction for 10 ppm: 99.95% ethylene, 3 hours, 40°C; Reaction for 3 ppm: 99.95% ethylene, 3-6 hours, 40°C; Reaction for 0.5 ppm: 99.995% ethylene, 6 hours, 40°C (10 bar ethylene pressure)

[0115] 1 Grubbs et al., Organometallics 2008, 27, 563-566. 2 Zhang et al., Chem. Commun., 2013, 49, 9491-9493. 3 Bertrandt et al., Angew. Chem. Int. Ed., 2015, 54, 1919-1923. 4 Gawin et al., Angew. Chem. Int. Ed. 2017, 56, 981-986.

[0116] Example VI Testing the activity of the ruthenium complex in the ethenolysis of methyl oleate outside the glove box under conditions that do not require an inert gas protective atmosphere (Figure 3). Figure 3 shows A) the assembled autoclave in air and B) the open autoclave prior to the ethenolysis reaction.

[0117] The corresponding ethenolysis reaction described in Example V was carried out outside the glovebox in an autoclave placed under a fume hood and exposed to air. The reaction system is shown in Figure 3. Subsequent reaction steps were carried out in air without an inert gas protective atmosphere. Ethylene of varying purity was used during the reaction, and the purity of the ethylene was lower than that described in previous literature reports. The new ruthenium complexes Ru1a–Ru22a were observed to be tolerant to the use of low-quality ethylene, without compromising the reaction results as determined by TON and selectivity.

[0118] Example VII Synthesis of CAAC ligands and spirocarbon catalysts [ka]

[0119] Synthesis of Compound I Aluminum(III) chloride (14.3 g, 105 mmol, 1.00 equiv.) and anhydrous DCM (100 mL) were placed in a three-necked flask equipped with a stir bar under an argon atmosphere, and the suspension was cooled to -40 °C. In a two-necked flask equipped with a stir bar under an argon atmosphere, ferrocene (20.0 g, 105 mmol, 1.00 equiv.) was dissolved in anhydrous DCM (155 mL) and added dropwise to the aluminum(III) chloride suspension in DCM with stirring at -40 °C. The mixture was then cooled to -78 °C, and acryloyl chloride (9.81 mL, 116 mmol, 1.10 equiv.) was added dropwise at -78 °C for 30 min. The reaction was carried out at -78 °C for 18 h, after which the contents of the flask were poured into water at 0 °C. The organic layer was separated, washed with brine, dried over MgSO4, filtered through neutral Celite, and the solvent was evaporated. The crude product was purified by column chromatography (Al2O3 x 5% H2O) to give the product as an orange solid (7.99 g, 33.3 mmol, 31%). 1H NMR (400 MHz, CDCl3):δ 4.87 - 4.79 (m, 2H), 4.66 - 4.56 (m, 2H), 4.43 - 4.30 (m, 2H), 4.10 - 3.94 (m, 2H), 3.06 - 2.86 (m, 4H). 13 C NMR (101 MHz, CDCl3):δ 212.0, 88.2, 74.1, 72.8, 71.2, 70.4, 69.4, 44.3, 31.9.

[0120] Synthesis of Compound II Ketone I (1.16 g, 4.83 mmol, 1.0 equiv.), MeSBr (0.98 g, 6.28 mmol, 1.3 equiv.), KOH (0.70 g, 12.6 mmol, 2.6 equiv.), distilled water (0.25 mL), and MeCN (10 mL) were placed in a reaction vessel equipped with a stir bar under an argon atmosphere. The contents of the vessel were stirred at 60 °C for 16 h. After the reaction was complete, 5 mL of diethyl ether (EtO) was added, the precipitate was filtered, the precipitate was washed again with diethyl ether (10 mL), and the solvent was evaporated under reduced pressure. The residue was washed with diethyl ether (10 mL), the solvent was evaporated, and the residue was washed with n-hexane (10 mL). The solvent was evaporated under reduced pressure to give the product as an orange solid (1.02 g, 4.01 mmol, 83%). 1 H NMR (400 MHz, CDCl3):δ 4.44 - 4.35 (m, 1H), 4.25 - 4.22 (m, 1H), 4.19 - 4.16 (m, 2H), 4.10 - 4.04 (m, 4H), 2.95 (d, J = 5.5 Hz, 1H), 2.90 (dd, J = 0.6, 5.4 Hz, 1H), 2.33 - 2.16 (m, 3H), 2.09 - 1.99 (m, 1H). 13 C NMR (101 MHz, CDCl3):δ 86.6, 81.8, 70.9, 69.1, 68.9, 68.8, 68.7, 68.5, 68.4, 67.7, 56.4, 55.0, 42.5, 22.9.

[0121] Synthesis of Compound III Epoxide II (0.94 g, 3.68 mmol, 1 equiv.), zinc(II) chloride (0.50 g, 3.68 mmol, 1 equiv.), and toluene (16 mL) were placed in a reaction vessel equipped with a stirrer. The reaction was carried out at room temperature for 2 h. The reaction mixture was filtered through a Schottky funnel, and the solvent was distilled off under reduced pressure to give the product as a bright orange solid (0.77 g, 3.04 mmol, 82%). 1 H NMR (400 MHz, CDCl3):δ 9.82 (d, j = 1.5 Hz, 1H), 4.22 - 4.19 (m, 1H), 4.18 - 4.15 (m, 1H), 4.14 - 4.11 (m, 3H), 4.10 - 4.07 (m, 1H), 4.06 - 4.01 (m, 2H), 2.82 - 2.74 (m, 1H), 2.54 -2.39 (m, 2H), 2.05 - 1.93 (m, 1H), 1.86 - 1.72 (m, 1H). 13 C NMR (101 MHz, CDCl3):δ 201.4, 86.4, 81.4, 71.5, 71.4, 70.0, 69.8, 68.9, 68.1, 68.0, 67.3, 50.4, 35.8, 23.9.

[0122] Synthesis of Compound IV A preheated round-bottom flask under vacuum was charged with aldehyde III (0.7 g, 2.76 mmol, 1.0 equiv.), 2-ethyl-6-methylaniline (0.38 g, 2.76 mmol, 1.0 equiv.), 4 Å molecular sieves (0.7 g), and methylene chloride (5.5 mL) under an argon atmosphere. The reaction was carried out at room temperature for 16 h. The molecular sieves were filtered, and the solvent was evaporated under reduced pressure to give the product as an orange solid (0.56 g, 1.49 mmol, 54%). 1H NMR (400 MHz, CD2Cl2):δ 7.75 (d, j = 4.7 Hz, 1H), 7.05 - 6.96 (m, 2H), 6.91 (t, J = 7.5 Hz, 1H), 4.22 - 4.18 (m, 1H), 4.16 - 4.12 (m, 2H), 4.13 - 4.05 (m, 4H), 4.06 - 4.00 (m, 1H), 3.08 -2.94 (m, 1H), 2.57 - 2.47 (m, 2H), 2.43 (q, J = 7.5 Hz, 2H), 2.30 - 2.16 (m, 1H), 2.04 (s, 3H), 2.01 - 1.90 (m, 1H), 1.08 (t, j = 7.5 Hz, 3H). 13 C NMR (101 MHz, CD2Cl2):δ 169.2, 151.0, 133.5, 128.2, 127.0, 126.6, 123.7, 86.9, 85.2, 71.6, 71.0, 69.6, 68.5, 68.2, 68.1, 67.2, 43.9, 39.2, 24.9, 24.4, 18.5, 14.9.

[0123] Synthesis of Compound V Imine IV (0.55 g, 1.47 mmol, 1.00 equiv.) and anhydrous tetrahydrofuran (3.0 mL) were placed in a round-bottom flask preheated under reduced pressure under an argon atmosphere. The mixture was then cooled to −78° C. in a dry ice-acetone cooling bath. n-BuLi solution (2.30 M solution in n-hexane, 0.77 mL, 1.76 mmol, 1.20 equiv.) was then added dropwise with vigorous stirring and then heated to room temperature. After 1 h, the reaction mixture was again cooled to −78° C. in a dry ice-acetone cooling bath, and 3-chloro-2-methylpropene (0.22 mL, 2.2 mmol, 1.50 equiv.) was added dropwise. The reaction was carried out at room temperature for 16 h. The solvent was evaporated under reduced pressure. The crude product was filtered through a syringe filter to give the product as a red oil (0.51 g, 1.19 mmol, 80%). 1H NMR (400 MHz, CDCl3): δ 7.84 (s, 1H), 7.10 - 7.03 (m, 1H), 7.06 - 6.99 (m, 1H), 7.00 -6.92 (m, 1H), 4.85 - 4.80 (m, 1H), 4.80 - 4.75 (m, 1H), 4.25 - 4.18 (m, 2H), 4.16 - 4.11 (m, 3H), 4.11 - 4.05 (m, 1H), 4.08 - 4.03 (m, 2H), 2.76 (d, J = 14.5 Hz, 1H), 2.70 - 2.64 (m, 1H), 2.58 (d, J = 14.5 Hz, 1H), 2.5 1 (qd, J = 1.6, 7.5 Hz, 2H), 2.43 - 2.32 (m, 2H), 2.24 - 2.19 (m, 1H), 2.15 (s, 3H), 1.69 (s, 3H), 1.16 (t J = 7.5 Hz, 3H). 13 C NMR (101 MHz, CDCl3): δ 171.3, 150.4, 142.0, 133.3, 128.2, 127.0, 126.3, 123.7, 115.3, 89.6, 87.4, 68.8, 68.8, 683, 68.5, 68.4, 68.4, 67.7, 67.7, 46.2, 42.9, 29.8, 25.1, 24.6, 20.6, 19.1, 14.9.

[0124] Synthesis of compound L22 The imine from the previous step (0.49 g, 1.15 mmol, 1 equiv.) was dissolved in anhydrous PhMe (C = 500 mM) and placed in a round-bottom flask under an argon atmosphere. The mixture was cooled to -78 °C in a dry ice-acetone cooling bath. HCl solution (0.7 mL, 4 M solution in dioxane, 2.88 mmol, 2.5 equiv.) was then added dropwise, and the reaction was carried out at 85 °C for 16 h with vigorous stirring. The solvent was evaporated under reduced pressure. The crude product was dissolved in methylene chloride (approximately 5 mL), and a saturated aqueous solution of NaBF (0.25 g, 2.30 mmol, 2 equiv.) was added. The ion exchange was carried out for 2 h with vigorous stirring. The mixture was extracted three times with methylene chloride, dried over anhydrous magnesium sulfate, and filtered through neutral Celite. The solvent was then evaporated under reduced pressure. The product was precipitated from a DCM:Et2O mixture to give the product as a light brown solid (0.27 g, 0.53 mmol, 45%).

[0125] Synthesis of compound Ru22a Under an argon atmosphere, CAAC×BF4 ligand L22 (174 mg, 340 μmol, 1.20 equiv.), the first-generation Hoveyda-Grubbs complex (170 mg, 283 μmol, 1.00 equiv.), and anhydrous THF (C CAAC (=0.1 M) was placed in a preheated Schlenk flask and stirred for 1 min. LiHMDS (56 mg, 340 μmol, 1.20 equiv.) was then added and stirred until complete conversion was achieved (5 min). Copper(I) chloride (56 mg, 566 μmol, 2.00 equiv.) was then added. The crude mixture was filtered through neutral alumina (Al2O3, neutral, Brockman Grade I) using methylene chloride as the eluent. The green fraction was collected, and the solvent was evaporated under reduced pressure. A small amount of n-pentane was then added, and the mixture was placed in an ultrasonic bath. The product was drained and washed with cold n-pentane. This process was repeated twice, followed by diethyl ether. After drying under vacuum, a green crystalline solid was obtained (164 mg, 220 μmol, 77%).

[0126] [Table 5] TIFF2025531833000056.tif94155

Claims

1. Formula CAAC-1 【Chemical 1】 In the formula, X is a halogen atom, BF 4 - , P.F. 6 - , ClO 4 - , C.F. 3 SO 2 O - represents an anion selected from the group comprising: R 1 , R 2 , R 3 , R 4 , and R 5 are independently a hydrogen atom, C 1 -C 12 Alkyl group, C 3 -C 12 Cycloalkyl group, C 5 -C 20 Aryl group or C 5 -C 20 Heteroaryl group, C 5 -C 25 aralkyl groups, which are hydrogen atoms, halogen atoms, C 1 -C 12 Alkyl group, C 1 -C 12 Perfluoroalkyl group, C 5 -C 20 Aryl group, C 5 -C 20 Perfluoroaryl group, C 5 -C 20 Heteroaryl group, C 1 -C 12 Alkoxyl group, C 5 -C 24 Aryloxyl group, C 5 -C 20 Heteroaryloxyl group, sulfide (-SR") group, amino (-NR") group 2 and R′ groups may be independently substituted by one and / or more substituents selected from the group comprising a hydrogen atom, C 1 -C 5 Alkyl, C 6 -C 24 Aryl, C 7 -C 24 Aralkyl may be independently represented by R 1 , R 2 , R 3 , R 4 , and R 5 are combined to form C 5 -C 25 Forming a ring; Each substituent R 6 , R 7 , and R 8 is a hydrogen atom, a halogen atom, or C 1 -C 12 Alkyl group or C 5 -C 20 aryl groups, which may be hydrogen-containing groups, C 1 -C 12 Alkyl group, C 1 -C 12 Perfluoroalkyl group, C 5 -C 20 Aryl group, C 5 -C 20 Perfluoroaryl group, C 5 -C 20 Heteroaryl group, C 1 -C 12 Alkoxyl group, C 5 -C 24 Aryloxyl group, C 5 -C 20 Heteroaryloxyl group or halogen atom, sulfide group (-SR"), amino group (-NR") 2 and R″ groups may be independently substituted by one and / or more substituents selected from a hydrogen atom, C 1 -C 5 Alkyl, C 6 -C 24 Aryl, C 7 -C 24 independently denoting aralkyl; R 9 The substituents are substituted or unsubstituted heterocyclic groups or organometallic complex groups such as ferrocene, and these are selected from the group consisting of hydrogen atoms, halogen atoms, C 1 -C 12 Alkyl group, C 1 -C 12 Perfluoroalkyl group, C 5 -C 20 Aryl group, C 5 -C 20 Perfluoroaryl group, C 5 -C 20 Heteroaryl group, C 1 -C 12 Alkoxyl group, C 5 -C 24 Aryloxyl group, C 5 -C 20 Heteroaryloxyl group, sulfide group (-SR"), amino group (-NR") 2 and wherein the R″ groups are independently substituted by one and / or more substituents selected from the group comprising a hydrogen atom, C 1 -C 5 Alkyl, C 6 -C 24 Aryl, C 7 -C 24 Aralkyl can be independently represented, Alternatively, R 6 and R 7 and / or R 8 and R 9 are joined together to form C 5 -C 25 Form a ring; A precursor of cyclic alkylamine carbene (CAAC) represented by the formula:

2. X and the substituent R 1 ~R 8 has the meaning defined above, and the substituent R 9 represents a substituted or unsubstituted heterocyclic group selected from thiophene, benzothiophene, furan, benzofuran, pyrrole, benzopyrrole, aziridine, oxirane, thiirane, azetidine, oxetane, thietane, pyrrolidine, tetrahydrofuran, tetrahydrothiophene, piperidine, tetrahydropyran, thiane, pyridine, azepane, oxepane, thiepane, azepine, oxepine, thiepine, oxazole, imidazole, thiazole, isoxazole, pyrazole, isothiazole, triazine, pyrrolidine, pyridine, pyrimidine, hydantoin, quinoline, isoquinoline, chromonyl, coumarin, indole, indolizine, indazole, purine, quinolizine, isoquinol, quinol, phthalazine, naphthyridine, carbazole, β-carboline, or R 9 2. The precursor of formula CAAC-1 according to claim 1, wherein the substituents represent a substituted or unsubstituted organometallic complex group comprising a cyclopentyl ring and a metal atom selected from iron, cobalt, nickel, chromium, titanium, zirconium (metallocene).

3. X and the substituent R 1 ~R 8 has the meaning defined above, and the substituent R 9 3. The precursor of formula CAAC-1 according to claim 1 or 2, wherein represents a substituted or unsubstituted heterocyclic group selected from thiophene, benzothiophene, furan, benzofuran, or ferrocene.

4. A precursor of formula CAAC-1 according to any one of claims 1 to 3, having a structure represented by formula L1, L2, L3, L4, L5, L6, L7, L8, L9, L10, L11, L12, L13, L14, L15, L16, L17, L18, L19, L20, L21, or L22: 【Chemistry 2】

5. Formula 1-Ru 【Chemistry 3】 During the ceremony, X 1 and X 2 are each independently a halogen anion, —CN, —SCN, —OR a , -SR a , —O(C═O)R a , -O(SO 2 ) R a , and —OSi(R a ) 3 and R represents an anionic ligand selected from the group comprising the group a But C 1 -C 12 Alkyl, C 3 -C 12 Cycloalkyl, C 2 -C 12 alkenyl, or C 5 -C 20 aryl, which are at least one C 1 -C 12 Alkyl, C 1 -C 12 Perfluoroalkyl, C 1 -C 12 Alkoxyl, C 5 -C 24 Aryloxyl, C 5 -C 20 optionally substituted with heteroaryloxyl or halogen atoms; R 1 , R 2 , R 3 , R 4 , and R 5 are independently a hydrogen atom, C 1 -C 12 Alkyl group, C 3 -C 12 Cycloalkyl group, C 5 -C 20 Aryl group or C 5 -C 20 Heteroaryl group, C 5 -C 25 aralkyl groups, which are hydrogen atoms, halogen atoms, C 1 -C 12 Alkyl group, C 1 -C 12 Perfluoroalkyl group, C 5 -C 20 Aryl group, C 5 -C 20 Perfluoroaryl group, C 5 -C 20 Heteroaryl group, C 1 -C 12 Alkoxyl group, C 5 -C 24 Aryloxyl group, C 5 -C 20 Heteroaryloxyl group, sulfide group (-SR"), amino group (-NR") 2 and wherein the R″ groups are independently substituted with one and / or more substituents selected from the group comprising: a hydrogen atom, C 1 -C 5 Alkyl, C 6 -C 24 Aryl, C 7 -C 24 Indicates aralkyl or Alternatively, R 1 , R 2 , R 3 , R 4 , and R 5 are bonded to each other, C 5 -C 25 Forming a ring; Each substituent R 6 , R 7 , and R 8 is a hydrogen atom, a halogen atom, or C 1 -C 12 Alkyl group or C 5 -C 20 aryl groups, which are hydrogen atoms, C 1 -C 12 Alkyl group, C 1 -C 12 Perfluoroalkyl group, C 5 -C 20 Aryl group, C 5 -C 20 Perfluoroaryl group, C 5 -C 20 Heteroaryl group, C 1 -C 12 Alkoxyl group, C 5 -C 24 Aryloxyl group, C 5 -C 20 Heteroaryloxyl group or halogen atom, sulfide group (-SR"), amino group (-NR") 2 and wherein the group R″ is independently substituted with one and / or more substituents selected from the group comprising a hydrogen atom, C 1 -C 5 Alkyl, C 6 -C 24 Aryl, C 7 -C 24 independently denoting aralkyl; R 9 The substituents represent substituted or unsubstituted heterocyclic groups and / or organometallic complex groups, and these are selected from the group consisting of hydrogen atoms, halogen atoms, C 1 -C 12 Alkyl group, C 1 -C 12 Perfluoroalkyl group, C 5 -C 20 Aryl group, C 5 -C 20 Perfluoroaryl group, C 5 -C 20 Heteroaryl group, C 1 -C 12 Alkoxyl group, C 5 -C 24 Aryloxyl group, C 5 -C 20 Heteroaryloxyl group, sulfide group (-SR"), amino group (-NR") 2 and wherein the R″ groups are independently substituted with one and / or more substituents selected from the group comprising a hydrogen atom, C 1 -C 5 Alkyl, C 6 -C 24 Aryl, C 7 -C 24 Aralkyl can be independently represented, Alternatively, R 6 and R 7 and / or R 8 and R 9 are joined together to form C 5 -C 25 Forming a ring; R 16 and R 17 are independently a hydrogen atom, a halogen atom, or C 1 -C 25 Alkyl, C 3 -C 25 Cycloalkyl, C 1 -C 12 Perfluoroalkyl, C 2 -C 25 Alkene, C 2 -C 25 Alkenyl, C 3 -C 25 Cycloalkenyl, C 2 -C 25 Alkynyl, C 3 -C 25 Cycloalkynyl, C 1 -C 25 Alkoxy, C 5 -C 25 Aryl, C 5 -C 25 Aryloxyl, C 6 -C 25 Aryl alkyl, C 5 -C 25 Heteroaryl, C 5 -C 25 Heteroaryloxyl, C 5 -C 25 represents a 3- to 12-membered heterocycle containing a perfluoroaryl, sulfur, oxygen, nitrogen, selenium, or phosphorus atom; This allows the substituent R 16 and R 17 can be concatenated together to form C 3 -C 25 Cycloalkyl, C 3 -C 25 Cycloalkenyl, C 3 -C 25 Cycloalkynyl, C 5 -C 25 Aryl, C 5 -C 25 Heteroaryl, C 5 -C 25 Forms a ring selected from the group consisting of perfluoroaryl, 3- to 12-membered heterocycles containing sulfur, oxygen, nitrogen, selenium, or phosphorus atoms, which is selected from the group consisting of hydrogen atoms, halogen atoms, C 1 -C 25 Alkyl, C 3 -C 25 Cycloalkyl, C 1 -C 12 Perfluoroalkyl, C 2 -C 25 Alkene, C 2 -C 25 Alkenyl, C 3 -C 25 Cycloalkenyl, C 2 -C 25 Alkynyl, C 3 -C 25 Cycloalkynyl, C 1 -C 25 Alkoxyl, C 5 -C 25 Aryl, C 5 -C 25 Aryloxyl, C 6 -C 25 Aryl alkyl, C 5 -C 25 Heteroaryl, C 5 -C 25 Heteroaryloxyl, C 5 -C 25 optionally independently substituted with one or more substituents selected from the group including perfluoroaryl, 3- to 12-membered heterocycle; G is selected from the following: - Ligand of formula CAAC-1: 【Chemistry 4】 In the formula, X and the substituent R 1 ~R 9 has the meaning defined above, or - 1 heteroatom an oxygen atom, a sulfur atom, a selenium atom; a hydrogen atom, a fluorine atom, an oxygen atom, a C 1 -C 25 Alkyl, C 1 -C 25 Perfluoroalkyl, C 3 -C 25 Cycloalkyl, C 5 -C 20 Alkoxyl, C 5 -C 20 Aryl, C 5 -C 20 Perfluoroaryl, C 7 -C 20 Aralkyl, C 5 -C 24 Aryloxyl, C 2 -C 12 Alkenyl, C 6 -C 20 Heteroaryl or C 5 -C 24 and optionally substituted with a group selected from the group consisting of an acyl group (—COR′), a cyano group (—CN), a carboxyl group (—COOH), an ester group (—COOR′), an ester group (—CH 2 COOR'), ester group (-CHR'COOR'), ester group (-C(R') 2 COOR'), amide group (-CONR' 2 ), Weinreb amide (—CON(R′)(OR′)), sulfone group (—SO 2 R'), formyl group (-CHO), sulfonamide group (-SOiNR' 2 ), a ketone group (—COR′), a thioamide group (—CSNR′ 2 ), thioketone (-CSR'), thionoester group (-CSOR'), thioester group (-COSR'), dithioester group (-CS 2 R'), wherein the groups R' are independently selected from the group C 1 -C 25 Alkyl, C 1 -C 25 Perfluoroalkyl, C 3 -C 25 Cycloalkyl, C 5 -C 20 Alkoxyl, C 5 -C 20 Aryl, C 5 -C 20 Perfluoroaryl, C 7 -C 20 Aralkyl, C 5 -C 24 Aryloxyl, C 2 -C 12 Alkenyl, C 6 -C 20 Heteroaryl, C 5 -C 24 The dashed line indicates the heteroatom and the substituent R 17 a direct bond between, or a methylene bridge, -CH 2 -, -CHR'-, or -CR' 2 Substituent R via - 17 and the heteroatom, and the substituent R 14 But C 5 -C 15 aryl, optionally containing a hydrogen atom, a halogen atom, C 1 -C 25 Alkyl, C 3 -C 25 Cycloalkyl, C 2 -C 25 Alkenyl, C 3 -C 25 Cycloalkenyl, C 2 -C 25 Alkynyl, C 3 -C 25 Cycloalkynyl, C 1 -C 25 Perfluoroalkyl, C 5 -C 20 Alkoxyl, C 5 -C 20 Aryl, C 5 -C 20 Perfluoroaryl, C 7 -C 20 Aralkyl, C 5 -C 24 Aryloxyl, C 6 -C 20 Heteroaryl or C 5 -C 24 Heteroaryloxyl, 3- to 12-membered heterocycle, alkoxyl group (-OR"), sulfide group (-SR"), sulfoxide group (-S(O)R"), sulfonium group (-S + R'' 2 ), sulfonic acid group (—SO 2 R″), sulfonamide group (—SO 2 NR'' 2 ), an amino group (—NR″ 2 ), ammonium group (-N + R'' 3 ), nitro group (-NO 2 ), cyano group (—CN), phosphine group (—P(O)(OR″) 2 ), phosphinic acid group (-P(O)R"(OR")), phosphonic acid group (-P(OR") 2 ), a phosphine group (-PR'' 2 ), a phosphine oxide group (—P(O)R″ 2 ), a phosphonium group (-P + R'' 3 ), a carboxyl group (-COOH), an ester group (-COOR"), an amide group (-CONR") 2 ), amide group (-NR"C(O)R"), formyl group (-CHO), ketone group (-COR"), thioamide group (-CSNR") 2 ), thioketone group (-CSR"), thionoester group (-CSOR"), thioester group (-COSR"), dithioester group (-CS 2 and R″ is substituted with 1 to 4 substituents independently selected from groups containing C 1 -C 5 Alkyl, C 1 -C 5 Perfluoroalkyl, C 6 -C 24 Aryl, C 7 -C 24 Aralkyl, C 5 -C 24 denotes a perfluoroaryl, or -Heteroatom 2 and optionally, the substituents R′, C 1 -C 25 Alkyl, C 1 -C 25 Perfluoroalkyl, C 3 -C 25 Cycloalkyl, C 5 -C 20 Alkoxyl, C 5 -C 20 Aryl, C 5 -C 20 Perfluoroaryl, C 7 -C 20 Aralkyl, C 5 -C 24 Aryloxyl, C 2 -C 12 Alkenyl, C 6 -C 20 Heteroaryl or C 5 -C 24 Heteroaryloxyl, 3- to 12-membered heterocycle, acyl group (—COR′), ester group (—COOR′), tert-butylbutyloxycarbonyl group (t-Boc) or 9-fluorenylmethoxycarbonyl group (Fmoc), carbamine group (—CONR′ 2 ), sulfonic acid group (—SO 2 R'), substituted with a formyl group (-CHO), and the R' group is C 1 -C 25 Alkyl, C 1 -C 25 Perfluoroalkyl, C 3 -C 25 Cycloalkyl, C 5 -C 20 Alkoxyl, C 5 -C 20 Aryl, C 5 -C 20 Perfluoroaryl, C 7 -C 20 Aralkyl, C 5 -C 24 Aryloxyl, C 2 -C 12 Alkenyl, C 6 -C 20 Heteroaryl or C 5 -C 24 represents a heteroaryloxyl group, and optionally represents an acyl group (—COR′), a cyano group (—CN), a carboxyl group (—COOH), an ester group (—COOR′), an ester group (—CH 2 COOR'), ester group (-CHR'COOR'), ester group (-C(R') 2 COOR'), amide group (-CONR' 2 ), sulfonic acid group (—SO 2 R'), formyl group (-CHO), sulfonamide group (-SO 2 NR' 2 ), a ketone group (—COR′), a thioamide group (—CSNR′ 2 ), thioketone group (-CSR'), thionoester group (-CSOR'), thioester group (-COSR'), dithioester group (-CS 2 R'), and the R' group is C 1 -C 25 Alkyl, C 1 -C 25 Perfluoroalkyl, C 3 -C 25 Cycloalkyl, C 5 -C 20 Alkoxyl, C 5 -C 20 Aryl, C 5 -C 20 Perfluoroaryl, C 7 -C 20 Aralkyl, C 5 -C 24 Aryloxyl, C 2 -C 12 Alkenyl, C 6 -C 20 heteroaryl, or C 5 -C 24 The dashed line indicates the heteroatom and the substituent R 14 A direct bond between, or a methylene bridge, (CH 2 )-, -(CHR')-, or -(CR' 2 )-substituted group R 17 and the heteroatom, and the substituent R 17 But C 5 -C 15 aryl, optionally containing a hydrogen atom, a halogen atom, C 1 -C 25 Alkyl, C 3 -C 25 Cycloalkyl, C 2 -C 25 Alkenyl, C 3 -C 25 Cycloalkenyl, C 2 -C 25 Alkynyl, C 3 -C 25 Cycloalkynyl, C 1 -C 25 Perfluoroalkyl, C 5 -C 20 Alkoxyl, C 5 -C 20 Aryl, C 5 -C 20 Perfluoroaryl, C 7 -C 20 Aralkyl, C 5 -C 24 Aryloxyl, C 6 -C 20 Heteroaryl or C 5 -C 24 Heteroaryloxyl, 3- to 12-membered heterocycle, alkoxyl group (-OR"), sulfide group (-SR"), sulfoxide group (-S(O)R"), sulfonium group (-S + R'' 2 ), sulfonic acid group (—SO 2 R″), sulfonamide group (—SO 2 NR'' 2 ), an amino group (—NR″ 2 ), ammonium group (-N + R'' 3 ), nitro group (-NO 2 ), cyano group (—CN), phosphine group (—P(O)(OR″) 2 ), phosphinic acid group (-P(O)R"(OR")), phosphonic acid group (-P(OR") 2 ), a phosphine group (-PR'' 2 ), a phosphine oxide group (—P(O)R″ 2 ), a phosphonium group (-P + R'' 3 ), a carboxyl group (-COOH), an ester group (-COOR"), an amide group (-CONR") 2 ), amide group (-NR"C(O)R"), formyl group (-CHO), ketone group (-COR"), thioamide group (-CSNR") 2 ), thioketone group (-CSR"), thionoester group (-CSOR"), thioester group (-COSR"), dithioester group (-CS 2 and R″ is substituted with 1 to 4 substituents independently selected from the group comprising C 1 -C 5 Alkyl, C 1 -C 5 Perfluoroalkyl, C 6 -C 24 Aryl, C 7 -C 24 Aralkyl, C 5 -C 24 denotes a perfluoroaryl, or - 3 heteroatoms halogen atoms, and the dashed line indicates the heteroatom and R 17 indicates a direct bond between the substituents, and R 17 The substituent is C 5 -C 15 aryl, or C 5 -C 25 polyaryl, optionally containing hydrogen atoms, halogen atoms, C 1 -C 25 Alkyl, C 3 -C 25 Cycloalkyl, C 2 -C 25 Alkenyl, C 3 -C 25 Cycloalkenyl, C 2 -C 25 Alkynyl, C 3 -C 25 Cycloalkynyl, C 1 -C 25 Perfluoroalkyl, C 5 -C 20 Alkoxyl, C 5 -C 20 Aryl, C 5 -C 20 Perfluoroaryl, C 7 -C 20 Aralkyl, C 5 -C 24 Aryloxyl, C 6 -C 20 Heteroaryl or C 5 -C 24 Heteroaryloxyl, 3- to 12-membered heterocycle, alkoxy group (—OR″), sulfide group (—SR′), sulfoxide group (—S(O)R″), sulfonium group (—S + R'' 2 ), sulfonic acid group (—SO 2 R″), sulfonamide group (—SO 2 NR'' 2 ), an amino group (—NR″ 2 ), ammonium group (-N + R'' 3 ), nitro group (-NO 2 ), cyano group (—CN), phosphonic acid group (—P(O)(OR″) 2 ), phosphinic acid group (-P(O)R"(OR")), phosphonic acid group (-P(OR") 2 ), a phosphine group (-PR'' 2 ), a phosphine oxide group (—P(O)R″ 2 ), a phosphonium group (-P + R'' 3 ), a carboxyl group (-COOH), an ester group (-COOR"), an amide group (-CONR") 2 ), amide group (-NR"C(O)R"), formyl group (-CHO), ketone group (-COR"), thioamide group (-CSNR") 2 ), thioketone group (-CSR"), thionoester group (-CSOR"), thioester group (-COSR"), dithioester group (-CS 2 and R″ is substituted with 1 to 4 substituents independently selected from the group comprising C 1 -C 5 Alkyl, C 1 -C 5 Perfluoroalkyl, C 6 -C 24 Aryl, C 7 -C 24 Aralkyl, C 5 -C 24 Indicates perfluoroaryl; A ruthenium complex represented by the formula:

6. The ruthenium complex is represented by the formula 1a-Ru 【Chemistry 5】 In the formula, X 1 and X 2 , and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 the substituents have the meanings defined above; "n" means 1 or 0; Z is selected from the group comprising a halogen atom, an O atom, an S atom, an Se atom, or an NR'" group, and R'" is methylidene, C 1 -C 25 Alkyl, C 1 -C 25 Perfluoroalkyl, C 3 -C 25 Cycloalkyl, C 5 -C 20 Alkoxyl, C 5 -C 20 Aryl, C 5 -C 20 Perfluoroaryl, C 7 -C 20 Aralkyl, C 5 -C 24 Aryloxyl, C 2 -C 12 Alkenyl, C 6 -C 20 Heteroaryl or C 5 -C 24 Heteroaryloxyl, 3- to 12-membered heterocycle, acyl group (—COR′), ester group (—COOR′), tert-butyloxycarbonyl group (t-Boc) or 9-fluorenylmethoxycarbonyl group (Fmoc), carbamine group (—CONR′ 2 ), sulfonic acid group (—SO 2 R'), formyl group (-CHO), and R' group is C 1 -C 25 Alkyl, C 1 -C 25 Perfluoroalkyl, C 3 -C 25 Cycloalkyl, C 5 -C 20 Alkoxyl, C 5 -C 20 Aryl, C 5 -C 20 Perfluoroaryl, C 7 -C 20 Aralkyl, C 5 -C 24 Aryloxyl, C 2 -C 12 Alkenyl, C 6 -C 20 Heteroaryl or C 5 -C 24 represents heteroaryloxyl; or a halogen atom, and when Z represents a halogen atom, R 18 does not exist; R 18 are independently a hydrogen atom, C 1 -C 25 Alkyl, C 1 -C 25 Cycloalkyl, C 5 -C 20 Alkoxyl, C 5 -C 20 Aryl, C 5 -C 24 Aryloxyl, -COOR''' group, -CH 2 COOR''' group, -CONR''' 2 group, -CH 2 CONR''' 2 group, -COR''' group, -CH 2 COR''' group, -CON(OR''') (R''') group, -CH 2 CON(OR''')(R''') group or a halogen atom, where R''' is C 1 -C 12 Alkyl, C 3 -C 12 Cycloalkyl, C 2 -C 12 Alkenyl, C 6 -C 20 aryl, which optionally contain at least one C 1 -C 12 Alkyl, C 1 -C 12 Perfluoroalkyl, C 1 -C 12 Alkoxyl, C 6 -C 24 substituted with an aryloxyl or halogen atom; R 19 , R 20 , R 21 , and R 22 are independently a hydrogen atom, a halogen atom, or C 1 -C 25 Alkyl group, C 2 -C 25 Alkenyl group, C 5 -C 25 Aryl group, alkoxy group (-OR"), sulfide group (-SR"), sulfoxide (-S(O)R"), sulfonium group (-S + R'' 2 ), sulfonic acid group (—SO 2 R″), sulfonamide group (—SO 2 NR'' 2 ), an amino group (—NR″ 2 ), ammonium group (-N + R'' 3 ), nitro group (-NO 2 ), cyano group (—CN), phosphonic acid group (—P(O)(OR″) 2 ), phosphinic acid group (-P(O)R"(OR")), phosphonic acid group (-P(OR") 2 ), a phosphine group (-PR'' 2 ), a phosphine oxide group (—P(O)R″ 2 ), a phosphonium group (-P + R'' 3 ), a carboxyl group (-COOH), an ester group (-COOR"), an amide group (-CONR") 2 ), amide group (-NR"C(O)R'), formyl group (-CHO), ketone group (-COR"), thioamide group (-CSNR") 2 ), thioketone group (-CSR"), thionoester group (-CSOR"), thioester group (-COSR"), dithioester group (-CS 2 R″), wherein the R″ group is C 1 -C 5 Alkyl, C 1 -C 5 Perfluoroalkyl, C 6 -C 24 Aryl, C 7 -C 24 Aralkyl, C 5 -C 24 represents a perfluoroaryl, and R 16 , R 17 , R 18 , and R 19 The substituents may be bonded, thus forming a substituted or unsubstituted C 4 -C 10 Cyclic or C 4 -C 12 Forming polycyclic ring systems; The ruthenium complex according to claim 5, represented by the formula:

7. The ruthenium complex is represented by the formula 1b-Ru 【Chemistry 6】 In the formula, X 1 and X 2 , and the substituent R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 has the meaning defined above; R 16 and R 17 are independently a hydrogen atom, a halogen atom, an optionally substituted C 1 -C 25 Alkyl, optionally substituted C 3 -C 25 Cycloalkyl, optionally substituted C 1 -C 12 Perfluoroalkyl, optionally substituted C 2 -C 25 Alkenes, optionally substituted C 2 -C 25 Alkenyl, optionally substituted C 3 -C 25 Cycloalkenyl, optionally substituted C 2 -C 25 Alkynyl, optionally substituted C 3 -C 25 Cycloalkyl, optionally substituted C 1 -C 25 Alkoxy, optionally substituted C 5 -C 25 Aryl, optionally substituted C 5 -C 25 Aryloxyl, optionally substituted C 6 -C 25 Arylalkyl, optionally substituted C 5 -C 25 Heteroaryl, optionally substituted C 5 -C 25 Heteroaryloxyl, optionally substituted C 5 -C 25 perfluoroaryl, an optionally substituted 3- to 12-membered heterocycle containing a sulfur, oxygen, nitrogen, selenium, or phosphorus atom; R 16 and R 17 Substituents may be attached to C 3 -C 25 Cycloalkyl, C 3 -C 25 Cycloalkenyl, C 3 -C 25 Cycloalkynyl, C 5 -C 25 Aryl, C 5 -C 25 Heteroaryl, C 5 -C 25 forming a ring selected from the group consisting of perfluoroaryl, 3- to 12-membered heterocycles containing sulfur, oxygen, nitrogen, selenium, or phosphorus atoms, which are selected from the group consisting of hydrogen atoms, halogen atoms, C 1 -C 25 Alkyl, C 3 -C 25 Cycloalkyl, C 1 -C 12 Perfluoroalkyl, C 2 -C 25 Alkene, C 2 -C 25 Alkenyl, C 3 -C 25 Cycloalkenyl, C 2 -C 25 Alkynyl, C 3 -C 25 Cycloalkynyl, C 1 -C 25 Alkoxyl, C 5 -C 25 Aryl, C 5 -C 25 Aryloxyl, C 6 -C 25 Aryl alkyl, C 5 -C 25 Heteroaryl, C 5 -C 25 Heteroaryloxyl, C 5 -C 25 may be independently substituted with one or more substituents selected from the group including perfluoroaryl, 3- to 12-membered heterocycle; The ruthenium complex according to claim 5 or 6, represented by:

8. The ruthenium complex may be of the formula Ru1a, Ru2a, Ru3a, Ru4a, Ru5a, Ru6a, Ru7a, Ru8a, Ru9a, Ru10a, Ru11a, Ru11a, Ru12a, Ru13a, Ru14a, Ru15a, Ru16a, Ru17a, Ru18a, Ru19a, Ru20a, Ru21a, Ru22a: 【Chemistry 7】 The ruthenium complex according to any one of claims 5 to 6, selected from complexes represented by the formula:

9. Formula 10 【Chemistry 8】 During the ceremony, L 1 is pyridine or substituted pyridine, P(R') 3 , P(OR′) 3 , O(R') 2 , N(R′) 3 and each R′ independently represents a neutral ligand selected from the group comprising: 1 -C 12 Alkyl, C 3 -C 12 Cycloalkyl, C 5 -C 20 Aryl, C 7 -C 24 Aralkyl, C 5 -C 24 perfluoroaryl, 5-12 membered heteroaryl; N, Z, X 1 , X 2 and a substituent R 18 , R1′, R 20 , R 21 , and R 22 has the meaning defined above; The alkylidene ruthenium complex represented by the formula 8 【Chemistry 9】 In the formula, the substituent R 1 ~R 9 has the meaning defined above; 10. The compound of formula 1a-Ru as defined in claim 6, characterized in that it reacts with a carbene of formula 1a-Ru 【Chemistry 10】 A method for synthesizing a ruthenium complex represented by the formula:

10. Use of a compound of formula 1-Ru as defined in any one of claims 5 to 8 as a precatalyst and / or catalyst in olefin metathesis reactions, in particular ring-conversion metathesis (RCM), cross-metathesis (CM), homometathesis (cross-metathesis between two molecules of the same olefin), ethenolysis, isomerization, diastereoselective ring rearrangement metathesis (DRRM) reactions, alkene-alkyne (ene-yne) metathesis, or ROMP or ADMET polymerization reactions.

11. 11. The use according to claim 10, wherein the reaction is carried out in an organic solvent such as toluene, mesitylene, hexane, cyclohexane, ethyl acetate, methyl acetate, methyl carbonate, ethyl carbonate, tert-butyl methyl ether, cyclopentyl methyl ether, diethyl ether, THF, 2 Me-THF, 4-Me-THP, dioxane, DME, PAO, PEG, paraffin, esters of saturated fatty acids, and the like.

12. 11. The use according to claim 10, wherein the reaction is carried out in a solvent-free system.

13. 10. The use according to any one of the preceding claims, wherein the reaction is carried out at a temperature between 20°C and 200°C.

14. 10. The use according to any one of the preceding claims, wherein the reaction is carried out for a period of from 5 minutes to 48 hours.

15. 10. The use according to any one of the preceding claims, wherein the compound 1-Ru is applied in an amount not exceeding 10 mol %.

16. 10. The use according to any one of the preceding claims, wherein the compound 1-Ru is applied in an amount not exceeding 0.1 mol %.

17. 10. The use according to any one of the preceding claims, wherein the compound 1-Ru is added to the reaction mixture as a solution in an organic solvent, in solid portions and / or continuously using a pump.

18. 10. The use according to any one of the preceding claims, wherein the gaseous by-products of the reaction, selected from ethylene, propylene, butylene, are actively removed from the reaction mixture using barbotage of an inert gas or by vacuum.

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