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

[0002] Remarkable progress has been made in the use of olefin metathesis in organic synthesis in recent years [RH Grubbs (eds.), AG Wenzel (eds.), DJ O'Leary (eds.), E. Khosravi (eds.), Handbook of Olefin Metathesis, 2nd edition, Vol. 3, 2015, Wiley-VCH Verlag GmbH&Co. KGaA1608]. At the forefront of technology, many ruthenium-based homogeneous olefin metathesis catalysts are known that exhibit high activity in various types of metathesis reactions and high resistance to functional groups present in the substrate / product. The combination of these characteristics makes metathesis catalysts extremely important in modern organic synthesis and industry. The most widely existing and most widely used ruthenium complexes in the literature for olefin metathesis reactions include Grubbs-type ruthenium complexes (Gru-I, Gru-II, and Gru-III), Hov-Grubbs complexes (Hov-I and Hov-II), and 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, most of the structures of olefin metathesis catalysts are derived from the aforementioned ruthenium complexes.

[0003] Recently, NHC ligands in ruthenium catalyst structures have been replaced with cyclic (alkyl)(amino)carbene ligands (CAACs), and the resulting complexes occupy an important position in modern organic synthesis, namely in cross-metathesis reactions and ring-closing metathesis [Grubbs et al., Chem. Rev, 2010, 110, 1746-1787; International Publication No. 2017 / 055945].

[0004] [ka]

[0005] In modern organic synthesis, in an era of increasing scarcity of resources, including fossil fuels, and a risk of shortages 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 ethenorysis reactions, particularly the ethenorysis of methyl / ethyl derivatives of long-chain fatty acids. In particular, ruthenium complexes having CAAC ligands in the ruthenium coordination sphere are used for this purpose. The first literature report on ruthenium catalysts for olefin metathesis with CAAC ligands dates back to 2005 [Bertrandt et al., Angew. Chern. Int Ed., 2005, 44, 5705-5709]. In this scientific publication, Bertrandt first described CAAC ligands and their 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 method for synthesizing ruthenium complexes with CAAC ligands. In both cases, the ligand contained 2,6-diisopropylbenzene on the nitrogen atom and either two methyl substituents (Ru5) or cyclohexyl substituents (Ru10) on the 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, where the CAAC ligands contained symmetric substituents on the nitrogen atom, namely mesityl, 2,6-diisopropylbenzene, and 2,6-diethylbenzene, as well as asymmetric substituents, namely 2-ethyl-6-methylbenzene, 2-isopropyl-6-methylbenzene, and 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 exhibited high activity against the CC double bond of methyl oleate in the presence of ethylene overpressure, which led to the formation of methyl 1-decene and 9-decenoate esters, 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 having two CAAC ligands [Gawin et al., Angew. Chem. Int Ed. 2017, 56, 981-986; European Patent No. 3356379]. This publication presents a method for the preparation of indenylidene complexes having two CAAC ligands, and tests the activity of the complexes in selected reactions including macrocyclization, etenolysis, and cross-metathesis reactions of α-olefins. The document also discloses a novel approach to the synthesis of Hoveider-Grubbs catalysts having CAAC ligands, involving the reaction of an intermediate with associated styrene following the thermal dissociation of one CAAC ligand in the indenylidene complex.

[0008] [ka]

[0009] In 2017, Gawin et al. published a method for synthesizing a Hoveida-Grubbs analog with a nitro group at the para position as a substrate using a bis-CAAC complex [Gawin et al., ACS Catal. 2017, 7, 5443-5449]. This complex was proven effective for macrocyclization and cross-metathesis reactions with acrylonitrile.

[0010] [ka]

[0011] The European Patent [European Patent No. 3356379] discloses a structure Ru35-Ru37 having a modified benzylidene fragment.

[0012] [ka]

[0013] Subsequent modifications of the ruthenium catalyst included Hoveida-Grubbs type complexes, in which the hydrogen atoms of the styrene moiety were replaced with EWG or EDG groups. Mignagni et al. studied the reactivity of Ru38 and Ru39 catalysts by modifying the properties of the styrene ether ligand [French Patent Publication No. 2947189; French Patent Publication No. 2934178]. The presence of electron-donating amino groups was shown to adversely affect catalytic activity. On the other hand, modification of Ru40 with an electron-accepting SO2NMe2 group (Zhan type catalyst) enabled the synthesis of highly active catalysts in the ethenorysis reaction of fatty acids [European Patent No. 1905777; US Patent Publication No. 2011 / 0306815].

[0014] [ka]

[0015] Verpoort et al. studied the effects of unstable chelating groups, namely benzyl ethers, benzyl thioethers, and benzylamines [International Publication 2017 / 185324]. All catalysts converted methyl oleate with high selectivity and high TON values ​​[turnover rate - number of catalyst cycles, calculated number of moles of substrate reacted per mole of catalyst] (180,000–210,000). The reaction with ethylene in the presence of benzylamine chelated Ru43 and an activator (HSiCl3) (99.995%) yielded the highest TON value ever recorded (390,000).

[0016] [ka]

[0017] Lemcoff et al. demonstrated that an analogue of the Hoveida-Grubbs type catalyst, chelated with sulfur at the benzylidene moiety, exists in a cis / transparent Ru44-Ru47 configuration. The activity of the complex was studied, specifically in the polymerization reaction 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 in state-of-the-art techniques. Their use is mainly limited to simple aldehydes, including isobutanal or 2-phenylpropanal. In addition to the high cost and low availability of other aldehyde derivatives, particularly heterocyclic derivatives, where the expected product is obtained in low yield, the long and complex synthetic routes of these and other derivatives significantly limit the possibility of designing novel ruthenium catalysts containing modified CAAC ligands. These characteristics impose a major limitation on the further development of organometallic catalysts based on ruthenium with novel CAAC ligands. In particular, obtaining novel catalysts for olefin metathesis using ligands based on various types of aldehydes with the desired properties has become difficult to implement in chemical synthesis and is no longer economically justifiable in terms of scaling up to industrial scale.

[0020] In the investigation of novel ruthenium complexes with improved stability and selectivity that enable high catalytic activity and 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 scaling, it is also important that the planned synthesis is efficient at every stage, and that the reaction products can be purified in simple ways using techniques such as crystallization or distillation. It is also important to expand the ligand library, whose use includes alternative and / or improved sources of structures for ruthenium complexes used as catalysts in ethenorysis reactions of fatty acid ester derivatives.

[0021] From an industrial perspective, it is crucial that the activity of novel ruthenium complexes makes it possible to carry out the ethenolysis process in unrefined vegetable oil through a cumbersome, multi-step procedure of purifying the raw materials from compounds that inactivate the active catalyst molecule, such as oxygen, water, amines, sulfur compounds, halogen compounds, and peroxides. From an industrial perspective, it is equally important that the metathesis process can be carried out 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 procedures carried out in a glove box under an argon atmosphere, as described in prestigious academic journals by numerous prominent scientists, are impossible to reproduce and apply under industrial conditions. Therefore, it is essential to investigate novel ruthenium catalysts that are robust under reaction conditions and simultaneously active and efficient in carrying out the metathesis process.

[0022] Equally important is the ease with which catalysts can be transported and stored under normal atmospheric conditions, without the use of inert gases and low temperatures. The properties of such catalysts, as expected by industry, will enable their easy use on a large-scale industrial basis, 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 by the industry. Unexpectedly, the ethenolysis process catalyzed by the novel ruthenium complex tolerates the presence of oxygen, thereby allowing the assembly of the device in air and also enabling the use of ethylene of lower purity than the processes known in the literature. In addition, derivatives of fatty esters (plant-derived oils) can also be used without the need for a long purification process up to high purity of the raw materials.

Summary of the Invention

[0024] The subject of the present invention is of the formula CAAC-1

Chemical formula

[0025] Preferably, substituent R 9 This represents a substituted or unsubstituted heterocyclic group selected from heterocyclic groups selected from thiophene, benzothiophene, furan, benzofuran, pyrrole, benzopyrrole, aziridine, oxiran, thiran, azetidine, oxetane, thietan, pyrrolidine, tetrahydrofuran, tetrahydrothiophene, piperidine, tetrahydropyran, thian, pyridine, azepan, oxepane, thiepan, azepine, oxepine, thiepin, oxazole, imidazole, thiazole, isoxazole, pyrazole, isothiazole, triazine, pyrrolidine, pyridine, pyrimidine, hydantoin, quinoline, isoquinoline, chromonyl, coumarin, indole, indidine, indazole, purine, quinolidine, isoquinol, quinol, phthalazine, naphthyridine, carbazole, β-carbolin, or a substituent R 9 This represents a substituted or unsubstituted organometallic complex group comprising a cyclopentyl ring and a metal atom selected from iron, cobalt, nickel, chromium, titanium, and zirconium (metallocene).

[0026] Preferably, 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 formulas 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 matter of the present invention is also formula 1-Ru [ka] During the ceremony, X 1 and X 2 These are, independently of each other, halogen anions, -CN, -SCN, and -OR a , -SR a -O(C=O)R a ,-O(SO2)R a , and -OSi(R a ) Indicates an anionic ligand selected from the group containing the 3 group, R a C1-C 12 Alkyl, C3-C 12 Cycloalkyl, C2-C 12 Alkenyl, or C5-C 20 These indicate that the aryl group has at least one C1-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 These are, independently, hydrogen atoms, C1-C12 an alkyl group, C3-C 12 a cycloalkyl group, C5-C 20 an aryl group or C5-C 20 a heteroaryl group, C5-C 25 an aralkyl group, and these may be a hydrogen atom, a halogen atom, C1-C 12 an alkyl group, C1-C 12 a perfluoroalkyl group, C5-C 20 an aryl group, C5-C 20 a perfluoroaryl group, C5-C 20 a heteroaryl group, C1-C 12 an alkoxy group, C5-C 24 an aryloxy group, C5-C 20 a heteroaryloxy group, a sulfide group (-SR''), an amino group (-NR''2), and may be independently substituted by one and / or more substituents selected from the group consisting of, and the R'' group is a hydrogen atom, C1-C5 alkyl, C6-C 24 an aryl, C7-C 24 an aralkyl, independently, or alternatively, R 1 R 2 R 3 R 4 and R 5 are bonded to form a C5-C 25 ring;<000,0609>each substituent R 6 R 7 and R 8 is a hydrogen atom, a halogen atom, C1-C 12 an alkyl group or C5-C 20 an aryl group, and these are a hydrogen atom, C1-C 12 an alkyl group, C1-C 12 a perfluoroalkyl group, C5-C 20 an aryl group, C5-C 20 a perfluoroaryl group, C5-C 20 a heteroaryl group, C1-C 12 an alkoxy group, C5-C 24 an aryloxy group, C5-C 20The R'' group may be independently substituted by one and / or more substituents selected from the group including heteroaryloxy groups or halogen atoms, sulfide groups (-SR''), and amino groups (-NR''2), where the R'' group is a hydrogen atom, a C1-C5 alkyl group, or a C6-C 24 Aryl, C7-C 24 Alarquil means independently; Substituent R 9 This indicates substituted or unsubstituted heterocyclic groups and / or organometallic complex groups, which are hydrogen atoms, halogen atoms, C1-C 12 Alkyl alkyl group, C1-C 12 Perfluoroalkyl groups, C5-C 20 Aryl group, C5-C 20 Perfluoroaryl group, C5-C 20 Heteroaryl group, C1-C 12 Alkoxy group, C5-C 24 Aryloxy group, C5-C 20 The R'' group may be independently substituted by one and / or more substituents selected from the group including heteroaryloxy groups, sulfide groups (-SR''), and amino groups (-NR''2), where the R'' group is a hydrogen atom, a C1-C5 alkyl group, or a C6-C 24 Aryl, C7-C 24 Should we show Aralquil independently? Alternatively, R 6 and R 7 and / or R 8 and R 9 These are joined together, C5-C 25 Forming a ring; R 16 and R 17 These are, independently, hydrogen atoms, halogen atoms, and C1-C 25 Alkyl, C3-C 12 Cycloalkyl, C1-C 12 Perfluoroalkyl, C2-C 25 Alkene, C2-C 25 Alkenil, C3-C 25 Cycloalkenyl, C2-C 25 Alkinyl, C3-C 25 Cycloalkynyl, C1-C 25 Alkoxy, C5-C25 Aryl, C5-C 25 Aryloxyl, C6-C 25 Arylalkyl, C5-C 25 Heteroaryl, C5-C 25 Heteroaryloxyl, C5-C 25 It represents a 3- to 12-membered heterocycle containing a perfluoroaryl, sulfur, oxygen, nitrogen, selenium, or phosphorus atom; Substituent R 16 and R 17 C3-C 25 Cycloalkyl, C3-C 25 Cycloalkenyl, C3-C 25 Cycloalkynyl, C5-C 25 Aryl, C5-C 25 Heteroaryl, C5-C 25 A ring is formed, selected from the group comprising a 3- to 12-membered heterocycle containing a perfluoroaryl, sulfur, oxygen, nitrogen, selenium, or phosphorus atom, which includes a hydrogen atom, a halogen atom, and a C1-C2 ring. 25 Alkyl, C3-C 25 Cycloalkyl, C1-C 12 Perfluoroalkyl, C2-C 25 Alkene, C2-C 25 Alkenil, C3-C 25 Cycloalkenyl, C2-C 25 Alkinyl, C3-C 25 Cycloalkynyl, C1-C 25 Alkoxyl, C5-C 25 Aryl, C5-C 25 Aryloxyl, C6-C 25 Arylalkyl, C5-C 25 Heteroaryl, C5-C 25 Heteroaryloxyl, C5-C 25 It may also be independently substituted by one or more substituents selected from the group including perfluoroaryl compounds and 3- to 12-membered heterocycles; G is selected from the following: - Ligand of formula CAAC-1 [ka] In the formula, X and substituent R 1 ~R 9 However, it has the meaning defined above. or -heteroatom 1 Selected from the group containing oxygen, sulfur, or selenium atoms, and including hydrogen atoms, halogen atoms, oxygen atoms, 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 Aralkil, C5C 24 Aryloxyl, C2-C 12 Alkenyl, C6-C 20 Heteroaryl or heteroaryloxyl C5-C 24 It is substituted with a group selected from 3-12 membered heterocycles, and optionally with an acyl group (-COR'), cyano group (-CN), carboxyl group (-COOH), ester group (-COOR'), ester group (-CH2COOR'), ester group (-CHR'COOR'), ester group (-C(R')2COOR'), amide group (-CONR'2), Weinlev amide (-CON(R')(OR')), sulfone group (-SO2R'), formyl group (-CHO), sulfonamide group (-SOiNR'2), ketone group (-COR'), thioamide group (-CSNR'2), thioketone (-CSR'), thionoester group (-CSOR'), thioester group (-COSR'), dithioester group (-CS2R'), where the group R' is 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 Aralkil, C5C 24 Aryloxyl, C2-C 12 Alkenyl, C6-C20 Heteroaryl, C5-C 24 This shows a heteroaryloxyl, with the dashed line indicating the heteroatom and substituent R. 17 Direct bonding between or via methylene bridges, or substituent R via -CH2-, -CHR'-, or -CR'2- 17 It shows a bond between and a heteroatom, and substituent R 14 However, C5-C 15 It is an aryl group, and optionally contains a hydrogen atom, a halogen atom, and a C1-C group. 25 Alkyl, C3-C 25 Cycloalkyl, C2-C 25 Alkenil, C3-C 25 Cycloalkenyl, C2-C 25 Alkinyl, C3-C 25 Cycloalkynyl, C1-C 25 Perfluoroalkyl, C5-C 20 Alkoxyl, C5-C 20 Aryl, C5-C 20 Perfluoroaryl, C7-C 20 Aralkil, C5C 24 Aryloxyl, C6-C 20 Heteroaryl or C5-C 24 Heteroaryloxyl, 3-12 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'')), phosphonin group (-P(OR'')2), phosphine group (-PR''2), phosphine oxide group (-P(O)R''2), phosphonium group (-P +R''3) is substituted with 1 to 4 substituents independently selected from the group including 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''), and dithioester group (-CS2R''), wherein the R'' group is C1-C5 alkyl, C1-C5 perfluoroalkyl, C6-C 24 Aryl, C7-C 24 Aralkil, C5C 24 Showing perfluoroaryl, or -heteroatom 2 Selected from the group containing nitrogen or phosphorus atoms, substituted with a group selected from hydrogen atoms, methylidene, etc., optionally with 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 Aralkil, C5C 24 Aryloxyl, C2-C 12 Alkenyl, C6-C 20 Heteroaryl or C5-C 24 Heteroaryloxyls, 3-12 membered heterocyclic rings, substituted with an acyl group (-COR'), an ester group (-COOR'), a tert-butyloxycarbonyl group (t-Boc) or a 9-fluorenylmethoxycarbonyl group (Fmoc), a carbamin group (-CONR'2), a sulfone group (-SO2R'), or a formyl group (-CHO), where the 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 20Aralkil, C5C 24 Aryloxyl, C2-C 12 Alkenyl, C6-C 20 Heteroaryl or C5-C 24 It represents a heteroaryloxyl, optionally substituted with an acyl group (-COR'), cyano group (-CN), carboxyl group (-COOH), ester group (-COOR'), ester group (-CH2COOR'), ester group (-CHR'COOR'), ester group (-C(R')2COOR'), amide group (-CONR'2), sulfone group (-SO2R'), formyl group (-CHO), sulfonamide group (-SO2NR'2), ketone group (-COR'), thioamide group (-CSNR'2), thioketone group (-CSR'), thionoester group (-CSOR'), thioester group (-COSR'), or dithioester group (-CS2R'), where the 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 20 Aralkil, C5C 24 Aryloxyl, C2-C 12 Alkenyl, C6-C10 heteroaryl, or C5-C 24 This shows a heteroaryloxyl, with the dashed line indicating the heteroatom and substituent R. 14 Direct bonding between or via methylene bridges, or substituents R via (CH2)-, -(CHR')-, or -(CR'2)- 17 It shows a bond between and a heteroatom, and substituent R 17 However, C5-C 15 It is an aryl group, and optionally contains a hydrogen atom, a halogen atom, and a C1-C group. 25 Alkyl, C3-C 25 Cycloalkyl, C2-C 25 Alkenil, C3-C 25 Cycloalkenyl, C2-C 25 Alkinyl, C3-C 25 Cycloalkynyl, C1-C 25Perfluoroalkyl, C5-C 20 Alkoxyl, C5-C 20 Aryl, C5-C 20 Perfluoroaryl, C7-C 20 Aralkil, C5C 24 Aryloxyl, C6-C 20 Heteroaryl or C5-C 24 Heteroaryloxyl, 3-12 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'')), phosphonin group (-P(OR'')2), phosphine group (-PR''2), phosphine oxide group (-P(O)R''2), phosphonium group (-P + R''3) is substituted with 1 to 4 substituents independently selected from the group including 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''), and dithioester group (-CS2R''), wherein group R'' is C1-C5 alkyl, C1-C5 perfluoroalkyl, C6-C 24 Aryl, C7-C 24 Aralkil, C5C 24 Showing perfluoroaryl, or -heteroatom 3 Selected from the group containing halogen atoms, the dashed line represents heteroatoms and R 17 It shows a direct bond with the substituent, R 17 The substituent is C5-C 15 Aryl, or C5-C 25 It is a polyaryl compound, and optionally contains hydrogen atoms, halogen atoms, and C1-C25 Alkyl, C3-C 25 Cycloalkyl, C2-C 25 Alkenil, C3-C 25 Cycloalkenyl, C2-C 25 Alkinyl, C3-C 25 Cycloalkynyl, C1-C 25 Perfluoroalkyl, C5-C 20 Alkoxyl, C5-C 20 Aryl, C5-C 20 Perfluoroaryl, C7-C 20 Aralkil, C5C 24 Aryloxyl, C6-C 20 Heteroaryl or C5-C 24 Heteroaryloxyl, 3-12 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'')), phosphonin group (-P(OR'')2), phosphine group (-PR''2), phosphine oxide group (-P(O)R''2), phosphonium group (-P + R''3) is substituted with 1 to 4 substituents independently selected from the group including 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''), and dithioester group (-CS2R''), wherein the R'' group is C1-C5 alkyl, C1-C5 perfluoroalkyl, C6-C 24 Aryl, C7-C 24 Aralkil, C5C 24 It indicates a perfluoroaryl compound; This is a ruthenium complex represented by [formula].

[0029] The ruthenium complex is preferably 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 substituent has the meaning defined above; "n" means 1 or 0; Z is selected from the group containing halogen atoms, O atoms, S atoms, Se atoms, or NR''' groups, 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 Aralkil, C5C 24 Aryloxyl, C2-C 12 Alkenyl, C6-C 20 Heteroaryl or C5-C 24 Heteroaryloxyl, 3-12 membered heterocyclic, exhibiting an acyl group (-COR'), an ester group (-COOR'), a tert-butyl carboxycarbon group (t-Boc) or a 9-fluorenyl methoxycarbonyl group (Fmoc), a carbamin group (-CONR'2), a sulfone group (-SO2R'), or a formyl group (-CHO), where the 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 20Aralkil, C5C 24 Aryloxyl, C2-C 12 Alkenyl, C6-C 20 Heteroaryl or C5-C 24 Does it show heteroaryloxyl? Or it is a halogen atom, and if Z indicates a halogen atom, R 18 It does not exist; R 18 These 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''' group, -CH2COOR''' group, -CONR'''² group, -CH2CONR'''² group, -COR''' group, -CH2COR''' group, -CON(OR''')(R''') group, -CH2CON(OR''')(R''') group, or halogen atom, where R''' is C1-C 12 Alkyl, C3-C 12 Cycloalkyl, C2-C 12 Alkenyl, C6-C 20 These indicate an allele, and these are optionally at least one C1-C 12 Alkyl, C1-C 12 Perfluoroalkyl, C1-C 12 Alkoxyl, C6-C 24 Substituted with an aryloxyl or halogen atom; R 19 , R 20 , R 21 , and R 22 These are, independently, hydrogen atoms, halogen atoms, and C1-C 25 Alkyl alkyl group, C2-C 25 Alkenyl group, 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'')), phosphonin group (-P(OR'')2), phosphine group (-PR''2), phosphine oxide group (-P(O)R''2), phosphonium group (-P + R''3) represents a carboxyl group (-COOH), an ester group (-COOR''), an amide group (-CONR''2), an amide group (-NR''C(O)R'), a formyl group (-CHO), a ketone group (-COR''), a thioamide group (-CSNR''2), a thioketone group (-CSR''), a thionoester group (-CSOR''), a thioester group (-COSR''), and a dithioester group (-CS2R''). The R'' group represents C1-C5 alkyl, C1-C5 perfluoroalkyl, and C6-C 24 Aryl, C7-C 24 Aralkil, C5C 24 R indicates perfluoroaryl 16 , R 17 , R 18 , and R 19 Substituents can be attached, and therefore, substituted or unsubstituted C4-C 10 Ring system or C4-C 12 It forms a polycyclic system; It is represented as follows.

[0030] The ruthenium complex is preferably 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 substituent has the meaning defined above; R 16 and R 17 These are, independently, a hydrogen atom, a halogen atom, and an optionally substituted C1-C25 Alkyl, optionally substituted C3-C 25 Cycloalkyl, optionally substituted C1-C 12 Perfluoroalkyl, optionally substituted C2-C 25 Alkenes, C2-C substituted at will 25 Alkenyl, optionally substituted C3-C 25 Cycloalkenyls, optionally substituted C2-C 25 Alkinyl, optionally substituted C3-C 25 Cycloalkynyl, optionally substituted C1-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 compounds represent 3- to 12-membered heterocycles containing optionally substituted sulfur, oxygen, nitrogen, selenium, or phosphorus atoms; R 16 and R 17 The substituent can be bonded, C3-C 25 Cycloalkyl, C3-C 25 Cycloalkenyl, C3-C 25 Cycloalkynyl, C5-C 25 Aryl, C5-C 25 Heteroaryl, C5-C 25 A ring is formed, selected from the group containing a 3- to 12-membered heterocycle comprising a perfluoroaryl, sulfur, oxygen, nitrogen, selenium, or phosphorus atom, which includes a hydrogen atom, a halogen atom, and a C1-C2 ring. 25 Alkyl, C3-C 25 Cycloalkyl, C1-C 12 Perfluoroalkyl, C2-C 25 Alkene, C2-C 25 Alkenil, C3-C 25 Cycloalkenyl, C2-C 25 Alkinyl, C3-C 25 Cycloalkynyl, C1-C25 Alkoxyl, C5-C 25 Aryl, C5-C 25 Aryloxyl, C6-C 25 Arylalkyl, C5-C 25 Heteroaryl, C5-C 25 Heteroaryloxyl, C5-C 25 It can be independently substituted with one or more substituents selected from the group including perfluoroaryl compounds and 3- to 12-membered heterocycles; It is represented as follows.

[0031] Ruthenium complexes are sometimes represented by the formulas Ru1a, Ru2a, Ru3a, Ru4a, Ru5a, Ru6a, Ru7a, Ru8a, Ru9a, Ru10a, Ru11a, Ru11a, Ru12a, Ru13a, Ru14a, Ru15a, Ru16a, Ru17a, Ru18a, Ru19a, Ru20a, Ru21a, and Ru22a: [ka] TIFF0007898222000016.tif120160

[0032] The subject of the present invention is also a method for obtaining a ruthenium complex of formula 1a-Ru as defined above, [ka] Here, the method is Equation 10 [ka] During the ceremony, L 1 However, it represents a neutral ligand selected from the group including pyridine or substituted pyridine, P(R')3, P(OR')3, O(R')2, and N(R')3, where each R' independently corresponds to C1-C 12 Alkyl, C3-C 12 Cycloalkyl, C5-C 20 Aryl, C7-C 24 Aralkil, C5C 24These represent perfluoroaryl and 5-12 membered heteroaryl compounds. N, Z, X 1 , X 2 , and substituent R 18 , R1', R 20 , R 21 , and R 22 However, it has the meaning defined above. The alkylidene ruthenium complex represented by formula 8 [ka] In the formula, the substituent R 1 ~R 9 This has the meaning defined above. This is a method that involves a reaction with the carbene.

[0033] The subject matter of the present invention also relates to the use of compounds of formula 1-Ru as defined above as pre-catalysts and / or catalysts in olefin metathesis reactions, particularly ring-closed metathesis (RCM), cross-metathesis (CM), homometathesis (cross-metathesis between two molecules of the same olefin), etenolysis, isomerization, diastereoselective ring rearrangement metathesis (DRRM) reactions, "alkene-alkyne" (en-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, or esters of saturated fatty acids.

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

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

[0037] The reaction is preferably carried out over a period of 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 byproducts of the reaction, selected from ethylene, propylene, and butylene, are preferably actively removed from the reaction mixture using inert gas barbotage or under reduced pressure. [Brief explanation of the drawing]

[0042] The subject matter of the present invention will be described in the embodiments shown in the drawings.

[0043] [Figure 1] The structure of the Ru17a compound obtained based on X-ray structural analysis is shown. [Figure 2] This document outlines commercially available olefin metathesis pre-catalysts and catalysts, as well as a novel pre-catalyst and catalyst according to the present invention. [Figure 3] (A) A photograph showing the setup and sealed reaction system - autoclave, and (B) a photograph showing the reaction system (autoclave) that is opened before the ethenoresis reaction and does not require a glove box at any stage of the reaction process. [Modes for carrying out the invention]

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

[0045] Terms not defined herein have meanings provided and understood by experts in the art, taking into consideration the best available knowledge, this disclosure, and the description of this patent application.

[0046] Unless otherwise specified, the following chemical terms are used in this specification and have the meanings set forth in the following definitions.

[0047] As used in this specification, the term “halogen atom” means an element selected from F, Cl, Br, and I.

[0048] The term "carbene" refers to an electrically inert molecule in which a carbon atom has two non-bonding electrons that occur in a singlet 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 saturated, linear or branched hydrocarbon substituents having a 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-chain -(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 This includes 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, etc.

[0050] The term "alkoxyl" refers to an alkyl substituent, as defined above, that is bonded via an oxygen atom.

[0051] The term "perfluoroalkyl" refers to alkyl groups as defined above, in which all hydrogen atoms are replaced by the same or different halogen atoms.

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

[0053] The term "alkenyl" refers to an unsaturated, linear or branched, acyclic hydrocarbon substituent that has a specified number of hydrogen atoms and contains 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, and 3-decenyl.

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

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

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

[0057] The term "heteroaryl" refers to an aromatic monocyclic or polycyclic hydrocarbon substituent having a specified number of carbon atoms, in which at least one carbon atom is replaced by 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, -azaindryl, -quinolyl, -isoquinolyl, and -carbazolyl.

[0058] The term "heterocyclic" refers to a saturated, unsaturated, or partially unsaturated hydrocarbon substituent having a specified number of carbon atoms, wherein at least one carbon atom is replaced by a heteroatom selected from O, N, and S atoms. Examples of heterocyclic substituents include -furyl, -thiophenyl, -pyrrolyl, -oxazolyl, -imidazolyl, -thiazolyl, -isoxazolyl, -pyrazolyl, -isothiazolyl, -triazinyl, -pyrrolidinol, -pyrrolidinyl, -hydantoinyl, -oxylanil, -oxetanyl, -tetrahydrofuranil, -tetrahydrothiophenyl, -quinolinyl, -isoquinolinyl, -chromonyl, -coumalinyl, -indolyl, -indoridine, -benzo[b]furanil, -benzo[b]thiophenyl, -indazolyl, -purinyl, -4H-quinoridine, -isoquinolyl, -quinolyl, -phthalazinyl, -naphthyridinyl, -carbazolyl, and -β-carbolinyl.

[0059] The term "neutral ligand" refers to an uncharged substituent that can coordinate with a metal center (transition metal atom). Examples of such ligands include N-heterocyclic carbenes (NHCs), cyclic (alkyl)(amino)carbenes (CAACs), amines, phosphines and their oxides, alkyl and aryl phosphates and phosphates, arsines and their oxides, ethers, alkyl and aryl sulfides, coordination 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 that can coordinate with a charged metal center (transition metal atom) and can partially or completely compensate for the charge of the charged metal center. Examples of such ligands include anions of fluorides, chlorides, bromides, iodides, cyanides, cyanates and thiocyanates, carboxylic acid anions, alcohol anions, phenol anions, thiols and thiophenol anions, anions of hydrocarbons with delocalized charges (e.g., cyclopentadiene anions), anions of (organic) sulfuric acids and (organic) phosphoric acids and their esters (e.g., anions of alkyl sulfonic acids and aryl sulfonic acids, anions of alkyl phosphoric acids and aryl phosphoric acids, anions of alkyl and aryl esters of sulfuric acids, anions of alkyl and aryl esters of phosphoric acids, and anions of alkyl and aryl esters of alkyl phosphoric acids and aryl phosphoric acids).

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

[0062] The term "PAO" is an abbreviation for polyolefin or poly-alpha-olefin, and in the context of this invention, it is an abbreviation used for low molecular weight polyolefins used as high-boiling point solvents. It also refers to a class of solvents and / or lubricants that are products of polymerization of ethylene derivatives, leading to the formation of branched saturated hydrocarbons, and are used as heat-resistant, non-polar, high-boiling point solvents.

[0063] Embodiments of the Invention The following examples are included solely to illustrate the present invention and to clarify specific aspects of the invention, and are not intended to limit the invention or be considered equivalent to the entire 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 recommendations regarding specific reactants and methods were followed.

[0064] If necessary, model compounds for metathesis reactions were purified by fractional distillation and then stored under an inert gas atmosphere on activated neutral aluminum oxide. Tetrahydrofuran was purified by sodium-potassium alloy distillation in the presence of benzophenone and then stored on a 4 Å molecular sieve. If 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 aldehyde derivatives were commercially available.

[0066] Example I Synthesis of a new aldehyde, a precursor of CAAC ligands. The following Scheme 9 illustrates the first three steps in the synthesis of CAAC ligand precursors for synthesizing ruthenium catalysts (general formulas Ru1a to Ru21a, Scheme 9) for olefin metathesis, which is the subject of the present invention. [ka]

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

[0068] Reaction R1 Step R1 (Scheme 9) is used to synthesize an epoxide of general formula BX. For this purpose, a ketone and trimethylsulfonyl salt of general formula AX, preferably trimethylsulfonyl bromide (Me3SBr) or iodide (Me3SI), are used. The conversion is carried out in an organic solvent, preferably acetonitrile (MeCN) or other organic solvent, using stoichiometric amounts of a sulfonium salt and a metal hydroxide, preferably potassium hydroxide (KOH). The reaction mixture is carried out at a high temperature, preferably 60°C, for 2 to 16 hours. The product is separated by filtration from the reaction mixture and distillation of the solvent.

[0069] R1 Embodiment [ka]

[0070] In a reaction vessel equipped with a stirring bar, 2-acetylthiophene (7.01 g, 6.00 mL, 55.0 mmol, 1.0 equivalent), Me3SI (14.9 g, 71.5 mmol, 1.3 equivalents), KOH (9.44 g, 0.14 mmol, 2.6 equivalents), distilled water (0.25 mL), and MeCN (55 mL) were added under an argon atmosphere. The contents of the vessel were stirred at 60°C for 16 hours. 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), the solvent was evaporated, washed with n-hexane (40 mL), and the solvent was evaporated under reduced pressure to obtain the expected product as 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 Step R2 (Scheme 9) is used to synthesize an aldehyde of general formula CX. For this purpose, an epoxide of 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 (siRNA), chloroform, or toluene (PhMe). The reaction mixture is carried out at room temperature until the substrate is completely converted (2.5 to 48 hours). The product is purified by distillation of the solvent and then used in the next step without further purification.

[0072] Embodiment of carrying out reaction R2 [ka]

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

[0074] Another embodiment of carrying out reaction R2 [ka]

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

[0076] Another embodiment of carrying out reaction R2 [ka]

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

[0078] Reaction R3 Step R3 (Scheme 9) is used to synthesize an aldehyde of general formula FX. For this purpose, an aldehyde and alkenyl halide of general formula CX, preferably a chloride, a metal hydroxide, preferably NaOH, a quaternary ammonium salt, preferably tetra-N-butylammonium bromide is used. The conversion is carried out in an organic solvent, preferably toluene. The reaction mixture is carried out at a high temperature, preferably 40-60°C, for 30 minutes to 5 hours. The product is separated from the reaction mixture by extraction. This is then dried with a drying agent, preferably sodium sulfate or magnesium sulfate, the solid is filtered, and the solvent is removed by distillation under reduced pressure. The product is used in the next step without further purification.

[0079] Embodiment of carrying out reaction R3 [ka]

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

[0081] [Table 1] TIFF0007898222000027.tif251160 TIFF0007898222000028.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 a suitable Wittig reagent, preferably chloride, and a strong base, preferably potassium tert-butoxide, are used. The conversion is carried out in an anhydrous organic solvent, preferably tetrahydrofuran. The reaction mixture is carried out at a temperature range of -78 °C to room temperature (RT) for 16 hours. Thereafter, n-heptane is added to precipitate phosphine oxide. The solid is filtered, the solvent is removed by distillation, and the product is separated by column chromatography.

[0083] Another embodiment of carrying out reaction R4

Chemical formula

[0084] The Wittig reagent (13.2 g, 385 mmol, 1.35 equivalents), potassium tert-butoxide (20.4 g, 38.5 mmol, 1.35 equivalents), and anhydrous tetrahydrofuran (57 mL) were placed in a reaction vessel equipped with a stir bar under an argon atmosphere. The reaction was carried out at -78 °C for 1 hour. The mixture was then warmed to room temperature and stirred vigorously for 30 minutes. The mixture was cooled again to -78 °C, and then a solution of acetylferrocene (6.50 g, 285 mmol, 1 equivalent) 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, n-heptane (250 mL) was added to the residue to precipitate phosphine oxide and filtered. The solvent was removed by distillation under reduced pressure, and the crude product was purified by column chromatography (Al2O3 × 5% H2O), and fractions were collected using an eluent from 0 to 20% ethyl acetate in n-hexane. The expected product was obtained as a red-orange oil in a 96% yield (6.98 g, 27.2 mmol). 11H NMR (400 MHz, CDCl3) δ ppm: 6.22 - 6.20 (m, 0.53×1H), 5.96 - 5.94 (m, 0.47×1H), 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, 0.53×3H), 1.93 (d, J = 1.4 Hz, 0.53×3H), 1.84 (d, J = 1.4 Hz, 0.47×3H). 13 13C 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 aldehyde 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 - water, preferably acetone - 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 stirred vigorously for an additional 2 hours 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 with a desiccant, preferably sodium sulfate or magnesium sulfate. The solid is filtered, the solvent is evaporated under reduced pressure, and then the product is obtained.

[0086] Embodiments for carrying out Reaction R5

Chemical formula

[0087] In a reaction vessel equipped with a stirring bar, ether (2.60 g, 10.2 mmol, 1 equivalent), acetone (12 mL), and water (3 mL) were added. The mixture was cooled to below -50°C, and HBr (48% aqueous solution, 2.30 mL, 2 equivalents) was added dropwise under an argon atmosphere. The reaction was then carried out at 45°C for 2 hours. Aqueous solution of NaHCO3 was added to the reaction mixture until the pH became 8. The product was extracted with methylene chloride, dried over magnesium sulfate, and then filtered. The solvent was removed by distillation under reduced pressure to obtain the expected product as chestnut 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 The following scheme 15 illustrates the synthesis of CAAC ligands that enable the preparation of ruthenium catalysts (general formulas Ru1a to Ru21a, scheme 18) for olefin metathesis, which is the subject of the present invention.

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

[0090] [ka]

[0091] In step R6 (Scheme 15), the synthesis of imine HX is carried out, using suitable aniline and an aldehyde of general formula FX in the presence of an acid, preferably p-toluenesulfonic acid (PTSA). The reaction is carried out preferably in toluene or other organic solvents. The reaction mixture is carried out at the boiling point of the solvent. The product is separated 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 CAAC ligand of general formula LX is synthesized, and for this purpose, the imine of general formula HX from step R6 or R9 is used in the presence of an acid, preferably 4N hydrochloric acid in dioxane. The reaction is carried out at 85°C in anhydrous toluene under an argon atmosphere. Chloride ions are then preferably replaced with tetrafluoroborate ions, and the crude product is precipitated from a mixture of organic solvents, preferably methanol:diethyl ether.

[0093] Step R8 (Scheme 15) is used to synthesize imine GX. For this purpose, suitable aniline and aldehyde of 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 in the range of 25–45°C. The product is separated by precipitation and filtration through neutral Celite and distillation of the solvent. The product is used in the next step without further purification.

[0094] In step R9 (Scheme 15), imine HX is synthesized, using imine GX, an alkyl halide, preferably a 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, the alkyl halide is added, and then the mixture is heated to room temperature and the reaction is carried out for 16 hours. The product is separated by filtration through neutral Celite and distillation of the solvent. The product is used in the next step without further purification.

[0095] [ka]

[0096] In a round-bottom flask equipped with a stirring bar, 2,4-dimethyl-2-thiophenylpent-4-enal (2.11 g, 9.00 mmol, 1.00 equivalent), aniline (1.87 g, 9.00 mmol, 1.00 equivalent), and PTSA (17 mg, 0.09 mmol, 1 mol%) dissolved in PhMe (C=0.30 M) were added. The reaction was carried out at the boiling point of toluene until the substrate was completely converted (water was recovered 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 obtain the imine (1.50 g, 3.94 mmol) in 44% yield, which was used in the next step without further purification.

[0097] The imine from the previous step, 4M HCl (solution in dioxane, 2.53 g, 2.46 mL, 9.83 mmol, 2.5 equivalents), 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 hours. The solvent was evaporated under reduced pressure. The crude product was dissolved in a mixture of methylene chloride and water, NaBF4 (0.86 g, 7.86 mmol, 2.0 equivalents) was added, and ion exchange was carried out for 2 hours. The organic fraction was collected, washed with water, and dried over sodium sulfate. The product was precipitated from a MeOH:Et2O mixture to obtain 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] Embodiment of performing reaction R8 - R9 - R7

Chemical formula

[0099] Into a round - bottom flask under argon atmosphere, 2 - ferrocenylpropanal (5.45 g, 22.5 mmol, 1.00 equivalent) and anhydrous methanol (150 mL) were added, and then titanium(IV) isopropanolate (13.3 mL, 45 mmol, 2.00 equivalents) was added. To the reaction mixture thus prepared, 2,6 - diethylaniline (4.27 mL, 25.8 mmol, 1.15 equivalents) was added dropwise. 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 obtain the crude product as a maroon oily liquid in a yield of 73% (6.15 g, 16.5 mmol).

[0100] Imine (6.36 g, 17.1 mmol, 1.00 equivalent) and anhydrous tetrahydrofuran (835 mL) were placed under argon atmosphere into a round - bottom flask pre - heated under reduced pressure. 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 equivalents) was then added dropwise with vigorous stirring and then warmed to room temperature. After 1 hour, the reaction mixture was cooled again to - 78 °C in a dry - ice / acetone cooling bath, and 3 - chloro - 2 - methylpropene (2.50 mL, 25.6 mmol, 1.50 equivalents) 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 obtain a maroon oily liquid in a yield of 100% (7.30 g, 17.1 mmol).

[0101] The imine from the previous step (7.30 g, 17.1 mmol, 1 equivalent) 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 equivalents) was then added dropwise, and the reaction was carried out at 85°C for 16 hours with vigorous stirring. The solvent was evaporated under reduced pressure. The crude product was dissolved in methylene chloride (approximately 10 mL), a saturated aqueous solution of NaBF4 (3.75 g, 34.1 mmol, 2 equivalents) was added, and ion exchange was carried out for 2 hours with vigorous stirring. The mixture was extracted three times with methylene chloride, dried over anhydrous magnesium sulfate, filtered through neutral Celite, and then the solvent was evaporated under reduced pressure. The product was precipitated from a DCM:Et2O mixture to obtain red crystals in 47% yield (4.14 g, 8.05 mmol).

[0102] [Table 2] TIFF0007898222000035.tif233151 TIFF0007898222000036.tif248153 TIFF0007898222000037.tif240151 TIFF0007898222000038.tif248153 TIFF0007898222000039.tif228151 TIFF0007898222000040.tif248154 TIFF0007898222000041.tif46151

[0103] [ka]

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

[0105] Under an argon atmosphere, CAAC × BF4 ligand (430 mg, 916 μmol, 2.20 equivalents), first-generation Hoveida-Grubbs complex (250 mg, 416 μmol, 1.00 equivalent), anhydrous THF (C) CAAC The solution (0.1M) was placed in a heated Schlenk container and stirred for 1 minute. Then, LiHMDS (153 mg, 916 μmol, 2.20 equivalents) was added and stirred until complete conversion was achieved (20 minutes). 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. Then, a small amount of n-pentane was 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 vacuum drying, a green crystalline solid was obtained in 91% yield (267 mg, 380 μmol).

[0106] Using the method described in Example III, a series of complexes from Ru1a to Ru21a were obtained, and their structures are shown below.

[0107] All the complexes listed in the table below were characterized by nuclear magnetic resonance spectroscopy. Table 3 shows the complexes in a given solvent. 1 This shows the benzylidene proton shifts of each complex in the 1H NMR spectrum.

[0108] [Table 3] TIFF0007898222000045.tif248155 TIFF0007898222000046.tif248155 TIFF0007898222000047.tif248155 JPEG0007898222000048.jpg213155

[0109] Example V Research on the activity of complexes in the ethenorysis reaction of methyl oleate Methyl oleate was degassed by stirring under reduced pressure (using an oil pump) for at least 30 minutes. During this time, a sealed Schlenk container was prepared, weighed, and its weight calculated. The oil was then filtered through a syringe filter into the Schlenk container, and the weight of the oil was calculated by weighing the container together with the oil. The container containing the substrate was subjected to reduced pressure. In a separate container, a catalyst solution (~3 mg in 2 mL of degassed toluene) was prepared. A preheated glass insert for the Amar reactor, equipped with a stirring bar, was placed inside the Amar reactor, which was immersed in a preheated oil bath. The reactor was sealed, and the gas inside was removed using an oil pump. A portion of the catalyst (10 ppm, 3 ppm, or 500 ppb) was added to the Schlenk container containing the oil, and the mixture was immediately transferred to the reactor using a Teflon tube. The reactor was filled with ethylene to a dynamic pressure of 10 bar, and stirring was started to allow the reaction to run for 3 or 6 hours. A glove box and an inert gas atmosphere (argon) were not used during the reaction.

[0110] Subsequently, the pressure was normalized and the autoclave was disassembled. SnatchCat metal scavenger solution was immediately added, and the contents of the container were stirred for several minutes. Then, a sample was taken, diluted with toluene, and subjected to GC analysis.

[0111] [ka]

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

[0113] [Table 4] TIFF0007898222000051.tif248155 TIFF0007898222000052.tif232155 TIFF0007898222000053.tif201155

[0114] Example 1: 99.9% ethylene, <30 minutes, 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 to 10 ppm: 99.95% ethylene, 3 hours, 40°C; Reaction to 3 ppm: 99.95% ethylene, 3-6 hours, 40°C; Reaction to 0.5 ppm: 99.995% ethylene, 6 hours, 40°C (ethylene pressure of 10 bar)

[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 of the activity of ruthenium complexes in the ethenorysis reaction of methyl oleate outside a glove box under conditions that do not require an inert gas protective atmosphere (Figure 3). Figure 3 shows A) an autoclave assembled in air and B) an open autoclave before the ethenorysis reaction.

[0117] The corresponding etenolysis reaction described in Example V was carried out outside the glove box, under a fume hood, in an autoclave placed in air, and the reaction system is shown in Figure 3. Subsequent reaction steps were carried out in air without an inert gas protective atmosphere. Various purities of ethylene were used during the reaction, and the purity of the ethylene was lower than that reported in previous literature. It was observed that the use of the new ruthenium complexes Ru1a-Ru22a was tolerant of the use of low-quality ethylene, and the reaction results, as determined by TON and selectivity, were not impaired.

[0118] Example VII Synthesis of CAAC ligand and spirocarbon catalyst [ka]

[0119] Synthesis of compound I Aluminum(III) chloride (14.3 g, 105 mmol, 1.00 equivalent) and anhydrous DCM (100 mL) were placed in a three-necked flask equipped with a stirring bar under an argon atmosphere, and the suspension was cooled to -40°C. In a two-necked flask equipped with a stirring bar under an argon atmosphere, ferrocene (20.0 g, 105 mmol, 1.00 equivalent) was dissolved in anhydrous DCM (155 mL) and added dropwise to the aluminum(III) chloride suspension in DCM while stirring at -40°C. The mixture was then cooled to -78°C, and acryloyl chloride (9.81 mL, 116 mmol, 1.10 equivalent) was added dropwise at -78°C for 30 minutes. The reaction was carried out at -78°C for 18 hours, 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 × 5% H2O) to obtain 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 equivalent), Me3SBr (0.98 g, 6.28 mmol, 1.3 equivalents), KOH (0.70 g, 12.6 mmol, 2.6 equivalents), distilled water (0.25 mL), and MeCN (10 mL) were placed in a reaction vessel equipped with a stirring bar under an argon atmosphere. The contents of the vessel were stirred at 60°C for 16 hours. After the reaction was complete, 5 mL of diethyl ether (Et2O) 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 mixture was washed with n-hexane (10 mL), and the solvent was evaporated under reduced pressure to obtain 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 equivalent), zinc(II) chloride (0.50 g, 3.68 mmol, 1 equivalent), and toluene (16 mL) were placed in a reaction vessel equipped with a stirring bar. The reaction was carried out at room temperature for 2 hours. The reaction mixture was filtered through a shot funnel, and the solvent was removed by distillation under reduced pressure to obtain 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 In a round-bottom flask preheated under reduced pressure, aldehyde III (0.7 g, 2.76 mmol, 1.0 equivalent), 2-ethyl-6-methylaniline (0.38 g, 2.76 mmol, 1.0 equivalent), 4 Å molecular sieve (0.7 g), and methylene chloride (5.5 mL) were added under an argon atmosphere. The reaction was carried out at room temperature for 16 hours. The molecular sieve was filtered, and the solvent was evaporated under reduced pressure to obtain 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 equivalent) 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 equivalent) was then added dropwise with vigorous stirring, and the mixture was heated to room temperature. After 1 hour, the reaction mixture was cooled again to -78°C in a dry ice-acetone cooling bath, and 3-chloro-2-methylpropene (0.22 mL, 2.2 mmol, 1.50 equivalent) 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 filtered through a syringe filter to obtain 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 (0.49 g, 1.15 mmol, 1 equivalent) from the previous step 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 equivalents) was then added dropwise, and the reaction was carried out at 85°C for 16 hours with vigorous stirring. The solvent was evaporated under reduced pressure. The crude product was dissolved in methylene chloride (approximately 5 mL), a saturated aqueous solution of NaBF4 (0.25 g, 2.30 mmol, 2 equivalents) was added, and ion exchange was carried out for 2 hours with vigorous stirring. The mixture was extracted three times with methylene chloride, dried over anhydrous magnesium sulfate, filtered through neutral Celite, and then the solvent was evaporated under reduced pressure. The product was precipitated from the DCM:Et2O mixture, and the product was obtained 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 equivalents), first-generation Hoveida-Grubbs complex (170 mg, 283 μmol, 1.00 equivalent), and anhydrous THF (C) were mixed. CAAC The solution (0.1M) was placed in a preheated Schlenk flask and stirred for 1 minute. Then, LiHMDS (56 mg, 340 μmol, 1.20 equivalents) was added and stirred until complete conversion was achieved (5 minutes). Then, copper(I) chloride (56 mg, 566 μmol, 2.00 equivalents) was 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. Then, a small amount of n-pentane was 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, and then diethyl ether was used. After vacuum drying, a green crystalline solid was obtained (164 mg, 220 μmol, 77%).

[0126] [Table 5] TIFF0007898222000056.tif94155

Claims

1. Formula CAAC-1 【Chemistry 1】 where X represents an anion selected from the group consisting of a halogen atom, BF 4 - , PF 6 - , ClO 4 - , CF 3 SO 2 O - ; R 1 , R 2 , R 3 , R 4 , and R 5 However, independently, hydrogen atoms, C 1 -C 12 alkyl group, C 3 -C 12 Cycloalkyl groups, C 5 -C 20 Aryl group or C 5 -C 20 heteroaryl group, C 5 -C 25 It shows an aralkyl group, and these are hydrogen atoms, halogen atoms, and C 1 -C 12 alkyl group, C 1 -C 12 Perfluoroalkyl groups, 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'') 2 The R'' group may be independently substituted by one and / or more substituents selected from the group including the ) group, where the R'' group is a hydrogen atom, C 1 -C 5 Alkyl, C 6 -C 24 Ariel, C 7 -C 24 Either show the aralkyl independently, or alternatively, R 1 , R 2 , R 3 , R 4 , and R 5 However, when combined, C 5 -C 25 Forming a ring; Each substituent R 6 , R 7 , and R 8 However, hydrogen atoms, halogen atoms, C 1 -C 12 Alkyl or C 5 -C 20 These are aryl groups, and these are hydrogen-containing groups, C 1 -C 12 alkyl group, C 1 -C 12 Perfluoroalkyl groups, 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 ) may be independently substituted by one and / or more substituents selected from, where the R'' group is a hydrogen atom, C 1 -C 5 Alkyl, C 6 -C 24 Ariel, C 7 -C 24 Show the arachil independently; R 9 The substituent means a substituted or unsubstituted heterocyclic group, or an organometallic complex group selected from thiophene, benzothiophene, furan, benzofuran, or ferrocene, and these are hydrogen atom, halogen atom, 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 ) can be independently substituted by one and / or a plurality of substituents selected from the group containing, and the R'' group independently represents a hydrogen atom, C 1 -C 5 alkyl, C 6 -C 24 aryl, C 7 -C 24 aralkyl; A precursor of cyclic alkylamine carbene (CAAC), represented by [formula].

2. A precursor of formula CAAC-1 according to claim 1, 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】

3. Formula 1-Ru 【Transformation 3】 During the ceremony, X 1 and X 2 However, the halogen anions, -CN, -SCN, and -OR are independent of each other. a , -SR a -O(C=O)R a , -O(SO 2 ) R a , and -OSi(R a ) 3 It shows an anionic ligand selected from the group containing the group R a However, C 1 -C 12 Alkyl, C 3 -C 12 Cycloalkyl, C 2 -C 12 Alkenyl, or C 5 -C 20 These indicate an allele, and these 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 However, independently, hydrogen atoms, C 1 -C 12 alkyl group, C 3 -C 12 Cycloalkyl groups, C 5 -C 20 Aryl group or C 5 -C 20 heteroaryl group, C 5 -C 25 These show an aralkyl group, consisting of a hydrogen atom, a halogen atom, and C. 1 -C 12 alkyl group, C 1 -C 12 Perfluoroalkyl groups, 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 The R'' group may be independently substituted with one and / or more substituents selected from the group including ), and the R'' group may independently be substituted with a hydrogen atom, C 1 -C 5 Alkyl, C 6 -C 24 Ariel, C 7 -C 24 Does it show Aralkir? Alternatively, R 1 , R 2 , R 3 , R 4 , and R 5 However, when combined with each other, C 5 -C 25 Forming a ring; Each substituent R 6 , R 7 , and R 8 However, hydrogen atoms, halogen atoms, C 1 -C 12 Alkyl or C 5 -C 20 These are aryl groups, which consist of a hydrogen atom and a carbon atom. 1 -C 12 alkyl group, C 1 -C 12 Perfluoroalkyl groups, 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 The group R'' may be independently substituted with one and / or more substituents selected from the group including ), where the group R'' is a hydrogen atom, C 1 -C 5 Alkyl, C 6 -C 24 Ariel, C 7 -C 24 Show the arachil independently; R 9 The substituents represent substituted or unsubstituted heterocyclic groups and / or organometallic complex groups selected from thiophene, benzothiophene, furan, benzofuran, or ferrocene, which include hydrogen atoms, halogen atoms, and C 1 -C 12 alkyl group, C 1 -C 12 Perfluoroalkyl groups, 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 The R'' group may be independently substituted with one and / or more substituents selected from the group including ), where the R'' group is a hydrogen atom, C 1 -C 5 Alkyl, C 6 -C 24 Ariel, C 7 -C 24 Show the arachil independently; R 16 and R 17 However, independently, hydrogen atoms, halogen atoms, and C 1 -C 25 Alkyl, C 3 -C 25 Cycloalkyl, C 1 -C 12 Perfluoroalkyl, C 2 -C 25 Alken, C 2 -C 25 Alkenil, C 3 -C 25 Cycloalkenyl, C 2 -C 25 Alkinyl, C 3 -C 25 Cycloalkynyl, C 1 -C 25 Alkoxy, C 5 -C 25 Ariel, C 5 -C 25 Aryloxyl, C 6 -C 25 Arylalkyl, C 5 -C 25 Heteroaryl, C 5 -C 25 Heteroaryloxyl, C 5 -C 25 It represents a 3- to 12-membered heterocycle containing a perfluoroaryl, sulfur, oxygen, nitrogen, selenium, or phosphorus atom; This results in substituent R 16 and R 17 However, because they can be linked together, C 3 -C 25 Cycloalkyl, C 3 -C 25 Cycloalkenyl, C 3 -C 25 Cycloalkynyl, C 5 -C 25 Ariel, C 5 -C 25 Heteroaryl, C 5 -C 25 A ring is formed, selected from the group comprising a 3- to 12-membered heterocycle containing a perfluoroaryl, sulfur, oxygen, nitrogen, selenium, or phosphorus atom, which contains a hydrogen atom, a halogen atom, and C 1 -C 25 Alkyl, C 3 -C 25 Cycloalkyl, C 1 -C 12 Perfluoroalkyl, C 2 -C 25 Alken, C 2 -C 25 Alkenil, C 3 -C 25 Cycloalkenyl, C 2 -C 25 Alkinyl, C 3 -C 25 Cycloalkynyl, C 1 -C 25 Alkoxyl, C 5 -C 25 Ariel, C 5 -C 25 Aryloxyl, C 6 -C 25 Arylalkyl, C 5 -C 25 Heteroaryl, C 5 -C 25 Heteroaryloxyl, C 5 -C 25 They may be independently substituted by one or more substituents selected from the group including perfluoroaryl and 3- to 12-membered heterocycles; G is selected from the following, etc. - The following carven 【Chemistry 4】 In the formula, the substituent R 1 ~R 9 However, it has the meaning defined above, Here, the dashed line between G and R 17 in equation 1-Ru represents the absence of a bond, and the dashed line between G and Ru represents a coordinate bond. or - Heteroatom 1 Selected from the group including oxygen atoms, sulfur atoms, and selenium atoms, and containing hydrogen atoms, fluorine atoms, oxygen atoms, and C 1 -C 25 Alkyl, C 1 -C 25 Perfluoroalkyl, C 3 -C 25 Cycloalkyl, C 5 -C 20 Alkoxyl, C 5 -C 20 Ariel, C 5 -C 20 Perfluoroaryl, C 7 -C 20 Aralkil, C 5 -C 24 Aryloxyl, C 2 -C 12 Alkenil, C 6 -C 20 Heteroaryl or C 5 -C 24 Substituting with a group selected from heteroaryloxyls, 3- to 12-membered heterocycles, etc., optionally including an acyl group (-COR'), cyano group (-CN), carboxyl group (-COOH), ester group (-COOR'), or ester group (-CH2). 2 COOR'), ester group (-CHR'COOR'), ester group (-C(R') 2 COOR'), amide group (-CONR') 2 ), Weinlev-type amide (-CON(R')(OR')), sulfone group (-SO 2 R'), formyl group (-CHO), sulfonamide group (-SOiNR') 2 ), ketone group (-COR'), thioamide group (-CSNR') 2 ), thioketone (-CSR'), thionoester group (-CSOR'), thioester group (-COSOR'), dithioester group (-CS 2 Substituting with R', the base R' independently becomes C 1 -C 25 Alkyl, C 1 -C 25 Perfluoroalkyl, C 3 -C 25 Cycloalkyl, C 5 -C 20 Alkoxyl, C 5 -C 20 Ariel, C 5 -C 20 Perfluoroaryl, C 7 -C 20 Aralkil, C 5 -C 24 Aryloxyl, C 2 -C 12 Alkenil, C 6 -C 20 Heteroaryl, C 5 -C 24 This shows a heteroaryloxy, with the dashed line representing heteroatom 1 and substituent R. 17 Direct bonding between, or methylene bridge, -CH 2 -, -CHR'-, or -CR' 2 - substituent R 17 The bond between and heteroatom 1 is shown, and substituent R 14 However, C 5 -C 15 It is an aryl group, and optionally contains a hydrogen atom, a halogen atom, or C 1 -C 25 Alkyl, C 3 -C 25 Cycloalkyl, C 2 -C 25 Alkenil, C 3 -C 25 Cycloalkenyl, C 2 -C 25 Alkinyl, C 3 -C 25 Cycloalkynyl, C 1 -C 25 Perfluoroalkyl, C 5 -C 20 Alkoxyl, C 5 -C 20 Ariel, C 5 -C 20 Perfluoroaryl, C 7 -C 20 Aralkil, C 5 -C 24 Aryloxyl, C 6 -C 20 Heteroaryl or C 5 -C 24 Heteroaryloxyl, 3-12 membered heterocycle, alkoxyl group (-OR''), sulfide group (-SR''), sulfoxide group (-S(O)R''), sulfonium group (-S + R'' 2 ), sulfone group (-SO 2 R''), sulfonamide group (-SO 2 NR'' 2 ), 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'')), 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 (-COS''), dithioester group (-CS 2 Substituted with 1 to 4 substituents independently selected from the group containing R'', where the R'' group is C 1 -C 5 Alkyl, C 1 -C 5 Perfluoroalkyl, C 6 -C 24 Ariel, C 7 -C 24 Aralkil, C 5 -C 24 Showing perfluoroaryl, or - Heteroatom 2 Selected from the group containing a nitrogen atom or a phosphorus atom, substituted with a group selected from a hydrogen atom, methylidene, etc., optionally with 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 Ariel, C 5 -C 20 Perfluoroaryl, C 7 -C 20 Aralkil, C 5 -C 24 Aryloxyl, C 2 -C 12 Alkenil, C 6 -C 20 Heteroaryl or C 5 -C 24 Heteroaryloxyl, 3-12 membered heterocycle, acyl group (-COR'), ester group (-COOR'), tert-butylbutyloxycarbonyl group (t-Boc) or 9-fluorenylmethoxycarbonyl group (Fmoc), carbamin group (-CONR') 2 ), sulfone 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 Ariel, C 5 -C 20 Perfluoroaryl, C 7 -C 20 Aralkil, C 5 -C 24 Aryloxyl, C 2 -C 12 Alkenil, C 6 -C 20 Heteroaryl or C 5 -C 24 It represents a heteroaryloxyl, and optionally includes an acyl group (-COR'), a cyano group (-CN), a carboxyl group (-COOH), an ester group (-COOR'), or an ester group (-CH2). 2 COOR'), ester group (-CHR'COOR'), ester group (-C(R') 2 COOR'), amide group (-CONR') 2 ), sulfone group (-SO 2 R'), formyl group (-CHO), sulfonamide group (-SO 2 NR' 2 ), ketone group (-COR'), thioamide group (-CSNR') 2 ), thioketone group (-CSR'), thionoester group (-CSOR'), thioester group (-COSOR'), dithioester group (-CS 2 Substituted with R', 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 Ariel, C 5 -C 20 Perfluoroaryl, C 7 -C 20 Aralkil, C 5 -C 24 Aryloxyl, C 2 -C 12 Alkenil, C 6 -C 20 Heteroaryl, or C 5 -C 24 This shows a heteroaryloxyl, with the dashed line representing the heteroatom 2 and substituent R. 14 Direct bonding between, or methylene bridge, (CH 2 )-, -(CHR')-, or -(CR' 2 )- substituent R 17 The bond between the heteroatom 2 and the substituent R 17 However, C 5 -C 15 It is an aryl group, and optionally contains a hydrogen atom, a halogen atom, or C 1 -C 25 Alkyl, C 3 -C 25 Cycloalkyl, C 2 -C 25 Alkenil, C 3 -C 25 Cycloalkenyl, C 2 -C 25 Alkinyl, C 3 -C 25 Cycloalkynyl, C 1 -C 25 Perfluoroalkyl, C 5 -C 20 Alkoxyl, C 5 -C 20 Ariel, C 5 -C 20 Perfluoroaryl, C 7 -C 20 Aralkil, C 5 -C 24 Aryloxyl, C 6 -C 20 Heteroaryl or C 5 -C 24 Heteroaryloxyl, 3-12 membered heterocycle, alkoxyl group (-OR''), sulfide group (-SR''), sulfoxide group (-S(O)R''), sulfonium group (-S + R'' 2 ), sulfone group (-SO 2 R''), sulfonamide group (-SO 2 NR'' 2 ), 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'')), 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 (-COS''), dithioester group (-CS 2 Substituting with 1 to 4 substituents independently selected from the group including R'', where the group R'' is C 1 -C 5 Alkyl, C 1 -C 5 Perfluoroalkyl, C 6 -C 24 Ariel, C 7 -C 24 Aralkil, C 5 -C 24 Showing perfluoroaryl, or - Heteroatom 3 Selected from the group containing halogen atoms, the dashed line represents heteroatom 3 and R 17 R shows a direct bond with the substituent. 17 The substituent is C 5 -C 15 Aryl, or C 5 -C 25 It is a polyaryl compound, and optionally contains hydrogen atoms, halogen atoms, and C 1 -C 25 Alkyl, C 3 -C 25 Cycloalkyl, C 2 -C 25 Alkenil, C 3 -C 25 Cycloalkenyl, C 2 -C 25 Alkinyl, C 3 -C 25 Cycloalkynyl, C 1 -C 25 Perfluoroalkyl, C 5 -C 20 Alkoxyl, C 5 -C 20 Ariel, C 5 -C 20 Perfluoroaryl, C 7 -C 20 Aralkil, C 5 -C 24 Aryloxyl, C 6 -C 20 Heteroaryl or C 5 -C 24 Heteroaryloxyl, 3-12 membered heterocycle, alkoxy group (-OR''), sulfide group (-SR'), sulfoxide group (-S(O)R''), sulfonium group (-S + R'' 2 ), sulfone group (-SO 2 R''), sulfonamide group (-SO 2 NR'' 2 ), 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'')), 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 (-COS''), dithioester group (-CS 2 Substituting with 1 to 4 substituents independently selected from the group including R'', where the R'' group is C 1 -C 5 Alkyl, C 1 -C 5 Perfluoroalkyl, C 6 -C 24 Ariel, C 7 -C 24 Aralkil, C 5 -C 24 It shows perfluoroaryl; A ruthenium complex represented by [the symbol].

4. The ruthenium complex is, Formula 1a-Ru 【Transformation 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 substituent has the meaning defined above; "n" means 1 or 0; Z is selected from the group containing halogen atoms, O atoms, S atoms, Se atoms, or NR''' groups, 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 Ariel, C 5 -C 20 Perfluoroaryl, C 7 -C 20 Aralkil, C 5 -C 24 Aryloxyl, C 2 -C 12 Alkenil, C 6 -C 20 Heteroaryl or C 5 -C 24 Heteroaryloxyl, 3-12 membered heterocycle, acyl group (-COR'), ester group (-COOR'), tert-butyloxycarbonyl group (t-Boc) or 9-fluorenylmethoxycarbonyl group (Fmoc), carbamin group (-CONR') 2 ), sulfone group (-SO 2 R'), showing 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 Ariel, C 5 -C 20 Perfluoroaryl, C 7 -C 20 Aralkil, C 5 -C 24 Aryloxyl, C 2 -C 12 Alkenil, C 6 -C 20 Heteroaryl or C 5 -C 24 Does it show heteroaryloxyl? Or it is a halogen atom, and if Z represents a halogen atom, R 18 It does not exist; R 18 However, independently, hydrogen atoms, C 1 -C 25 Alkyl, C 1 -C 25 Cycloalkyl, C 5 -C 20 Alkoxyl, C 5 -C 20 Ariel, 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''') means a group or halogen atom, where R''' is C 1 -C 12 Alkyl, C 3 -C 12 Cycloalkyl, C 2 -C 12 Alkenil, C 6 -C 20 These represent an allele, and these optionally include 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 However, independently, hydrogen atoms, halogen atoms, and 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 ), sulfone group (-SO 2 R''), sulfonamide group (-SO 2 NR'' 2 ), 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'')), 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 (-COS''), dithioester group (-CS 2 R'') indicates that the R'' group is C 1 -C 5 Alkyl, C 1 -C 5 Perfluoroalkyl, C 6 -C 24 Ariel, C 7 -C 24 Aralkil, C 5 -C 24 R indicates perfluoroaryl. 16 , R 17 , R 18 , and R 19 Substituents may be attached, and therefore, substituted or unsubstituted C 4 -C 10 Ring system or C 4 -C 12 It forms a polycyclic system; The ruthenium complex according to claim 3, represented as shown.

5. The ruthenium complex is, Formula 1b-Ru 【Transformation 6】 In the formula, X 1 and X 2 , and substituent R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 However, it has the meaning defined above; R 16 and R 17 However, independently, hydrogen atoms, halogen atoms, and arbitrarily 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, C which can be substituted at will 2 -C 25 Alkenyl, C which can be substituted at will. 3 -C 25 Cycloalkenyl, optionally substituted C 2 -C 25 Alkinyl, C which can be substituted at will. 3 -C 25 Cycloalkyl, optionally substituted C 1 -C 25 Alkoxy, optionally substituted C 5 -C 25 Aryl, C can be substituted as desired. 5 -C 25 Aryloxyl, optionally substituted C 6 -C 25 Arylalkyl, optionally substituted C 5 -C 25 Heteroaryls, optionally substituted C 5 -C 25 Heteroaryloxyl, optionally substituted C 5 -C 25 Perfluoroaryls represent 3- to 12-membered heterocycles containing optionally substituted sulfur, oxygen, nitrogen, selenium, or phosphorus atoms; R 16 and R 17 The substituent can be bonded to C 3 -C 25 Cycloalkyl, C 3 -C 25 Cycloalkenyl, C 3 -C 25 Cycloalkynyl, C 5 -C 25 Ariel, C 5 -C 25 Heteroaryl, C 5 -C 25 A ring is formed, selected from the group containing a 3- to 12-membered heterocycle comprising a perfluoroaryl, sulfur, oxygen, nitrogen, selenium, or phosphorus atom, which comprises a hydrogen atom, a halogen atom, and C 1 -C 25 Alkyl, C 3 -C 25 Cycloalkyl, C 1 -C 12 Perfluoroalkyl, C 2 -C 25 Alken, C 2 -C 25 Alkenil, C 3 -C 25 Cycloalkenyl, C 2 -C 25 Alkinyl, C 3 -C 25 Cycloalkynyl, C 1 -C 25 Alkoxyl, C 5 -C 25 Ariel, C 5 -C 25 Aryloxyl, C 6 -C 25 Arylalkyl, C 5 -C 25 Heteroaryl, C 5 -C 25 Heteroaryloxyl, C 5 -C 25 It can be independently substituted with one or more substituents selected from the group including perfluoroaryl and 3- to 12-membered heterocycles; The ruthenium complex according to claim 3 or 4, represented by the following:

6. Ruthenium complexes are given by the formulas Ru1a, Ru2a, Ru3a, Ru4a, Ru5a, Ru6a, Ru7a, Ru8a, Ru9a, Ru10a, Ru11a, Ru11a, Ru12a, Ru13a, Ru14a, Ru15a, Ru16a, Ru17a, Ru18a, Ru19a, Ru20a, Ru21a, Ru22a: 【Transformation 7】 A ruthenium complex according to any one of claims 3 to 4, selected from the complexes represented by [the formulas].

7. Formula 10 【Transformation 8】 During the ceremony, L 1 However, pyridine or substituted pyridine, P(R') 3 , P(OR') 3 , O(R') 2 , N(R') 3 It shows a neutral ligand selected from the group including, where each R' is independently C 1 -C 12 Alkyl, C 3 -C 12 Cycloalkyl, C 5 -C 20 Ariel, C 7 -C 24 Aralkil, C 5 -C 24 These represent perfluoroaryl and 5-12 membered heteroaryl groups; N, Z, X 1 , X 2 , and substituent R 18 , R1', R 20 , R 21 , and R 22 However, it has the meaning defined above; The alkylidene ruthenium complex represented by formula 8 【Chemistry 9】 In the formula, the substituent R 1 ~R 9 However, it has the meaning defined above; A carbene represented by formula 1a-Ru as defined in claim 4, characterized by reacting with a carbene represented by formula 1a-Ru 【Chemistry 10】 A method for synthesizing ruthenium complexes represented by [formula].

8. Use of a compound represented by formula 1-Ru as defined in any one of claims 3 to 6 as a pre-catalyst and / or catalyst in an olefin metathesis reaction.

9. The use according to claim 8, 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, or esters of saturated fatty acids.

10. The use according to claim 8, wherein the reaction is carried out in a solvent-free system.

11. The use according to claim 8, wherein the reaction is carried out at a temperature of 20°C to 200°C.

12. The use according to claim 8, wherein the reaction is carried out over a period of time from 5 minutes to 48 hours.

13. The use according to claim 8, wherein compound 1-Ru is applied in an amount not exceeding 10 mol%.

14. The use according to claim 8, wherein compound 1-Ru is applied in an amount not exceeding 0.1 mol%.

15. The use according to claim 8, wherein compound 1-Ru is added to the reaction mixture in a solid portion and / or continuously using a pump as a solution in an organic solvent.

16. The use according to claim 8, wherein a gaseous byproduct of the reaction, selected from ethylene, propylene, and butylene, is actively removed from the reaction mixture using inert gas vapotage or by vacuum.

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