Novel ruthenium complex, method for synthesizing the same, intermediate compound used in this method, method for synthesizing the same, and use of the novel ruthenium complex in olefin metathesis reaction

Abstract

The subject matter of the present invention is a novel ruthenium complex having the general formula Ru-1, wherein all variables have the meanings defined in the present disclosure. The subject matter of the present invention is also a method for synthesizing the ruthenium complex, an intermediate which is a precursor of the ligand used in the synthesis reaction of the ruthenium complex CAAC-1, and the use of this ruthenium complex as a (pre)catalyst in olefin metathesis reactions.

Description

Technical Field

[0001] The subject of the present invention is a novel ruthenium complex having a CAAC ligand (cyclic alkylaminocarbene) which has been found to be useful as a catalyst and / or (pre)catalyst in olefin metathesis reactions, and its use in olefin metathesis reactions. The subject of the present invention also includes intermediate compounds used to synthesize novel ruthenium complexes having CAAC ligands, as well as methods for the synthesis of novel ruthenium complexes having CAAC ligands. This invention is used as a desired means in the selective synthesis of olefins having C═C bonds in well-known organic synthesis, in particular in cross-metathesis reactions using ethylene-ethenolysis.

Background Art

[0002] In recent years, there have been significant advancements in the use of olefin metathesis in organic synthesis [R.H. Grubbs (Editor), A.G. Wenzel (Editor), D.J. O’Leary (Editor), E. Khosravi (Editor), Handbook of Olefin Metathesis, 2nd Edition, 3 volumes, 2015, Wiley-VCH Verlag GmbH & Co. KGaA, 1608 pages]. Many state-of-the-art ruthenium-based homogeneous olefin metathesis catalysts are known that exhibit high activity in various types of metathesis reactions and high tolerance towards functional groups present in the substrate / product. Due to this combination of features, metathesis catalysts are quite important in modern organic synthesis as well as in industry. The most widely present ruthenium complexes in the literature, and the most widely used ones in olefin metathesis reactions, include Grubbs-type ruthenium complexes (Gru-I, Gru-II, and Gru-III), Hoveyda-Grubbs complexes (Hov-I and Hov-II), and indenylidene complexes (Ind-I, Ind-II, and Ind-III), including the first, second, and third generations [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. Recently, Bertrand-type catalysts with cyclic(alkyl)(amino)carbenes (CAAC) have found an important place in modern organic synthesis, i.e., in cross-metathesis reactions and in ring-closing metathesis, due to their use [Grubbs et al. Chem. Rev., 2010, 110, 1746 - 1787; International Publication 2017 / 055945A1].

Chem.

[0003] In modern organic synthesis, in an era where resources, i.e., fossil fuels, are continuously decreasing even more, and thus there is a risk of a shortage of raw materials for synthesis (e.g., polymers based on crude oil derivatives), it is extremely important to develop new technologies and reactions that enable the synthesis of target compounds. Such processes include the enolysis reaction, specifically the enolysis of methyl / ethyl esters of long-chain fatty acids. Ruthenium complexes having a CAAC ligand in the coordination sphere of ruthenium are particularly useful for this purpose. The first literature report on olefin metathesis ruthenium catalysts having a CAAC ligand dates back to 2005 [Bertrandt i in. Angew. Chem. Int. Ed., 2005, 44, 5705 - 5709]. In this research publication, Bertrand first described the CAAC ligand and its use in organic synthesis. In subsequent publications from 2007 [Bertrandt et al. Angew. Chem. Int. Ed., 2007, 46, 7262 - 7265], Bertrandt first described the synthesis of ruthenium complexes having a CAAC ligand. In both cases, the ligand contained 2,6 - diisopropylbenzene at the nitrogen atom, while on the one hand, at the carbon atom C2, it contained two methyl (Ru5) substituents and a cyclohexyl substituent (Ru10). Next, Professor Bertrandt's team collaborated with Professor Grubbs' team to obtain and test 17 structures regarding their activity in the enolysis reaction of methyl oleate. Here, the CAAC ligand had symmetric substituents at the nitrogen atom: mesityl, 2,6 - diisopropylbenzene, 2,6 - diethylbenzene, and the asymmetric substituents 2 - ethyl - 6 - methylbenzene, 2 - isopropyl - 6 - methylbenzene, 2 - methyl - 6 - tert - butylbenzene, while on the C2 carbon atom, it contained two of the following substituents: methyl, ethyl, n - propyl, cyclohexyl, adamantyl, or phenyl [Bertrandt et al. Angew. Chem. Int. Ed., 2015, 54, 1919 - 1923].These catalysts showed high activity towards the double C=C bond in methyl oleate in the presence of ethylene under positive pressure, leading to the formation of valuable industrial products in olefin metathesis reactions: methyl esters of 1-decene and 9-decenoic acid.

Chem.

[0004] In 2017, Gawin et al. first reported the synthesis of indenylidene-type complexes with two CAAC ligands [Gawin et al., Angew. Chem. Int. Ed. 2017, 56, 981 - 986 and European Patent 3356379 B1]. This publication demonstrated the synthesis of indenylidene complexes and their activity in selected metathesis reactions, including the macrocyclization, ethenolysis, or cross-metathesis reactions of α-olefins. This document also discloses a novel method for the synthesis of Hoveyda-Grubbs catalysts with CAAC ligands, including the thermal dissociation of one CAAC ligand in the indenylidene complex, followed by the reaction of this intermediate with the corresponding styrene.

Chem.

[0005] Also in 2017, Gawin et al. published a method for the synthesis of Hoveyda-Grubbs-type complex analogues with a nitro group in the para position, using the BisCAAC complex as a substrate [Gawin et al. ACS Catal. 2017, 7, 5443 - 5449]. These complexes were found to be effective in macrocyclization and cross-metathesis reactions with acrylonitrile.

Chem.

[0006] European Patent [European Patent 3356379 B1] discloses structures Ru35 - Ru37 with a modified benzylidene fragment.

Chem.

[0007] Subsequent modification of the ruthenium catalyst was related to Hoveyda-Grubbs type complexes in which the hydrogen atom in the styrene moiety was replaced by an EWG or EDG group. Mignagni et al. studied the reactivity of Ru38 and Ru39 catalysts by modulating the nature of the styrene ether ligand [FR2947189A1; FR2934178A1]. The presence of an electron-donating amine group was shown to have a negative impact on catalytic activity. On the other hand, the modification of Ru40 with an electron-accepting SO2NMe2 group (Zhan type catalyst) enabled the synthesis of a highly active catalyst in the enolysis reaction of fatty acids [European Patent 1905777B1; US Patent Application Publication 2011 / 0306815A1].

Chemical formula

[0008] Verpoort et al. studied the influence of labile chelating groups: benzyl ether, benzyl thioether, and benzylamine [International Publication 2017 / 185324A1]. All catalysis converted methyl oleate with high selectivity and high TON values [turnover number - the number of moles of substrate undergoing reaction per mole of catalyst, calculated for the number of catalyst cycles] (180,000 - 210,000). The reaction carried out with ethylene (99.995%) in the presence of Ru43 chelated with benzylamine and an activator (HSiCl3) has, so far, provided the highest TON value (390,000).

Chemical formula

[0009] Lemcoff et al. showed that analogs of Hoveyda-Grubbs type catalysts chelated with sulfur within the benzylidene moiety exist as cis / trans pairs Ru44–Ru47. The activity of the complexes was studied, i.e., in the polymerization reaction of norbornene derivatives [Rozenberg, I. et al. ACS Catal. 2018, 8, 8182–8191.].

Chem.

[0010] Tuba et al. developed a tandem ethenolysis / isomerization reaction using catalysts based on bicyclic(alkyl)(amino)carbene (BICAAC) (Ru48–Ru52) and the (RuHCl(CO)(PPh3)3 catalyst. Thanks to the methodology used and the use of methyl oleate as the substrate, they were able to obtain methyl acrylate and propylene as the main products and achieve a TON value of 1400 (Nagyhazi et al. Angew Chem. Int. Ed. 2022, 61, e202204413.).

Chem.

[0011] The limited availability of various anilines used as substrates in the synthesis of CAAC ligands is a significant problem known in the art. Their use is highly restricted to simple symmetric anilines, namely 2,4,6-trimethylaniline, 2,6-diethylaniline, or 2,6-diisopropylaniline. The high cost and low availability of asymmetric aniline derivatives, especially those containing branched alkyl substituents, such as anilines containing branched alkyl substituents, for example 2-isopropyl-6-methylaniline or 2-isopropyl-6-ethylaniline, are problems in the design and synthesis of novel CAAC ligands. Another problem is the long and complex synthetic routes of these and other aniline derivatives, where the desired products are obtained in low yields, significantly restricting the design options related to novel catalysts. These characteristics impose considerable limitations on the further development of organometallic catalysis based on ruthenium complexes with novel CAAC ligands. Obtaining novel catalysts for olefin metathesis using ligands based on asymmetric anilines, in particular, with planned properties, is difficult to implement in chemical synthesis and economically unjustifiable on an industrial scale.

[0012] In seeking novel ruthenium complexes having high catalytic activity and improved durability and selectivity that enable obtaining high TON values, it is important that these compounds be provided by a simple synthetic route based on readily available and inexpensive substrates. From an industrial scale perspective, it is also important that the planned synthesis be efficient at every stage and that the reaction products can be purified in a simple manner using techniques such as crystallization or distillation. It is also important to expand the library of ligands, the use of which will include alternative and / or improved structural sources of ruthenium complexes used as catalysts, namely in the ethenolysis reaction of fatty acid ester derivatives.

[0013] The low solubility of known ruthenium complexes in the nonpolar environment of the reaction (e.g., in paraffin, n - hexane, cyclohexane, n - heptane, n - decane, etc., or in many olefin metathesis substrates) is an equally important problem known in the art. Homogeneous metathesis reactions are usually carried out in polar media, in chlorinated solvents (dichloromethane, 1,2 - dichloroethane) or aromatic solvents (benzene, toluene), but these solvents are harmful to the environment and dangerous to users [Green Chem., 2014, 16, 1125 - 1130]. Therefore, alternative catalyst systems that can be used in solvents and whose use is compatible with the rules of "green chemistry" and the sustainable growth rules of modern large - scale chemical industries are being sought [R.A.Sheldon, Green Chem. 2017, 19, 18 - 43.]. It should also be noted that the solvents customarily used in olefin metathesis processes (dichloromethane, toluene, and benzene) are not acceptable by the pharmaceutical industry (where the removal of harmful solvents (classified as ICH class 1 and 2) is required at all stages of the synthesis of pharmaceutical active ingredients (APIs)) [Eur.J.Org.Chem. 2019, 640 - 646].

[0014] Furthermore, the solubility of known catalysts in some nonpolar monomers such as dicyclopentadiene (DCPD) and tricyclopentadiene (TCPD), or in n - olefins (including those obtained in the pyrolysis of polyethylene and polypropylene waste) is usually low, and it is important for the ruthenium complex to form a homogeneous system with the solvent.

[0015] In the art, there are clear technical problems related to the insufficient solubility of ruthenium complexes in nonpolar solvents, which pose limitations on the use of olefin metathesis processes in nonpolar environments (i.e., paraffin, vegetable oils, and others).

[0016] Surprisingly, it has been discovered that in a simple and efficient three-stage synthesis, the key stage of which is the synthesis of branched aniline derivatives in the aza-Claisen reaction, aniline derivatives having an alkyl, branched substituent can be easily obtained. The aniline derivatives obtained through this synthesis, and other similar organic compounds, can act as substrates for novel CAAC ligands used in the synthesis of ruthenium catalysts and / or (pre)catalysts for olefin metathesis. Summary of the Invention Means for Solving the Problems

[0017] Accordingly, the subject of this invention is a precursor of cyclic alkylamine carbene (CAAC) having the formula CAAC-1

Chemical formula

[0018] Preferably, the precursor of the cyclic alkylamine carbene (CAAC) is represented by formula CAAC-2 or CAAC-3 or CAAC-4

Chemical formula

[0019] Preferably, the precursor of the cyclic alkylamine carbene (CAAC) is represented by Formula CAAC - 5 or CAAC - 6 or CAAC - 7

Chemical formula

[0020] Preferably, the precursor of cyclic alkylamine carbene (CAAC) is of the formula CAAC-a, CAAC-b, CAAC-c, CAAC-d, CAAC-e, CAAC-f, CAAC-g, CAAC-h, CAAC-i, CAAC-j, CAAC-k, or CAAC-l:

Chemical formula

[0021] The subject of the present invention also includes the cyclic precursor of alkylamine carbene (CAAC) having the formula CAAC-2 or CAAC-3 defined above

Chemical formula

Chemical formula

[0022] Preferably, a Lewis acid selected from BF3, B(OR)3, AlCl3, MgCl2, TiCl4, Ti(OR)4 is used in the first step; in the second step, a reduction reaction is carried out in the presence of a catalyst selected from Pd, Pt, Rh, Ru, Ag, Au; in the third step, the reaction is carried out in the presence of a Brønsted acid selected from para-toluenesulfonic acid, sulfuric acid, hydrochloric acid, trifluoroacetic acid, trifluoromethanesulfonic acid, fluorosulfuric acid.

[0023] The subject of the present invention also relates to a ruthenium complex having formula 1-Ru [Chemical formula] comprising wherein: X 1 and X 2 are, independently of one another, a halogen anion, -CN, -SCN, -OR a 、-SR a, -O(C=O)R a , -O(SO2)R a , and -OSi(R a )3 group represents an anionic ligand selected from the group consisting of, where R a is at least one C1-C 12 alkyl, C1-C 12 perfluoroalkyl, C1-C 12 alkoxyl, C5-C 24 aryloxyl, C5-C 20 heteroaryloxyl, or C1-C optionally substituted with a halogen atom 12 alkyl, C3-C 12 cycloalkyl, C2-C 12 alkenyl, or C5-C 20 aryl; R 1 , R 2 , R 3 , R 4 , and R 5 are independently a hydrogen atom, a C1-C 12 alkyl group, a C3-C 12 cycloalkyl group, a C5-C 20 aryl group or a C5-C 20 heteroaryl group, a C5-C 25 aralkyl group, which may be a hydrogen atom, a halogen atom, a C1-C 12 alkyl group, a C1-C 12 perfluoroalkyl group, a C5-C 20 aryl group, a C5-C 20 perfluoroaryl group, a C5-C 20 heteroaryl group, a C1-C 12 alkoxy group, a C5-C 24 aryloxy group, a C5-C 20 heteroaryloxy group, a sulfide group (-SR''), an amine group (-NR''2), and may be independently substituted by one and / or more substituents selected from the group, where the R'' group is independently a hydrogen atom, a C1-C5 alkyl, a C6-C 24 aryl, a C7-C 24 aralkyl, or R 1 , R 2 , R3 , R 4 , and R 5 are linked to form a C5 - C 25 ring, wherein at least one substituent R 1 , R 2 , and R 5 has an alkyl substituent having at least one secondary, tertiary, or quaternary carbon atom, preferably, at least one substituent R 1 , R 2 , and R 5 has an alkyl substituent having at least two secondary, tertiary, or quaternary carbon atoms, more preferably, at least one substituent R 1 , R 2 , and R 5 has an alkyl substituent having at least three secondary, tertiary, or quaternary carbon atoms, most preferably, at least one substituent R 1 , R 2 , and R 5 has an alkyl substituent having at least four secondary, tertiary, or quaternary carbon atoms, each substituent R 6 , R 7 , R 8 , and R 9 represents a hydrogen atom, a halogen atom, an alkyl C1 - C 12 group, or a C5 - C 20 aryl group, and these are hydrogen, C1 - C 12 alkyl group, C1 - C 12 perfluoroalkyl group, 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 24 aryloxy group, C5 - C 20It may be independently substituted by one and / or more substituents selected from the group consisting of a heteroaryloxy group, or a halogen atom, a sulfide group (-SR''), and an amine group (-NR''2), where the R'' group is independently a hydrogen atom, C1-C5 alkyl, C6-C 24 aryl, C7-C 24 aralkyl, or R 6 and R 7 and / or R 8 and R 9 are linked to form a C5-C 25 ring group.

[0024] R 16 and R 17 are independently a hydrogen atom, a halogen atom, optionally substituted C1-C 25 alkyl, optionally substituted C3-C 25 cycloalkyl, optionally substituted C1-C 12 perfluoroalkyl, optionally substituted C2-C 25 alkene, optionally substituted C2-C 25 alkenyl, optionally substituted C3-C 25 cycloalkenyl, optionally substituted C2-C 25 alkynyl, 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; represents a 3- to 12-membered heterocyclic ring optionally containing sulfur, oxygen, nitrogen, selenium, or phosphorus atoms; wherein R 16 and R 17 substituents are linked and form a C3-C 25Cycloalkyl, C3-C 25 Cycloalkenyl, C3-C 25 Cycloalkynyl, C5-C 25 Aryl, C5-C 25 Heteroaryl, C5-C 25 Perfluoroaryl; may form a ring selected from the group containing a 3- to 12-membered heterocycle containing sulfur, oxygen, nitrogen, selenium, or phosphorus atoms, and these are hydrogen atoms, halogen atoms, C1-C 25 Alkyl, C3-C 25 Cycloalkyl, C1-C 12 Perfluoroalkyl, C2-C 25 Alkene, C2-C 25 Alkenyl, C3-C 25 Cycloalkenyl, C2-C 25 Alkynyl, C3-C 25 Cycloalkynyl, C1-C 25 Alkoxyl, C5-C 25 Aryl, C5-C 25 Aryloxyl, C6-C 25 Arylalkyl, C5-C 25 Heteroaryl, C5-C 25 Heteroaryloxyl, C5-C 25 Perfluoroaryl, may be independently substituted with one and / or more substituents selected from the group containing a 3- to 12-membered heterocycle; wherein the substituents R 16 and R 17 are independently and preferably a hydrogen atom and / or an aryl C5-C independently substituted with a hydrogen atom 25 halogen atom, C1-C 25 alkyl group, C2-C 25 alkenyl group, alkoxy group (-OR''), sulfide group (-SR''), sulfoxide group (-S(O)R''), sulfonium group (-S + R''2), sulfone group (-SO2R''), sulfonamide group (-SO2NR''2), amine group (-NR''2), ammonium group (-N +R’’3), nitro group (-NO2), cyanide 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), carboxy group (-COOH), ester group (-COOR’’), amide group (-CONR’’2), amide group (-NR’’C(O)R’’), formyl group (-CHO), ketone group (-COR’’), thioamide group (-CSNR’’2), thioketone group (-CSR’’), thionoester group (-CSOR’’), thioester group (-COSR’’), dithioester group (-CS2R’’), where here, the R’’ groups are independently a hydrogen atom, C1-C5 alkyl, C1-C5 perfluoroalkyl, C6-C 24 aryl, C7-C 24 aralkyl, C5-C 24 perfluoroaryl, and two R’’ groups are linked and contain a nitrogen, oxygen, or sulfur atom, optionally further substituted with a C1-C 12 alkyl group to form a C3-C 12 cycloalkyl or C3-C 25 heterocycloalkyl ring, or R’’ represents a ketone group (-COR c ), where R c is C1-C 12 perfluoroalkyl or an alkoxy group (-OR d ), where R d contains a nitrogen atom, oxygen atom, or sulfur atom and is optionally further substituted with a C1-C 12 alkyl group to form a C1-C 12 alkyl or C3-C 12 heterocycloalkyl; G is selected from entities such as the following - a ligand having formula CAAC-5 or CAAC-6 or CAAC-7

Chemical formula

[0025] The ruthenium complex is preferably of formula 1a-Ru [Chemical formula] represented by wherein X 1 and X 2 , and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 substituents have the meanings defined above; “n” means 1 or 0 Z is selected from the group consisting of a halogen atom, an O atom, an S atom, a Se atom, or an NR’’’ group, wherein R’’’ is methylidene, C1~C25 Alkyl, C1 - C 25 Perfluoroalkyl, C3 - C 25 Cycloalkyl, C5 - C 20 Alkoxyl, C5 - C 20 Aryl, C5 - C 20 Perfluoroaryl, C7 - C 20 Aralkyl, C5 - C 24 Aryloxyl, C2 - C 12 Alkenyl, C6 - C 20 Heteroaryl or C5 - C 24 Heteroaryloxyl, 3 - to 12 - membered heterocyclic ring, acyl group (-COR’), ester group (-COOR’), tert - butyl carboxy carbon group (t - Boc) or 9 - fluorenylmethoxycarbonyl group (Fmoc), carbamine group (-CONR’2), sulfone group (-SO2R’), formyl group (-COH), 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 Aralkyl, C5 - C 24 Aryloxyl, C2 - C 12 Alkenyl, C6 - C 20 Heteroaryl or C5 - C 24 Heteroaryloxyl, or represents a halogen atom. If Z represents a halogen atom in the formula, then R 18 is absent; R 18 is independently a halogen atom, C1 - C 25 Alkyl, C1 - C 25 Cycloalkyl, C5 - C 20 Alkoxyl, C5 - C 20 Aryl, C5 - C 24An aryloxy group, a -COOR''', -CH2COOR''', -CONR''2, -CH2CONR''2, -COR''', -CH2COR''', -CON(OR'')(R'''), -CH2CON(OR'')(R''') group, or a halogen atom, where R''' represents C1-C 12 alkyl, C3-C 12 cycloalkyl, C2-C 12 alkenyl, C6-C 20 aryl, which are optionally substituted with at least C1-C 12 alkyl, C1-C 12 perfluoroalkyl, C1-C 12 alkoxyl, C6-C 24 aryloxy, or a halogen atom; R 19 、R 20 、R 21 、and R 22 are independently a hydrogen atom, a halogen atom, a C1-C 25 alkyl group, a C2-C 25 alkenyl group, a C5-C 25 aryl group, an alkoxy group (-OR''), a sulfide group (-SR''), a sulfoxide (-S(O)R''), a sulfonium group (-S + R''2), a sulfone group (-SO2R''), a sulfonamide group (-SO2NR''2), an amine group (-NR''2), an ammonium group (-N + R''3), a nitro group (-NO2), a cyano group (-CN), a phosphonous acid group (-P(O)(OR'')2), a phosphinous acid group (-P(O)R''(OR'')), a phosphonin group (-P(OR'')2), a phosphine group (-PR''2), a phosphine oxide group (-P(O)R''2), a phosphonium group (-P +R’’3), carboxyl group (-COOH), ester group (-COOR’’), amide group (-CONR’’2), amide group (-NR’’C(O)R’), formyl group (-CHO), ketone group (-COR’’), thioamide group (-CSNR’’2), thioketone group (-CSR’’), thionoester group (-CSOR’’), thioester group (-COSR’’), dithioester group (-CS2R’’), where the R’’ group is C1-C5 alkyl, C1-C5 perfluoroalkyl, C6-C 24 aryl, C7-C 24 aralkyl, C5-C 24 perfluoroaryl, where R 16 , R 17 , R 18 , and R 19 substituents are linked and thus may form a substituted or unsubstituted C4-C 10 cyclic or C4-C 12 polycyclic system.

[0026] The ruthenium complex is preferably of formula 1b-Ru

Chemical formula

[0027] The ruthenium complex is preferably of formula 1c-Ru or 1d-Ru or 1e-Ru

Chemical formula

[0028] The ruthenium complex is preferably selected from the complexes represented by the formulas Ru-a, Ru-b, Ru-c, Ru-d, Ru-e, Ru-f, Ru-g, Ru-h, Ru-i, Ru-j, Ru-k, Ru-l:

Chemical formula

[0029] The present invention also relates to a method for the synthesis of a ruthenium complex having the formula 1a-Ru as defined above

Chemical formula

Chemical formula

Chemical formula

[0030] The subject of the present invention also includes the use of a compound having formula 1-Ru defined above as a pre-catalyst and / or catalyst in olefin metathesis reactions, in particular in diastereoselective ring-closing metathesis (DRRM) reactions, "alkene-alkyne" (en-yn) type metathesis, or ring-closing metathesis (RCM) reactions, cross-metathesis (CM), homometathesis (cross-metathesis between two molecules of the same olefin), ethenolysis, isomerization in ROMP or ADMET type polymerization reactions.

[0031] This reaction is preferably carried out in an organic solvent, such as toluene, mesitylene, hexane, cyclohexane, ethyl acetate, methyl acetate, methyl carbonate, ethyl carbonate, tert-butyl-methyl ether, cyclopentyl-methyl ether, diethyl ether, THF, 2-Me-THF, 4-Me-THP, dioxane, DME, PAO.PEG, paraffin, esters of saturated fatty acids.

[0032] This reaction is preferably carried out in a solvent-free system.

[0033] This reaction is preferably carried out at a temperature of 20 to 200 °C.

[0034] This reaction is preferably carried out over a period of 5 minutes to 48 hours.

[0035] The 1-Ru compound is preferably used in an amount of 10 mol% or less.

[0036] The 1-Ru compound is preferably used in an amount of 0.1 mol% or less.

[0037] The 1-Ru compound is preferably added to the reaction mixture as a solid in divided amounts and / or continuously using a pump as a solution in an organic solvent.

[0038] The gaseous by-products of the reaction, selected from ethylene, propylene, and butylene, are preferably actively removed from the reaction mixture using an inert gas barbotage or under reduced pressure.

[0039] The subject of the present invention also relates to a ruthenium complex represented by the formula 1aa-Ru

Chemical formula

[0040] The aforementioned ruthenium complex is preferably represented by Formula 1aaa-Ru

Chemical formula

[0041] The aforementioned ruthenium complex is preferably represented by Formula 1aaaa-Ru

Chemical formula

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

Brief Description of the Drawings

[0043]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Figure 7

Figure 8

Figure 9

Figure 10

Figure 11a

Figure 11b

Figure 12

Figure 13

Figure 14a

Figure 14b

Figure 15a

Figure 15b

Figure 16

MODE FOR CARRYING OUT THE INVENTION

[0044] The terms used in this disclosure have the following meanings.

[0045] Terms not defined in this document have the meanings provided and understood by those skilled in the art, taking into account the maximum retained knowledge, this disclosure, and the context of the disclosure of the patent application. Unless otherwise specified, the following conventions for chemical terms, having the meanings as provided in the following definitions, are used: The term "halogen atom" as used in this disclosure means an element selected from F, Cl, Br, and I.

[0046] The term "carbene" means an electrically neutral molecule in which the carbon atom has two non-bonding electrons in a singlet or triplet state and is linked to two groups via a single covalent bond or to a single group via a double covalent bond. The term "carbene" also includes carbene analogues in which the carbene carbon atom is replaced by a different chemical element such as boron, silicon, germanium, tin, lead, nitrogen, phosphorus, sulfur, selenium, or tellurium.

[0047] The term "alkyl" refers to a saturated straight-chain or branched hydrocarbon substituent having the indicated number of carbon atoms. Examples of alkyl substituents include -methyl, -ethyl, -n-propyl, -n-butyl, -n-pentyl, -n-hexyl, -n-heptyl, -n-octyl, -n-nonyl, and -n-decyl. Representative branched -(C1~C10) alkyls include -isopropyl, -sec-butyl, -isobutyl, -tert-butyl, -isopentyl, -neopentyl, -1-methylbutyl, -2-methylbutyl, -3-methylbutyl, -1,1-dimethylpropyl, -1,2-dimethylpropyl, -1-methylpentyl, -2-methylpentyl, -3-methylpentyl, -4-methylpentyl, -1-ethylbutyl, -2-ethylbutyl, -1,1-dimethylbutyl, -1,2-dimethylbutyl, -1,3-dimethylbutyl, -2,2-dimethylbutyl, -2,3-dimethylbutyl, -3,3-dimethylbutyl, -1-methylhexyl, -2-methylhexyl, -3-methylhexyl, -4-methylhexyl, -1,2-dimethylpentyl, -1,3-dimethylpentyl, -5-methylhexyl, -1,2-dimethylhexyl, -1,3-dimethylhexyl, -3,3-dimethylhexyl, -1,2-dimethylheptyl, -1,3-dimethylheptyl, -3,3-dimethylheptyl, and the like.

[0048] The term "alkoxyl" refers to an alkyl substituent as defined above, linked via an oxygen atom.

[0049] The term "perfluoroalkyl" represents an alkyl group as defined above in which all hydrogen atoms therein are replaced by the same or different halogen atoms.

[0050] The term "cycloalkyl" refers to a saturated monocyclic or polycyclic hydrocarbon substituent having the indicated number of carbon atoms. Examples of cycloalkyl substituents include -cyclopropyl, -cyclobutyl, -cyclopentyl, -cyclohexyl, -cycloheptyl, -cyclooctyl, -cyclononyl, -cyclodecyl, and the like.

[0051] The term "alkenyl" refers to an unsaturated straight-chain or branched cyclic hydrocarbon substituent having the indicated number of hydrogen atoms and containing at least one double carbon-carbon bond. Examples of alkenyl substituents include -vinyl, -allyl, -1-butenyl, -2-butenyl, -isobutenyl, -1-pentenyl, -2-pentenyl, -3-methyl-1-butenyl, -2-methyl-2-butenyl, -2,3-dimethyl-2-butenyl, -1-hexenyl, -2-hexenyl, -3-hexenyl, -1-heptenyl, -2-heptenyl, -3-heptenyl, -1-octenyl, -2-octenyl, -3-octenyl, -1-nonenyl, -2-nonenyl, -3-nonenyl, -1-decenyl, -2-decenyl, -3-decenyl, and the like.

[0052] The term "cycloalkenyl" refers to an unsaturated, cyclic or branched, cyclic hydrocarbon substituent having the indicated number of hydrogen atoms and containing at least one double carbon-carbon bond. Examples of cycloalkenyl substituents include -cyclopropene, -cyclobutene, -cyclopentene, -cyclohexene, -cycloheptene, -cyclooctene, -cyclononene, -cyclodecene, -methylcyclopropene, -ethylcyclobutene, -isopropylcyclopentene, -methylcyclohexene, and the like.

[0053] The term "aryl" refers to an aromatic monocyclic or polycyclic hydrocarbon substituent having the indicated number of carbon atoms. Examples of aryl substituents include -phenyl, -tolyl, -xylyl, -naphthyl, -2,4,6-trimethylphenyl, -2-fluorophenyl, -4-fluorophenyl, -2,4,6-trifluorophenyl, -2,6-difluorophenyl, -4-nitrophenyl, and the like.

[0054] The term "aralkyl" refers to an alkyl substituent as defined above substituted with at least one aryl as defined above. Examples of aralkyl substituents include -benzyl, -diphenylmethyl, -triphenylmethyl, and the like.

[0055] The term "heteroaryl" refers to an aromatic monocyclic or polycyclic hydrocarbon substituent having the indicated 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, -azaindolyl, -quinolyl, -isoquinolyl, -carbazolyl, and the like.

[0056] The term "heterocyclic ring" refers to a saturated, unsaturated, or partially unsaturated hydrocarbon substituent having the indicated number of carbon atoms, in which at least one carbon atom therein 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, -pyrolidinonyl, -pyrrolidinyl, -hydantoinyl, -oxiranyl, -oxetanyl, -tetrahydrofuranyl, -tetrahydrothiophenyl, -quinolinyl, -isoquinolinyl, -chromonyl, -coumarinyl, -indolyl, -indolysinyl, -benzo[b]furanyl, -benzo[b]thiophenyl, -indazolyl, -purinyl, -4H-quinolysinyl, -iso-quinolyl, -quinolyl, -phtalasinyl, -naphthyridinyl, -carbazolyl, -β-carbolynyl, and the like.

[0057] The term "neutral ligand" refers to an uncharged substituent capable of coordinating to a metal center (transition metal atom). Examples of such ligands can include N-heterocyclic carbenes (NHCs), cyclic (alkyl)(amine)carbenes (CAACs), amines, phosphines and their oxides, alkyl and aryl phosphites and phosphates, arsines and their oxides, ethers, alkyl and aryl sulfides, coordinated unsaturated or aromatic hydrocarbons, alkyl and aryl halides, nitriles, isonitriles, sulfides, sulfoxides, sulfones, thioketones, thioamides, thioesters, thionoesters, and dithioesters.

[0058] The term "anionic ligand" refers to a substituent capable of coordinating to a charged metal center (transition metal atom) that can partially or completely cancel the charge of the metal center. Examples of such ligands include fluoride, chloride, bromide, iodide, cyanide, cyanate and thiocyanate anions, carboxylate anions, alcohol anions, phenolate anions, thiol and thiophenolate anions, anions of hydrocarbons having delocalized charges (e.g., cyclopentadienyl anion), anions of (organo)sulfuric and (organo)phosphoric acids and their esters (e.g.,..., anions of alkylsulfonic and arylsulfonic acids, anions of alkylphosphoric and arylphosphoric acids, anions of alkyl and aryl esters of sulfuric acid, anions of alkyl and aryl esters of phosphoric acid, anions of alkyl and aryl esters of alkylphosphoric and arylphosphoric acids) may be included.

[0059] The term "heteroatom" means an atom selected from the group including oxygen, sulfur, nitrogen, phosphorus, boron, silicon, arsenic, selenium, tellurium.

[0060] Embodiment examples of the present invention The following examples are not intended to limit the present invention, but are provided only to illustrate the present invention and to explain its individual aspects, and should not be construed as defining the entire scope thereof as defined in the appended claims. Unless otherwise specified, the following examples used standard materials and methods used in the art or followed the manufacturer's recommendations for specific reagents and methods.

[0061] If necessary, the model compound for the metathesis reaction was purified using fractional distillation and then stored under an inert gas atmosphere through activated neutral aluminum oxide. Tetrahydrofuran was purified by distillation through a sodium - potassium alloy in the presence of benzophenone and then stored through a 4 Å molecular sieve. If appropriate, the selected reaction was carried out under an argon atmosphere using a reaction vessel heated at 130 °C. Aluminum oxide (Al2O3, neutral, Brockman grade I) was activated by heating at 150 °C for 16 hours under reduced pressure.

[0062] The starting compounds for the synthesis of the novel aniline derivatives were available as commercial products.

Example

[0063] Example I Synthesis of novel anilines having branched alkyl substituents using the aza - Claisen method Scheme 1 above illustrates the synthesis of CAAC ligand precursors (general formula from Ru - a to Ru - l in Figure 1) that enable the obtaining of ruthenium catalysts for olefin metathesis, which includes the subject matter of this invention. The reactions R - 1 to R - 2, R - 1' to R - 3', and R - 1'' to R - 3'' shown in Scheme 1 were carried out using commercially available substrates according to procedures described in the literature (including modifications developed by the author). Unless otherwise specified, these described reactions used commercially available solvents and the presence of oxygen and / or moisture was not considered. The individual conversions described in Scheme 1 are shown below.

Chemical formula

[0064] Reactions R - 1 to R - 2 The synthesis of the imine having the general formula b is carried out in the R-1 stage (Scheme 1). Aniline having the general formula a' and an aldehyde, preferably crotonaldehyde, are used for this purpose. This conversion is preferably carried out in methylene chloride (DCM) or other organic solvents using a stoichiometric amount of a desiccant, preferably magnesium sulfate (MgSO4). The reaction is carried out at room temperature (RT). The product is separated from the reaction mixture via filtration and solvent distillation.

[0065] In the R-2 stage, the crude product is dissolved in an organic solvent, preferably methanol (MeOH), and a reducing agent, preferably sodium borohydride (NaBH4), is added at 0 °C. The reaction is carried out at room temperature for 16 hours under an argon atmosphere. The product is separated via extraction with a water / n-hexane mixture.

[0066] Embodiment Examples R-1 to R-2

Chemical formula

[0067] An imine from the previous stage and 500 mL of MeOH were introduced into a reaction vessel containing a stir bar under argon. For the reaction, NaBH4 was added in portions at 0 °C. The reaction was carried out at room temperature for 16 h. The solvent was evaporated under reduced pressure. Next, the mixture was dissolved in n-hexane, transferred to a separatory funnel, water was added, and extraction was performed 3 times using n-hexane. The combined organic layers were dried over anhydrous MgSO4, filtered through a layer of neutral celite, and the solvent was evaporated under reduced pressure. This afforded the expected product in the form of a brown liquid in 78% yield (45.1 g, 0.28 mol). 1 1H NMR (400 MHz, CDCl3) δ ppm: 6.97 - 6.93 (m, 1H), 6.93 - 6.90 (m, 1H), 6.56 (d, J = 8 Hz, 1H), 5.80 - 5.60 (m, 2H), 3.75 - 3.70 (m, 2H), 3.42 (bs, 1H), 2.25 (s, 3H), 2.14 (s, 3H), 1.74 (dq, J = 6.2, 1.3 Hz, 3H). 13 13C NMR (100 MHz, CDCl3) δ ppm: 144.0, 131.0, 128.5, 127.9, 127.4, 126.2, 122.3, 110.3, 46.4, 20.5, 17.9, 17.6.

[0068] Reaction R-1’ The synthesis of the imine having the general formula c’ is carried out in the R-1’ stage (Scheme 1). An aniline having the general formula a’ and an alkyl halide, preferably bromide, chloride, or iodide, is used for this purpose. This conversion is preferably carried out in N,N-dimethylformamide (DMF) or in a different organic solvent. The reaction mixture is maintained at room temperature. The product is separated from the reaction mixture via filtration, solvent distillation, and column chromatography [Chem. Commun., 2013, 49, 4346].

[0069] Embodiment Example R-1’

Chemical formula

[0070] Reaction R-1'-substitution method The synthesis of the imine having the general formula c’ is carried out at the R-1’ stage (Scheme 1). Aniline having the general formula a’ and an alkyl halide, preferably bromide, chloride, or iodide, is used for this purpose. This conversion is preferably carried out in acetonitrile (MeCN) or in a different organic solvent in the presence of an inorganic salt, preferably potassium carbonate (K2CO3). The reaction is carried out at 60 °C. The product is separated from the reaction mixture via filtration, solvent distillation, and column chromatography [Angew. Chem. Int. Ed. 2019, 58, 4700].

[0071] Alternative embodiment R-1’ [Chemical formula] Scheme 1.2b To a reaction vessel equipped with a stir bar containing a solution of o-toluidine (18.8 g, 18.6 mL, 0.14 mol, 3.5 eq) in acetonitrile (MeCN) (50 mL), crotyl bromide (8.1 g, 6.2 mL, 0.05 mol, 1 eq), and K2CO3 (14 g, 0.10 mol, 2 eq) were added dropwise at room temperature. The reaction mixture was heated at 60 °C for 16 h. The reaction was monitored using TLC. At the end of the reaction, water (50 mL) and diethyl ether (Et2O) (50 mL) were added to the reaction mixture, which was extracted with diethyl ether (2 × 20 mL), the organic layer was washed with water (2 × 20 mL), dried over anhydrous Na2SO4, filtered, and the solvent was evaporated under reduced pressure. The crude product was purified using column chromatography on silica gel using n-hexane as the eluent to obtain a pale yellow oil in 45% yield (3.6 g, 22.3 mmol) [Chem. Commun., 2013, 49, 4346 - 4348]. 1 H NMR (400 MHz, CDCl3) δ ppm: 7.22 - 7.20 (m, 2H), 6.75 - 6.63 (m, 2H), 5.86 - 5.45 (m, 2H), 3.90 - 3.72 (m, 2H), 3.54 (s, 1H), 2.18 (s, 3H), 1.77 (m, 3H). 1313C NMR (100 MHz, CDCl3) δ ppm: 146.2, 130.1, 128.2, 128.0, 127.2, 122.0, 117.0, 110.0, 46.0, 17.9, 17.6.

[0072] Reaction R-2’ The aza-Claisen rearrangement leading to aniline having the general formula d’ is carried out at the R2’ stage (Scheme 1). Aniline having the general formula c’ and a Lewis acid, preferably boron trifluoride etherate, are used for this purpose. This reaction is preferably carried out in chlorobenzene, o-xylene, or other organic solvents. This reaction is carried out under reflux. The product was purified via filtration, solvent distillation, and column chromatography. [Chem. Commun., 2013, 49, 4346].

[0073] Embodiment Example R-2’

Chemical formula

[0074] Alternative Embodiment R-2’’

Chemical Structure

[0075] Alternative Embodiment R-2’’ [Chemical formula] Scheme 1.3c To a reaction vessel equipped with a stir bar containing a solution of N-2-butenyl-2,4-dimethylaniline (54.3 g, 0.26 mol, 1 equiv) in o-xylene (467 mL), boron trifluoride etherate (41.3 mL, 0.33 mol, 1.3 equiv) was slowly added dropwise and the mixture was heated at reflux for 12 h. The mixture was then cooled to room temperature, saturated NaHCO3 solution was added, the aqueous layer was extracted with EtOAc, and the combined organic fractions were washed successively with water (25 mL) and brine (25 mL), then dried over Na2SO4, filtered, and the solvent was evaporated. The crude product was purified by distillation to give a colorless oil in >99% yield (45 g, 0.26 mol). 1 1H NMR (400 MHz, CDCl3) δ ppm: 6.82 (d, J = 0.7 Hz, 2H), 6.02 - 5.92 (m, 1H), 5.13 (dt, J = 6.5, 1.6 Hz, 1H), 5.11 - 5.09 (m, 1H), 3.58 (bs, 2H), 3.54 - 3.43 (m, 1H), 2.25 (s, 3H), 2.18 (s, 3H), 1.41 (d, J = 7.0 Hz, 3H). 13 13C NMR (100 MHz, CDCl3) δ ppm: 142.6, 140.0, 129.3, 128.5, 127.4, 125.6, 122.8, 113.8, 38.5, 20.7, 19.0, 17.9.

[0076] Reaction R-3’ The hydrogenation reaction of the unsaturated C=C bond to yield aniline having the general formula e’ is carried out at the R-3’ stage (Scheme 1). Aniline having the general formula d’, a catalyst, preferably Pd / C, and hydrogen gas are used for this purpose. This reaction is preferably carried out in methanol or other organic solvents. The reaction is carried out at room temperature. The product is separated from the reaction mixture via filtration, solvent distillation and distillation, or column chromatography. [Chemical Formula] Scheme 1.4

[0077] Embodiment Example R-3’ To a reaction vessel equipped with a stir bar containing a solution of aniline (1.91 g, 13 mmol, 1 equiv) in MeOH (50 mL), Pd / C (0.14 g, 0.13 mmol, 0.01 equiv, 10 wt%) was added. The reaction flask was purged with hydrogen and the reaction was carried out at room temperature for 16 h in a H2 atmosphere (1 atm). Next, the reaction mixture was filtered through celite and the filtrate was concentrated. The crude product was purified by distillation under reduced pressure. A yellow oil was obtained in 89% yield (1.73 g, 11.6 mmol). [Eur. J. Med. Chem., 2019, 176, 162 - 174] 1 H NMR (400 MHz, CDCI3) δ ppm: 6.95 (d, J = 7.5, Hz, 2H), 6.68 (t, J = 7.5 Hz, 1H), 3.72 (brs., 2H), 2.50 (t, J = 7.5, Hz, 2H), 2.20 (s, 3H), 1.72 - 1.61 (m, 2H), 1.02 (t, J = 7.3 Hz, 3H). 13 C NMR (100 MHz, CDCI3) δ ppm: 142.1, 128.2, 127.3, 126.2, 122.2, 118.1, 33.7, 21.9, 17.8, 14.3.

[0078] Alternative Embodiment R-3’ [Chemical Formula] Scheme 1.4b To a reaction vessel equipped with a stir bar containing a solution of aniline (0.8 g, 5 mmol, 1 equiv) in MeOH (30 mL), Pd / C (0.05 g, 0.05 mmol, 0.01 equiv, 10 wt%) was added. The reaction flask was purged with hydrogen and the reaction was carried out at room temperature for 16 h in a H2 atmosphere (1 atm). The reaction mixture was filtered through celite and the filtrate was concentrated. The crude product was purified using column chromatography with n-hexane as the eluent to afford a yellow oil in 75% yield (0.61 g, 3.74 mmol). 1 1H NMR (400 MHz, CDCl3) δ ppm: 6.99 (d, J = 7.7 Hz, 1H), 6.94 (d, J = 7.7 Hz, 1H), 6.72 (t, J = 7.7 Hz, 1H), 3.63 (s, 2H), 2.71 - 2.60 (m, 1H), 2.20 (s, 3H), 1.77 - 1.51 (m, 2H), 1.24 (d, J = 7.0 Hz, 3H), 0.92 (t, J = 7.3 Hz, 3H). 13 13C NMR (100 MHz, CDCl3) δ ppm: 141.9, 131.2, 127.9, 124.0, 22.4, 118.4, 34.9, 29.6, 20.3, 18.2, 12.4.

[0079] Alternative Embodiment R-3’

Chemical Structure

[0080] Reaction R-1’’ The synthesis of bis-alkylated aniline having the general formula c’’ is carried out in the R-1’’ stage (Scheme 1). Aniline having the general formula a’ and an alkyl halide, preferably bromide, chloride, or iodide, is used for this purpose. This conversion is preferably carried out in DMF or in a different organic solvent in the presence of a base, preferably triethylamine. The reaction is carried out at 0 °C to room temperature. The product is separated from the reaction mixture via filtration, solvent distillation, and column chromatography.

[0081] Embodiment Example R-1’’ [Chemical formula] Scheme 1.2b A solution containing aniline (6.9 g, 6.8 mL, 75 mmol, 1.5 equiv) and triethylamine (3.2 g, 4.4 mL, 31.4 mmol, 0.63 equiv) in DMF (25 mL) was placed in a reaction vessel equipped with a stir bar, and allyl bromide (6.2 g, 4.5 mL, 50 mmol, 1 equiv) was added dropwise at 0 °C. The contents of the flask were stirred at room temperature for 5 h. The reaction was monitored using TLC. At the end of the reaction, water (50 mL) and EtOAc (50 mL) were added to the mixture, stirred for 5 min, and the layers were separated. The aqueous layer was extracted with EtOAc (2 × 25 mL). The combined organic layers were washed with water (2 × 30 mL) to remove traces of DMF, dried over anhydrous Na2SO4, filtered, and the solvent was evaporated under reduced pressure. The crude product was purified using column chromatography and n-hexane:EtOAc (99:1) as the eluent to obtain a pale yellow oil in 35% yield (3.05 g, 17.6 mmol) [Synlett 2008,19,3011-3015].

[0082] Reaction R-2’’ The aza-Claisen rearrangement to afford aniline having the general formula d’ is carried out at the R2’’ stage (Scheme 1). Aniline having the general formula c’’ and a Lewis acid, preferably boron trifluoride etherate, are used for this purpose. This reaction is preferably carried out in chlorobenzene, o-xylene, or other organic solvents. This reaction is carried out under reflux. The product is separated from the reaction mixture via filtration, solvent distillation, and column chromatography.

[0083] Embodiment Example R-2’’

Chemical formula

[0084] Reaction R-3’’ The hydrogenation reaction of the unsaturated C=C bond to give an aniline having the general formula e’’ is carried out in the R-3’ stage (Scheme 1). An aniline having the general formula d’’, a catalyst, preferably Pd / C, and hydrogen gas are used for this purpose. This reaction is preferably carried out in methanol or other organic solvents. The reaction is carried out at room temperature. The product is separated from the reaction mixture via filtration, solvent distillation and distillation, or column chromatography.

[0085] Embodiment Example R-3’’ [Chemical formula] Scheme 1.4a A reaction vessel equipped with a stir bar containing a solution of aniline (1.11 g, 6.4 mmol, 1 equiv) in MeOH (50 mL) was added with 10 wt% Pd / C (0.09 g, 0.08 mmol, 0.01 equiv, 10 wt%). The reaction flask was purged with hydrogen and the reaction was carried out at room temperature for 16 h in a H2 atmosphere (1 atm). The reaction mixture was filtered through celite and the filtrate was concentrated. The crude product was purified by distillation under reduced pressure. A colorless oil was obtained in 74% yield (0.84 g, 4.7 mmol) [Eur.J.Med.Chem.,2019,176,162-174]. 1 1H NMR (400 MHz, CDCI3) δ ppm: 6.97 (d, J = 7.5 Hz, 2H), 6.73 (t, J = 7.5 Hz, 1H), 3.64 (bs, 2H), 2.51 (t, J = 7.5 Hz, 4H), 1.75 - 1.63 (m, 4H), 1.04 (t, J = 7.4 Hz, 6H). 13 13C NMR (100 MHz, CDCI3) δ ppm: 141.8, 127.2, 126.5, 118.0, 33.8, 21.9, 14.3.

[0086] Example II Aldehyde synthesis Scheme 2 shown below illustrates the synthesis of aldehydes (general formulas Ru-a to Ru-l, Scheme 10) used as building blocks for the synthesis of CAAC ligands that enable the obtaining of ruthenium catalysts for olefin metathesis, which includes the subject matter of this invention.

[0087] Reaction R4 shown in Scheme 2 was carried out using commercially available substrates according to the procedures described in the literature (including modifications devised by the author). Unless otherwise described, these described reactions used commercially available solvents and the presence of oxygen and / or moisture was not considered.

Chemical formula

[0088] Reaction R-4 In the R-4 stage (Scheme 2), an aldehyde alkylation reaction is carried out to afford an aldehyde having the general formula g under PTC conditions. An alkyl halide having the general formula f, preferably an alkyl chloride, bromide, iodide, a base, preferably sodium hydroxide (NaOH) and a PTC catalyst, preferably tert-butylammonium bromide, are used for this purpose. This reaction is preferably carried out in a mixture of toluene (PhMe) and water. This reaction is carried out at 60 °C. The product is separated from the reaction mixture via filtration, solvent distillation, and distillation under reduced pressure.

[0089] Embodiment Example R4

Chemical Formula

[0090] Alternative Embodiment R-4 [Chemical Formula] Scheme 3b To a round-bottomed three-necked flask equipped with a reflux condenser, a dropping funnel, and a stir bar, NaOH (2.25 g, 38.0 mmol, 1.50 equiv), (n-Bu)4NBr (1.21 g, 3.7 mmol, 10 mol%), 5 mL of distilled water, and 30 mL of PhMe were added. The mixture was heated to 60 °C, and a mixture of 2-(4-isobutylphenyl)propionaldehyde (7.15 g, 37.6 mmol, 1.00 equiv) and 3-chloro-2-methylpropene (4.67 g, 5.65 mL, 56 mmol, 1.4 equiv) was added. The reaction was carried out at 60 °C for 5 h. After cooling to room temperature, 30 mL of distilled water was added, and then the reaction mixture was extracted with PhMe. The organic layers were combined, dried over anhydrous Na2SO4, the precipitate was filtered off, and the solvent was evaporated. The crude product was distilled under reduced pressure to give a colorless liquid in 55% yield (5.0 g, 20.5 mmol). 1 1H NMR (400 MHz, CDCl3): δ ppm 9.52 (s, 1H), 7.22 - 7.11 (m, 4H), 4.83 - 4.77 (m, 1H), 4.66 - 4.59 (m, 1H), 2.75 - 2.58 (m, H), 2.46 (d, J = 7.3 Hz, 2H), 1.92 - 1.77 (m, 1H), 1.45 (s, 3H), 1.41 - 1.36 (m, 3H), 0.89 (d, J = 6.6 Hz, 6H). 13 13C NMR (101 MHz, CDCl3): δ ppm 202.2, 129.6, 129.4, 129.2, 128.5, 128.4, 127.2, 53.3, 45.0, 44.3, 30.3, 24.2, 22.5, 18.6.

[0091] Another Alternative Embodiment R-4 [Chemistry] Scheme 2c To a round-bottomed three-necked flask equipped with a reflux condenser, a dropping funnel, and a stir bar, NaOH (4.16 g, 0.10 mol, 1.50 eq), (n-Bu)4NBr (2.24 g, 6.93 mmol, 10 mol%), 14 mL of distilled water, and 93 mL of toluene were added. The mixture was heated to 60 °C, and a mixture of 2-methylpropionaldehyde (5.0 g, 6.3 mL, 69.3 mmol, 1.00 eq) and 3-chloro-2-methylpropene (8.6 g, 9.3 mL, 92.2 mmol, 1.33 eq) was added. The reaction was carried out at 60 °C for 22 h. After cooling to room temperature, 90 mL of distilled water was added, and then the product was extracted with toluene. The organic layers were combined and dried over anhydrous Na2SO4. The precipitate was filtered off. The product was used in the next step as a toluene solution without further purification.

[0092] Example IIIa Synthesis of the CAAC Ligand Precursor The following Scheme 3 illustrates the synthesis of a CAAC ligand (the general formula of the CAAC ligand precursor is shown in Scheme 3) that enables the preparation of a ruthenium catalyst for olefin metathesis, which includes the subject matter of this invention.

[0093] Reactions R-5 and R-6 shown in Scheme 3 were carried out using commercially available compounds according to procedures described in the literature (including modifications devised by the author). Unless otherwise stated, these described reactions were carried out using commercially available solvents, and the presence of oxygen and / or moisture was ignored. [Chemistry] Scheme 3

[0094] Reactions R-5, R-6, R-5', and R-6' During step R-5 or R-5’ (Scheme 3), in the presence of trifluoroacetic acid, preferably para-toluenesulfonic acid, aniline having the general formula of e’ or e’’ and aldehyde having the general formula g were used for this purpose to carry out the synthesis of h’ or h’’ imine. This reaction is preferably carried out in PhMe or different organic solvents. The reaction mixture is stirred under reflux. The product is separated by filtration through neutral Al2O3 and solvent distillation. The product was used in the next step without further purification.

[0095] During step R-6 or R-6’, the synthesis of the CAAC ligand precursor having the general formula i’ or i’’ is carried out using the imine having the general formula h’ or h’’ obtained in step R-5 or R-5’ in the presence of trifluoroacetic acid, preferably 4N hydrochloric acid in dioxane. This reaction is carried out at 85 °C in toluene under a protective argon atmosphere. Next, the chloride ion is replaced with the tetrafluoroborate ion, and the crude product is precipitated from the MeOH / Et2O mixture.

[0096] Embodiment examples of the present invention

Chemical formula

[0097] Into a round-bottom flask, under a protective argon atmosphere, the imine from the previous step, 4M HCl (2.23 g, 2.27 mL, 9.06 mmol, 2.5 eq) (solution in dioxane and PhMe (concentration C = 0.50 M)) was added. The reaction was carried out at 85 °C for 16 h. The solvent was evaporated under reduced pressure. The crude product was dissolved in a water / methylene chloride mixture, NaBF4 (0.80 g, 7.25 mmol) was added, and ion exchange was carried out for 2 h. The organic fraction was collected, washed with water, and dried over anhydrous sodium sulfate. The product was precipitated from a MeOH:Et2O mixture, giving colorless crystals in 75% yield (1.19 g, 2.7 mmol). 1 H NMR (400 MHz, CDCl3): δ ppm δ 9.50 (s, 1H), 7.54 - 7.49 (m, 2H), 7.47 - 7.38 (m, 3H), 7.37 - 7.31 (m, 1H), 7.30 - 7.26 (m, 1H), 7.24 - 7.20 (m, 1H), 3.22 (d, J = 14.1 Hz, 1H), 2.67 (d, J = 14.1 Hz, 1H), 2.59 - 2.38 (m, 2H), 2.36 - 2.23 (m, 1H), 2.11 - 1.99 (m, 1H), 1.92 (s, 3H), 1.80 - 1.41 (m, 7H), 1.33 (s, 3H), 0.97 (t, J = 7.3 Hz, 3H), 0.71 (t, J = 7.3 Hz, 3H). 13 C NMR (101 MHz, CDCl3): δ ppm 189.6, 140.4, 138.6, 138.0, 131.2, 131.0, 130.1, 128.6, 128.4, 128.2, 125.9, 84.0, 55.6, 48.3, 34.3, 34.1, 29.2, 27.1, 6.9, 25.0, 24.1, 14.4, 14.1.

[0098] Alternative embodiments of the present invention

Chemical formula

[0099] Into the round-bottom flask, under a protective argon atmosphere, the imine from the previous step and 4M HCl (2.43 g, 3.33 mL, 13.3 mmol, 2.5 equiv) (a solution in dioxane and PhMe (concentration C = 0.50 M)) were added. The reaction was carried out at 85 °C for 16 h. The solvent was evaporated under reduced pressure. The crude product was dissolved in a water / methylene chloride mixture, NaBF4 was added (1.17 g, 10.6 mmol, 2.0 equiv), and ion exchange was carried out for 2 h. The organic fraction was collected, washed with water, and dried over anhydrous sodium sulfate. The product was precipitated from a MeOH:Et2O mixture, giving colorless crystals in 61% yield (1.51 g, 3.3 mmol). 1 H NMR (400 MHz, CDCl3): δ ppm 9.52 (s, 0.67×1H), 9.47 (s, 0.33×1H), 7.47 - 7.30 (m, 4H), 7.25 - 7.15 (m, 3H), 3.25 - 3.12 (m, 1H), 2.74 - 2.61 (m, 2H), 2.51 - 2.42 (m, H), 2.39 - 2.23 (m, 2H), 2.07 (s, 2H), 1.96 (s, 1H), 1.92 - 1.79 (m, 3H), 1.61 (s, 1H), 1.55 (s, 2H), 1.41 - 1.33 (m, 5H), 1.21 - 1.13 (m, 3H), 0.97 (d, J =.7 Hz, 1H), 0.92 - 0.85 (m, 6H). 1313C NMR (101 MHz, CDCl3): δ ppm 189.4, 140.7, 139.7, 139.2, 131.3, 130.6, 129.8, 128.3, 127.8, 127.6, 125.6, 83.9, 55.4, 48.0, 28.9, 26.9, 26.6, 24.9, 24.6, 15.4, 14.6.

[0100] Alternative Embodiment of the Present Invention [Chemical Formula] Scheme 3.3 In a round-bottom flask equipped with a magnetic stirrer, 2,4-dimethyl-2-phenylpent-4-enal (1.00 g, 5.3 mmol, 1.00 equiv), aniline (1.10 g, 5.3 mmol, 1.00 equiv), and PTSA (10 mg, 0.05 mmol, 1 mol%) were added and dissolved in PhMe (C = 0.30 M). The reaction was carried out at reflux until complete conversion of the substrate (while collecting water in a Dean-Stark apparatus). The solvent was evaporated under reduced pressure, and the crude reaction mixture was filtered through neutral aluminum oxide (Al2O3, Brockman grade I) and dried in vacuo. The imine used in the next step without further purification was obtained in 98% yield (1.95 g, 5.2 mmol).

[0101] In a round-bottom flask under a protective argon atmosphere, the imine from the previous step and 4M HCl (6.90 g, 6.57 mL, 26.3 mmol, 2.5 equiv) (a solution in dioxane and PhMe (C = 0.50 M)) were added. The reaction was carried out at 85 °C for 16 h. The solvent was evaporated under reduced pressure. The crude product was dissolved in a water / methylene chloride mixture, NaBF4 was added (2.31 g, 21.0 mmol, 2.0 equiv), and ion exchange was carried out for 2 h. The organic fraction was collected, washed with water, and dried over sodium sulfate. The product was precipitated from a MeOH:Et2O mixture, giving colorless crystals in 72% yield (1.73 g, 3.7 mmol).

[0102] Another Alternative Embodiment of the Present Invention [Chemical Formula] Scheme 3.4 Into a round-bottom flask equipped with a stir bar, 2,2,4-trimethylpent-4-enal (1.01 g, 8.0 mmol, 1.00 equiv), aniline (2.0 g, 9.6 mmol, 1.2 equiv), and PTSA (15 mg, 0.05 mmol, 1 mol%) were added and dissolved in toluene (C = 0.30 M). This reaction was carried out at reflux until total conversion of the substrate (while collecting water in a Dean–Stark apparatus). The solvent was evaporated under reduced pressure, and the crude reaction mixture was filtered through neutral aluminum oxide (Al2O3, Brockman grade I) and dried in vacuo. The imine used in the next step without further purification was obtained in 99% yield (2.5 g, 8.0 mmol).

[0103] Into a round-bottom flask, under a protective argon atmosphere, the imine from the previous step, 4M HCl (5.13 g, 4.98 mL, 19.9 mmol, 2.5 equiv) (a solution in dioxane and toluene (C = 0.50 M)) were added. The reaction was carried out at 85 °C for 16 h. The solvent was evaporated under reduced pressure. The crude product was dissolved in a water / methylene chloride mixture, NaBF4 was added (1.75 g, 15.9 mmol, 2.0 equiv), and ion exchange was carried out for 2 h. The organic fraction was collected, washed with water, and dried over anhydrous sodium sulfate. The product was precipitated from a MeOH:Et2O mixture, giving colorless crystals in 25% yield (0.8 g, 2.0 mmol). 1 H NMR (400 MHz, CDCl3): δ ppm δ 8.85 (s, 1H), 7.67 (d, J = 8.6 Hz, 1H), 7.58 (dd, J = 2.1, 8.7 Hz, 1H), 7.00 (d, J = 2.1 Hz, 1H), 2.47 (d, J = 13.8 Hz, 1H), 2.31 (d, J = 13.8 Hz, 1H), 1.72 (s, 3H), 1.64 (s, 3H), 1.53 (s, 3H), 1.48 (s, 3H), 1.37 (s, 9H), 1.32 (s, 9H). 1313C NMR (101 MHz, CDCl3): δ ppm 189.8, 150.7, 141.8, 131.9, 131.2, 128.8, 124.2, 83.0, 49.1, 47.7, 37.6, 34.6, 33.8, 30.9, 30.9, 27.0, 25.6, 25.6.

[0104] Using the reactions R-6 and R-6' shown above, the following compounds having the general formula of the CAAC ligand precursor were obtained.

Chemical formula

[0105] Example IIIb Synthesis of NHC Ligand Precursor The following scheme illustrates the synthesis of NHC ligands (General Formulas I to IV, Syntheses I to III) that enable the synthesis of olefin metathesis ruthenium catalysts, including the subject matter of this invention.

Chemical formula

[0106] Synthesis I To a reaction vessel equipped with a stir bar containing a solution of 2-(sec-butyl)-4,6-dimethylaniline (8.03 g, 45.3 mmol, 2 equiv) in methanol (MeOH) (9 mL), glyoxal solution (40% aqueous solution) (3.45 g, 2.73 mL, 23.8 mmol, 1.05 equiv) was added dropwise and the reaction was carried out at room temperature for 20 h. The crude product was filtered, washed with methanol and dried under reduced pressure. A yellow precipitate was obtained in 63% yield (5.43 g, 14.4 mmol).

[0107] Synthesis II Under a protective argon atmosphere, ethyl acetate (64 mL) was added to a reaction vessel equipped with a stir bar and heated to 70 °C. Next, imine I (2.71 g, 7.19 mmol, 1 equivalent) and paraformaldehyde (225 mg, 7.26 mmol, 1.01 equivalents) were added, followed by the addition of chlorotrimethylsilane (9.21 mL, 7.19 mmol, 1.00 equivalent), dissolved in ethyl acetate (0.7 mL). The reaction was carried out at 70 °C for 2 h. The mixture was cooled, the precipitate was filtered off and washed with ethyl acetate and tert-butyl-methyl ether. The precipitate was dissolved in dichloromethane (20 mL), and a solution of potassium tetrafluoroborate (2.71 g, 7.2 mmol, 1.0 equivalent) in water (15 mL) was added and the mixture was stirred for 2 h. The mixture was extracted using methylene chloride (3 × 30 mL). The organic fraction was collected, dried over anhydrous magnesium sulfate and filtered through neutral celite. The solvent was evaporated under reduced pressure and the crude product was recrystallized from a methanol / diethyl ether mixture. A colorless precipitate was obtained in 66% yield (2.27 g, 4.76 mmol).

[0108] Synthesis III Under a protective argon atmosphere, sodium borohydride (2.71 g, 70.1 mmol, 10.0 equivalents) was added in portions to a reaction vessel equipped with a stir bar containing imine I (2.64 g, 7.01 mmol, 1 equivalent) in a methanol-tetrahydrofuran mixture (36 mL + 53 mL) while maintaining a temperature below 0 °C. Next, the reaction was carried out at room temperature for 1.5 h. Ammonium chloride was added to the reaction mixture. The reaction mixture was extracted with diethyl ether (3 × 50 mL) and washed with distilled water (20 mL). The organic fraction was collected, dried over anhydrous magnesium sulfate and filtered through neutral celite, and the solvent was evaporated under reduced pressure. A yellow oil was obtained in 99% yield (3.13 g, 6.94 mmol).

[0109] Synthesis IV Under a protective argon atmosphere, amine III (2.53 g, 6.65 mmol, 1 equivalent), triethyl orthoformate (2.68 mL, 16.6 mmol, 2.5 equivalents), and ammonium tetrafluoroborate (767 mg, 7.32 mmol, 1.1 equivalents) were added to a reaction vessel equipped with a stir bar. The reaction was carried out at 110 °C for 1.5 hours. The mixture was cooled and extracted with methylene chloride (3 × 50 mL). The collected organic fractions were dried over magnesium sulfate, filtered through neutral celite, and the solvent was evaporated under reduced pressure. The crude product was crystallized from a chloroform / diethyl ether mixture. Colorless crystals were obtained in 49% yield (1.56 g, 3.27 mmol).

Chemical formula

[0110] Example IV Synthesis of ruthenium complexes Ru-a to Ru-o using CAAC ligands Embodiment examples of the present invention Method A

Chemical formula

[0111] Alternative embodiments of the present invention Method B

Chem.

[0112] Alternative Embodiments of the Present Invention Method C

Chem.

[0113] Alternative embodiments of the present invention Method D

Chemical formula

[0114] Using Methods A - D shown in Example IV, various complexes from Ru-a to Ru-n were obtained. Their structures are shown below.

[0115] All complexes in the following table were characterized using nuclear magnetic resonance spectroscopy. Table 1 includes the shifts of the benzylidene / indenylidene protons for each of the complexes in the 1H NMR spectrum in a given solvent. 1

Chemical formula

[0116]

Table 1

[0117] Example V Test of the Activity of Complexes in the Ethanolysis Reaction of Methyl Oleate A Schlenk flask equipped with a magnetic stirring element (pre-weighed with a stopper on a scale) [Photo A] was connected to a Schlenk line. Next, a sintered glass filtering funnel was placed on top of the Schlenk tube [Photo B] and filled with Al2O3 [Photos C and C']. This filtering funnel was suctioned for 30 minutes and filled with argon. Methyl oleate (95% purity) or FAME (containing 73% methyl oleate and 19.7% methyl linoleate) (15 mmol) was taken out from the ampoule using a syringe and transferred to the filtering funnel so as to be filtered through the pad of Al2O3 using pressurized argon [Photos D and D']. Next, the filtered methyl oleate or FAME [Photo E] was degassed in vacuo (p ca. 1×10 -2 mbar) for 10 minutes [Photo F], and the Schlenk flask was weighed again together with the substrate (also, the amount of methyl oleate or FAME was calculated from the mass difference). In another Schlenk flask, a pre-weighed sample of the catalyst (Ru5 - Ru10) was dissolved in anhydrous PhMe (c = 1 mg / mL) under an argon atmosphere. An appropriate amount of the catalyst solution (corresponding to 0.5 - 15 ppm of Ru) was added under argon to the Schlenk flask containing the filtered methyl oleate or FAME using a Hamilton syringe (the amount of the dissolved catalyst was accurately calculated with reference to the mass of the substrate in the Schlenk flask), and the Schlenk flask was mixed properly by shaking it for 5 seconds. The resulting mixture was immediately sucked using a vacuum through a Teflon tube [Photos H and I] into a steel autoclave containing a glass reaction vessel equipped with a magnetic stirring element [Photo G]. Next, the autoclave was filled with ethylene (10 bar), and the reaction mixture was stirred at 40 °C for 6 hours. After that time, the pressure was returned to normal and the autoclave was removed. SnatchCat 1,2A DCM (0.5 mL) solution was added to this reaction mixture, and it was stirred for 5 minutes. Next, a sample of the reaction mixture was taken out and subjected to GC analysis. Each sample was measured 4 times. The results are the average of the four measured values, and here, the deviation between the averaged result and each measured value is 0.5 - 1%.

Chemical formula

[0118] The results of the model reaction are shown in Table 2.

[0119]

Table 2

[0120] Example VI Test on the solubility of complexes in nonpolar solvents Into a round-bottom flask equipped with a stir bar, catalysts (Ru-a, Ru-b, Ru-c, Ru-d, Ru-h, Ru-15, Ru-16, and Hov-II) were placed in an amount of 5 mg each. To each flask, n-hexane was added in portions at room temperature, and the mixture was stirred using a magnetic stirrer. The Ru-a was dissolved in 6 mL, and the Ru-h complex was dissolved in 4 mL of the solvent. In the case of the Ru-15 complex, almost complete solubility was observed after adding 20 mL of n-hexane. The Hov-II complex did not dissolve even in 20 mL of the solvent even after thorough stirring for 4 hours.

[0121]

Table 3

[0122] Example VII Test on the activity of complexes in the self-cross metathesis reaction of 1-dodecene.

Chemical formula

[0123] Example VIII Individual reactions including a method for synthesizing a novel precursor of a CAAC ligand Method A In a round-bottom flask equipped with a magnetic stirring element, 2,4-dimethyl-2-phenylpent-4-enal (4b) (1.00 equiv.), aniline (1.00 equiv.), and PTSA (1 mol%) were dissolved in PhMe (C = 0.30 M). This reaction mixture was heated under reflux until sufficient consumption of the substrate (water was collected in a Dean - Stark apparatus). The reaction mixture was cooled to room temperature (RT), the solvent was evaporated under reduced pressure, the crude reaction mixture was filtered through neutral aluminum oxide (Al2O3, neutral, Brockman grade I), dried in vacuo, and the imine used in the next step was obtained without further purification.

[0124] Method B In a round-bottom flask equipped with a magnetic stirring element, the appropriate aldehyde (1.00 equiv) was dissolved in anhydrous DCM (c = 0.5 M), 4 Å molecular sieves were added, followed by the addition of aniline (1.00 equiv). The resulting solution was stirred at room temperature for 16 h. The reaction mixture was filtered through neutral celite and the solvent was evaporated under reduced pressure. The residue was dried in vacuo to afford the imine used in the next step without further purification.

[0125] General procedure for the imine alkylation reaction Under a protective argon atmosphere, in a Schlenk flask equipped with a magnetic stirring element, the imine (1.00 equiv) was dissolved in anhydrous THF (c = 0.5 M) and cooled to -78 °C. BuLi (1.20 equiv) was added dropwise and the resulting solution was stirred at -78 °C for 10 min, heated to room temperature and stirred for a further 1 h. The reaction mixture was cooled to -20 °C and 3-chloro-2-methylpropene (1.50 equiv) was added. The flask was then heated to room temperature and stirring was continued for 16 h. The solvent and volatiles were evaporated under reduced pressure and dried in vacuo. The crude reaction mixture was dissolved in n-hexane and passed through a short layer of neutral aluminum oxide (Al2O3, neutral, Brockmann grade I). The solvent was evaporated under reduced pressure and the residue was dried in vacuo to afford the imine used in the next step without further purification.

[0126] General procedure for the Wittig reaction Under a protective argon atmosphere, in a Schlenk flask equipped with a magnetic stirring element, (methoxymethyl)triphenylphosphonium chloride (1.60 equivalents) was suspended in anhydrous THF (c = 0.5 M), and the resulting mixture was cooled to 0 °C, followed by the addition of t-BuOK (1.60 equivalents). The resulting solution was stirred at 0 °C for 1 hour and then at room temperature for 30 minutes, during which time the color of the solution changed to dark red. Next, the reaction mixture was cooled to 0 °C, and the appropriate ketone (1.00 equivalent) dissolved in anhydrous THF was added dropwise, and the mixture was stirred for 16 hours. The solvent was evaporated under reduced pressure, n-heptane was added, and the mixture was stirred for 30 minutes. The resulting phosphine oxide was filtered through a short neutral celite layer. The crude product was purified using a combined flash chromatography method (SiO2, 0→5% EtOAc / n-hexane) to obtain the product.

[0127] General method for aldehyde synthesis The enol ether (1.00 equivalent) was dissolved in a 4:1 mixture of acetone and H2O, and the resulting solution was cooled to 0 °C. Next, HBr (48%) (1.00 equivalent) was added dropwise, and the reaction mixture was stirred at room temperature until the substrate was fully consumed (48 hours). The solvent was removed under reduced pressure, and the remaining aqueous residue was neutralized with NaHCO3 (aqueous solution) as clarified using test paper (pH = 8). This aqueous solution was extracted with DCM (3 × 10 mL). The organic layers were combined and dried over MgSO4. The solvent was evaporated under reduced pressure, and the residue was dried in vacuo, yielding the aldehyde used in the next step without further purification.

[0128] General synthetic protocol for CAAC-H×BF4. Under a protective argon atmosphere, in a round-bottom flask equipped with a magnetic stirring element, the imine (1.00 equiv) was dissolved in PhMe (c = 0.5 M), followed by the addition of HCl (c = 4.0 M in dioxane) (2.50 equiv) at 0 °C. The reaction mixture was stirred at 85 °C for 16 h, cooled to RT, and the solvent was evaporated under reduced pressure. The crude product was dissolved in DCM (10 mL), NaBF4 (2.00 equiv) dissolved in H2O (10 mL) was added, and the mixture was stirred at RT for 2 h. The reaction mixture was transferred to a separatory funnel, extracted with DCM (3 × 10 mL), the organic layers were combined, and dried over MgSO4. The solvent was evaporated under reduced pressure, the crude product was dissolved in a small amount of MeOH (1 - 2 mL), followed by the addition of Et2O. A precipitate was formed, filtered, and dried in vacuo to afford the final product.

[0129] Synthesis of CAAC ligand precursor

Chem.

[0130] General synthesis of CAAC-H×BF4 - Method 1. Synthesis of 1-(2-(tert-butyl)phenyl)-2,2,4-trimethyl-4-phenyl-3,4-dihydro-2H-pyrrol-1-ium tetrafluoroborate (9bB)

Chem.

[0131] N-(2-(tert-butyl)phenyl)-2,4-dimethyl-2-phenylpent-4-en-1-imine (7bB) The imine (7bB) was synthesized according to the "General imine synthesis procedure". Using 2,4-dimethyl-2-phenylpent-4-enal (1.85 g, 9.9 mmol), 2-(tert-butyl)aniline (1.50 g, 1.57 mL, 9.9 mmol), and PTSA (17 mg, 0.10 mmol), the product was obtained as a yellow oil (1.50 g, 4.7 mmol, 48%). [Chemical formula] 1 1H NMR (400 MHz, chloroform-d): δ 7.86 - 7.80 (m, 1H), 7.45 - 7.31 (m, 5H), 7.30 - 7.22 (m, 1H), 7.21 - 7.08 (m, 2H), 6.71 - 6.62 (m, 1H), 4.86 - 4.79 (m, 1H), 4.70 - 4.63 (m, 1H), 2.92 - 2.84 (m, 2H), 1.67 - 1.60 (m, 3H), 1.49 - 1.41 (m, 9H), 1.43 - 1.36 (m, 3H); 13 13C NMR (101 MHz, chloroform-d): δ 167.8, 151.2, 144.2, 142.8, 142.7, 128.6, 127.3, 127.1, 126.7, 126.1, 125.4, 119.9, 115.2, 47.6, 47.5, 35.7, 30.5, 24.6, 22.3.

[0132] Tetrafluoroborate 1-(2-(tert-butyl)phenyl)-2,2,4-trimethyl-4-phenyl-3,4-dihydro-2H-pyrrol-1-ium (9bB) CAAC-H×BF4 (9bB) was synthesized according to the "General Synthetic Protocol for CAAC-H×BF4". Using N-(2-(tert-butyl)phenyl)-2,4-dimethyl-2-phenylpent-4-en-1-imine (1.50 g, 4.69 mmol), HCl (3.02 g, 2.93 mL, 11.7 mmol), and NaBF4 (1.03 g, 9.39 mmol), the product was obtained as a colorless solid (1.00 g, 2.46 mmol, 52%). [Chemical formula] 11H NMR (400 MHz, chloroform-d): δ 9.80 (s, 0.61×1H), 9.37 (s, 0.39×1H), 7.74 (dd, J = 8.3, 1.4 Hz, 0.61×1H), 7.68 - 7.60 (m, 0.39×1H), 7.57 - 7.27 (m, 7H + 0.39×1H), 6.82 (dd, J = 8.1, 1.4 Hz, 0.61×1H), 3.21 (d, J = 13.9 Hz, 0.61×1H), 3.06 (d, J = 13.6 Hz, 0.39×1H), 2.78 (d, J = 13.5 Hz, 0.39×1H), 2.56 (d, J = 13.9 Hz, 0.61×1H), 1.99 (s, 0.39×3H), 1.86 (s, 0.39×3H),.84 (s, 0.61×3H), 1.52 (2s, 3H), 1.46 (s, 0.61×9H), 1.35 (s, 0.61×3H), 1.14 (s, 0.39×9H); 13 13C NMR (101 MHz, chloroform-d): δ 189.1, 187.6, 145.1, 144.4, 40.8, 140.1, 132.4, 131.5, 131.4, 131.3, 131.3, 130.2, 129.9, 28.6, 128.3, 128.2, 127.4, 127.2, 126.8, 125.7, 125.7, 82.6, 81.8, 55.3, 55.2, 8.7, 47.1, 38.1, 37.6, 33.8, 33.7, 30.3, 29.9, 28.4, 28.2, 27.2, 26.0; IR (film): 3059, 2971, 2937, 2876, 1643, 1462, 1265, 1037, 731, 700; HRMS-ESI ([M] + ): C 23 H 30 N + calculated for: 320.2373, found: 320.2371; elemental analysis for C 23 H 30 BF4N calculated: C, 67.82; H, 7.42; N, 3.44; found: C, 67.63; H, 7.35; N, 3.37.

[0133] Synthesis of 2,2,4-trimethyl-1-(2-(tert-pentyl)phenyl)-4-phenyl-3,4-dihydro-2H-pyrrol-1-ium tetrafluoroborate (9bC) [Chemistry]

[0134] 2,4 - Dimethyl - N-(2-(tert - pentyl)phenyl)-2 - phenylpent - 4 - en - 1 - imine (7bC) Imine (7bC) was synthesized according to the "General Imine Synthesis Protocol". The product was obtained as an orange - yellow oil (0.42 g, 1.3 mmol, 28%). 1 H NMR (400 MHz, chloroform - d): δ 7.77 s, 1H), 7.40 - 7.32 (m, 4H), 7.31 - 7.22 (m, 2H), 7.18 - 7.08 (m, 2H), 6.64 - 6.60 (m, 1H), 4.84 - 4.79 (m, 1H), 4.68 - 4.63 (m, 1H), 2.90 - 2.80 (m, 2H), 1.86 (qd, J = 7.5, 1.5 Hz, 2H), 1.61 (s, 3H), 1.41 (s, 3H), 1.40 - 1.38 (m, 3H), 1.37 (s, 3H), 0.57 (t, J = 7.5 Hz, 3H); 13 C NMR (101 MHz, chloroform - d): δ 167.5, 151.3, 144.3, 142.7, 140.9, 128.6, 127.5, 127.2, 127.0, 126.7, 125.2, 119.8, 115.2, 47.5, 47.4, 39.3, 34.0, 28.6, 28.4, 24.6, 22.2, 9.5.

[0135] 2,2,4 - Trimethyl - 1-(2-(tert - pentyl)phenyl)-4 - phenyl - 3,4 - dihydro - 2H - pyrrol - 1 - ium tetrafluoroborate (9bC) CAAC - H×BF4 (9bC) was synthesized according to the "General Synthesis Protocol for CAAC - H×BF4". Using N-(2-(tert - pentyl)phenyl)-2,4 - dimethyl - 2 - phenylpent - 4 - en - 1 - imine (0.80 g, 2.40 mmol), HCl (1.54 g, 1.50 mL, 6.0 mmol), and NaBF4 (0.53 g, 4.8 mmol), the product was obtained as a colorless solid (0.4 g, 2.46 mmol, 40%). [Chemical formula] 1 H NMR (400 MHz, chloroform-d): δ 9.69 (s, 0.53 × 1H), 9.30 s, 0.47 × 1H), 7.67 (dd, J = 8.3, 1.4 Hz, 0.53 × 1H), 7.59 - 7.27 (m, 8H), 6.86 (dd, J = 8.1, 1.4 Hz, 0.53 × 1H), 3.22 (d, J = 13.9 Hz, 0.53 × 1H), 3.07 (d, J = 3.5 Hz, 0.47 × 1H), 2.79 (d, J = 13.5 Hz, 0.47 × 1H), 2.57 (d, J = 13.9 Hz, 0.53 × 1H), 1.98 (s, 0.47 × 3H), 1.94 - 1.81 (m, 0.53 × 1H + 0.53 × 3H + 0.47 × 3H), 1.78 - 1.62 (m, 1H), 1.54 - 1.50 (m, 3H), 1.49 - 1.41 (m, 0.47 × 1H), 1.40 - 1.37 (m, 3H), 1.36 (0.53 × 3H), 1.12 (s, 0.47 × 3H), 0.89 (s, 0.53 × 3H), 0.79 (t, J = 7.4 Hz, 0.52 × 3H), 0.57 (t, J = 7.4 Hz, 0.48 × 3H); 13 C NMR (101 MHz, chloroform-d): δ 189.0, 187.5, 144.2, 143.3, 140.9, 140.3, 132.7, 132.6, 132.2, 31.6, 131.4, 131.3, 130.2, 130.0, 128.6, 128.3, 128.0, 127.4, 127.2, 126.9, 125.8, 125.6, 83.0, 81.9, 55.4, 55.1, 48.8, 47.1, 41.5, 41.0, 39.4, 39.4, 31.8, 31.1, 0.5, 30.2, 29.8, 29.7, 28.5, 28.1, 7.1, 26.2, 9.3, 9.2; IR (film): 3056, 2979, 2938, 2883, 1646, 1602, 1498, 1489, 1480, 1469, 463, 1446, 1376, 1397, 1368, 352, 1341, 1287, 1228, 1189, 1172, 1113, 054, 1028, 1020, 889, 777, 761, 748, 694, 677, 656, 611, 564, 39, 20, 501; HRMS-ESI ([M] + ): C24 H 32 N + Calculated for: 334.2529, Measured: 334.2526; Elemental analysis: C 24 H 32 Calculated for BF4N: C, 68.42; H, 7.66; N, 3.32; Measured: C, 68.19; H, 7.70; N, 3.29.

[0136] Synthesis of 1-(2,5-Di-tert-butylphenyl)-2,2,4-trimethyl-4-(naphthalen-1-yl)-3,4-dihydro-2H-pyrrol-1-ium tetrafluoroborate (9cD) - According to Method B

Chemical formula

[0137] Synthesis of 1-(1-Methoxyprop-1-en-2-yl)naphthalene The enol ether was synthesized according to the "General Wittig Reaction Protocol" from 1'-acetonaphthone (10.00 g, 9.00 mL, 57.0 mmol), potassium tert-butoxide (7.83 g, 68.4 mmol), and (methoxymethyl)triphenylphosphonium chloride (28.2 g, 79.8 mmol), and the product was obtained as a colorless oil (11.1 g, 55.8 mmol, 98%).

Chemical formula

[0138] 2-(Naphthalen-1-yl)propanal The aldehyde was synthesized according to the "General Aldehyde Synthesis Protocol". 1-(1-Methoxyprop-1-en-2-yl)naphthalene (5.00 g, 25.2 mmol) and HBr (4.25 g, 2.85 mL, 25.2 mmol) were used, and the product was obtained as a colorless oil (4.6 g, 24.9 mmol, 98%).

Chemical formula

[0139] N-(2,5-Di-tert-butylphenyl)-2-(naphthalen-1-yl)propan-1-imine (8cD) The imine was synthesized according to the "General Imine Synthesis Protocol" (Method B). Using 2-(naphthalen-1-yl)propanal (4c) (0.70 g, 3.8 mmol, 1.00 equiv) and 2,5-di-tert-butylaniline (0.79 g, 3.8 mmol, 1.00 equiv), the product was obtained as a yellow oil (1.41 g, 3.8 mmol, >99%). This imine was used directly in the subsequent stage without further purification.

[0140] N-(2,5-Di-tert-butylphenyl)-2,4-dimethyl-2-(naphthalen-1-yl)penta-4-en-1-imine (7cD) The imine was synthesized according to the "General Imine Alkylation Protocol". Using imine (8cD) (1.61 g, 4.34 mmol, 1.00 equiv), 3-chloro-2-methylpropene (0.60 g, 0.66 mL, 6.51 mmol, 1.50 equiv), and BuLi (1.54 g, 2.22 mL, 5.21 mmol, 1.20 equiv), the product was obtained as a yellow oil (1.50 g, 3.52 mmol, 81%). This imine was used directly in the subsequent stage without further purification.

[0141] Synthesis of 1-(2,5-Di-tert-butylphenyl)-2,2,4-trimethyl-4-(naphthalen-1-yl)-3,4-dihydro-2H-pyrrol-1-ium tetrafluoroborate (9cD) CAAC-H×BF4 was synthesized according to the "General Synthesis Protocol for CAAC-H×BF4". Using N-(2,5-di-tert-butylphenyl)-2,4-dimethyl-2-(naphthalen-1-yl)penta-4-en-1-imine (1.36 g, 3.2 mmol), HCl (2.06 g, 2.00 mL, 7.99 mmol), and NaBF4 (0.70 g, 6.4 mmol), the product was obtained as an off-white solid (0.20 g, 0.39 mmol, 12%).

Chemical Structure

[0142] Example IX [Ru]-CAAC complex general synthesis protocol. Under a protective argon atmosphere, in a Schlenk flask equipped with a magnetic stirring element, CAAC-H×BF4 (1.60 - 2.20 equivalents) and (Hov-I) (1.00 equivalent) were added to anhydrous THF (c [CAAC-H×BF4] ​It was suspended in THF (0.1 M) and stirred for 1 minute. Subsequently, LiHMDS (1.60 - 2.20 equivalents) was added and stirred until the complete consumption of Hov-1. This crude mixture was filtered through a short layer of neutral aluminum oxide (Al2O3, neutral, Brockman grade I) using Et2O as the eluent. The green fraction was collected and evaporated under reduced pressure. Next, a small amount (1 - 2 mL) of n-pentane was added and the mixture was placed in an ultrasonic bath. The product was filtered and washed with cold n-pentane (1 mL). After drying in vacuo, a green crystalline solid was obtained.

Chem.

[0143] In some cases, the carbon atom of Ru=CHAr appears as a doublet in the 13 13C NMR spectrum. This is caused by certain technical limitations of the NMR spectrometer. This sometimes causes {C,H} decoupling in the range of 300 ppm to be incorrect, which may lead to coupling between the alkylidene proton and the alkylidene carbon atom, resulting in the appearance of a doublet.

[0144] Synthesis of Ru16 Complex This complex was synthesized according to the "General Synthetic Protocol for [Ru]-CAAC Complexes". Using Ru1 (200 mg, 0.33 mmol), LiHMDS (139 mg, 0.83 mmol), and CAAC-H·BF4 (298 mg, 0.73 mmol), the product was obtained as a green powder (178 mg, 0.28 mmol, 84%).

Chem.

[0145] Synthesis of Ru-k complex This complex was synthesized according to the “General Synthetic Protocol for [Ru]-CAAC Complexes”. Using Ru1 (50 mg, 0.08 mmol), CAAC-H×BF4 (9bB) (75 mg, 0.18 mmol), and LiHMDS (30.6 mg, 0.18 mmol), the product was obtained as a green powder (40 mg, 0.06 mmol, 75%).

[0146] This complex was synthesized according to the "General Synthetic Protocol for [Ru]-CAAC Complexes". Using Ru1 (0.25 g, 0.42 mmol), CAAC-H×BF4 (9bB) (0.37 g, 0.92 mmol), and LiHMDS (0.16 g, 0.92 mmol), the product was obtained as a green powder (242 mg, 0.39 mmol, 91%).

Chemical formula

[0147] Synthesis of Ru-m complex This complex was synthesized according to the “General Synthetic Method for [Ru]-CAAC Complexes”. Using Ru1 (150 mg, 0.25 mmol), CAAC-H·BF4 (9bC) (231 mg, 0.55 mmol), and LiHMDS (95 mg, 0.55 mmol), the product was obtained as a green powder (132 mg, 0.20 mmol, 81%).

Chem.

[0148] Synthesis of Ru-n Complex This complex was synthesized according to the “General Synthetic Protocol for [Ru]-CAAC Complex”. Using Ru1 (129 mg, 0.21 mmol), CAAC-H×BF4 (9cD) (176 mg, 0.34 mmol), and LiHMDS (59 mg, 0.34 mmol), the product was obtained as a green powder (130 mg, 0.17 mmol, 81%).

Chemical Structure

[0149] Synthesis of Ru-o complex This complex was synthesized according to the “General Synthetic Protocol for [Ru]-CAAC Complexes”. Using Ru1 (300 mg, 499 μmol), CAAC-H·BF4 (9aD) (441 mg, 1.10 mmol), LiHMDS (184 mg, 1.10 mmol), and copper(I) chloride (98.9 mg, 999 μmol), the product was obtained as a green powder (218 mg, 244 μmol, 69%). [Chemical formula] 1 H NMR (400 MHz, chloroform-d) δ 16.59 (s, 1H), 7.73 (d, J = 8.6 Hz, 1H), 7.56 - 7.45 (m, 2H), 7.19 (s, 1H), 6.93 (d, J = 8.4 Hz, 1H), 6.83 (d, J = 5.9 Hz, 2H), 4.15 (hept, J = 5.4 Hz, 1H), 2.28 (s, 3H), 2.16 (s, 2H), 1.86 - 1.76 (m, 6H), 1.68 (d, J = 6.1 Hz, 3H), 1.51 - 1.44 (m, 12H), 1.29 (s, 3H), 1.06 (s, 9H); 13 C NMR (101 MHz, chloroform-d) δ 298.6, 198.4, 265.6, 152.5, 149.9, 144.3, 144.0, 139.0, 132.0, 130.6, 125.2, 123.1, 121.9, 113.2, 76.4, 44.9, 55.8, 52.1, 37.4, 34.2, 33.8, 31.1, 29.9, 28.1, 28.0, 22.4, 21.8; IR: 3069, 2972, 2954, 2939, 2868, 1627, 1610, 1589, 1577, 1502, 1476, 1455, 1440, 1432, 1398, 1385, 1376, 1363, 1316, 1294, 1268, 1237, 1224, 1199, 1159, 1129, 1112, 1095, 1087, 1068, 1037, 1019, 1012, 942, 880, 839, 806, 793, 751, 688, 657, 641, 580, 563, 485, 450, 38; HRMS-ESI ([M] + ): C 32 H 47 NOCl2Ru + Calculated for: 633.2073, Found: 633.2083.

[0150] Example X Methyl oleate ethenolysis Preparation and treatment of methyl oleate Oleic acid (500 g) was dissolved in acetone (1 g of acid was put into 11 mL of solvent). This mixture was cooled to -40 °C and stirred for 16 hours. The solid was filtered on a Buchner funnel, transferred to a round-bottom flask, and the remaining acetone was evaporated using a rotary evaporator, followed by evaporation under high vacuum. This process was repeated 2 - 4 times. The remaining oleic acid was dissolved in MeOH and stirred with a catalytic amount of PTSA for 16 hours under argon. After cooling to room temperature, MgSO4 was added, the reaction mixture was stirred for 2 hours, the solid was filtered, and MeOH was evaporated under reduced pressure. The newly prepared methyl oleate was placed in a round-bottom flask equipped with a magnetic stirring element. Activated aluminum oxide was added (2.5 wt%), and a distillation set was assembled. The contents of the flask were heated at 60 °C for 1 hour under high vacuum, and then distillation was started. The top 10% and bottom 10% were discarded. The newly distilled methyl oleate was treated with 2.5 wt% of activated aluminum oxide and 0.1 mol% of BHT, the gas was aspirated, and the contents of the flask were stirred at 100 °C for approximately 1 hour under a gentle stream of argon. After cooling to room temperature, the methyl oleate was filtered into the flask through a pad of activated aluminum oxide under argon and stored in the dark in a vial through the activated aluminum oxide.

[0151] FAME (Fatty Acid Methyl Ester) Preparation The FAME was treated with 2.5 wt% of activated aluminum oxide and 0.1 mol% of BHT, the gas was aspirated, and the contents of the flask were stirred at 100 °C for 1 hour under a gentle stream of argon. After cooling to room temperature, the FAME was filtered into the flask through a pad of activated aluminum oxide under argon and transferred and stored in the dark in a vial through the activated aluminum oxide. GC FAME composition: 73.1% methyl oleate, 19.7% methyl linoleate, 1.4% methyl stearate, methyl elaidate, and small amounts of other impurities.

[0152] General Ethenolysis Procedure for Methyl Oleate and FAME under Argon Atmosphere A Schlenk flask equipped with a magnetic stirring element (pre-weighed together with the stopper on a scale) [Photo A] was connected to a vacuum-argon line. Next, a filtering funnel with a frit [Photo B] was attached to the topmost part of the Schlenk vessel, and Al2O3 was poured [Photos C and C']. This filtering funnel was suctioned for 30 minutes and filled with argon. Methyl oleate (95% purity) or FAME (containing 73% methyl oleate and 19.7% methyl linoleate) (15 mmol) was collected from the vial using a syringe and transferred to the filtering funnel [Photos D and D'], and filtered through the Al2O3 layer using pressurized argon. Next, the filtered methyl oleate or FAME [Photo E] was degassed in vacuo (p ~ 1×10 -2 mbar) for 10 minutes [Photo F], and the Schlenk vessel was weighed again together with the substrate (the amount of methyl oleate or FAME was calculated from the mass difference). In another Schlenk vessel, a weighed sample of the catalyst (Ru-16, Ru-j, Ru-k, Ru-m, Ru-n, Ru-o) was dissolved in anhydrous PhMe (c = 1 mg / mL) under an argon atmosphere. An appropriate amount of the catalyst solution (corresponding to 0.5 - 15 ppm of Ru) was added, under an argon atmosphere, to the Schlenk vessel containing the filtered methyl oleate or FAME using a Hamilton syringe (the amount of the dissolved catalyst was accurately calculated based on the mass of the substrate in the Schlenk vessel), and the vessel was shaken and stirred appropriately at 5-second intervals. The resulting mixture was immediately suctioned, using a vacuum, through a Teflon tube [Photos H and I], into a steel autoclave containing a glass reaction vessel equipped with a magnetic stirring element [Photo G]. The autoclave was then filled with ethylene (10 bar), and the reaction mixture was stirred at 40 °C for 6 hours. After this period, the ethylene was removed and the autoclave was taken off. SnatchCat solution (in DCM (0.5 mL)) was added to this reaction mixture and stirred for 5 minutes. Next, a sample of the reaction mixture was collected and subjected to GC analysis. Each sample was measured 4 times. The results are the average of the 4 measured values, where the deviation between the average result and each measured value is 0.5 - 1%.

[0153] General Ethanolysis Procedure for Methyl Oleate and FAME in Air The setup for this reaction uses the same apparatus as above, but air is used instead of argon throughout the procedure. A Schlenk vessel equipped with a magnetic stirring element (previously weighed with the stopper on the scale) [Photo A as above] was connected to a vacuum pump. Next, a filtering funnel with a frit was attached to the top of the Schlenk vessel [Photo B], and Al2O3 [Photos C and C’] was poured in air. This filtering funnel was suctioned for 30 minutes and filled with air. A sample of methyl oleate (95% purity) or FAME (containing 73% methyl oleate and 19.7% methyl linoleate) was collected from the vial using a syringe (Note 1), transferred to the filtering funnel [Photos D and D’], and filtered through the Al2O3 layer using pressurized air. Next, the filtered methyl oleate or FAME [Photo E] was placed under vacuum (p ~ 1×10 -2Degassed for 10 minutes at [pressure value in mbar] [Photo F], and the Schlenk flask was weighed again (the amount of methyl oleate or FAME was calculated from the mass difference). In another Schlenk vessel, a weighed sample of the catalyst (Ru-16, Ru-j, Ru-k, Ru-m, Ru-n, Ru-o) was dissolved in anhydrous PhMe (c = 1 mg / mL) in air. An appropriate amount of the catalyst solution (corresponding to 0.5 - 15 ppm of Ru) was added, in air, using a Hamilton syringe, to the Schlenk vessel containing methyl oleate or FAME (the amount of dissolved catalyst was accurately calculated based on the weight of the substrate in the Schlenk flask), and the contents were mixed properly by shaking the Schlenk vessel for 5 seconds. The mixture was immediately transferred, under vacuum, using a Teflon tube, to a steel autoclave containing a glass reaction vessel equipped with a magnetic stirring element. The autoclave was then filled with ethylene (10 bar), and the reaction mixture was stirred at 40 °C for 6 hours. After this period, the ethylene was removed and the autoclave was taken out. SnatchCat solution (in DCM (2 mL)) was added to the reaction vessel, and the reaction mixture was stirred for 5 minutes. Then, samples of the reaction mixture were collected and subjected to GC analysis. Each sample was measured 4 times. The results are the average of the 4 measurements, where the deviation between the average result and each measurement is 0.5 - 1%.

[0154] Note 1: For longer storage, methyl oleate or FAME and anhydrous PhMe were stored in sealed vials under argon.

Chemical formula

[0155]

Table 4

[0156]

Table 5

[0157]

Table 6

[0158]

Table 7

[0159]

Table 8

[0160] Example XI General Catalyst Stability Test Procedure in the Presence of Ethylene - See Figure 10 15 mg (0.02 mmol) of ruthenium complex [Ru16 or Ru-k] was dissolved in 0.7 mL of CD2Cl2 placed in an NMR Young tube. Next, 1 mg of 1,3,5-trimethoxybenzene (0.006 mmol) was added [internal standard], and the contents of the tube were shaken until the ruthenium catalyst and the internal standard were dissolved. 1 When the 1H NMR "0" spectrum was recorded at 40 °C, the NMR tube with the cap removed was placed in an autoclave. The autoclave chamber was filled three times [each for 2 minutes] with ethylene under a pressure of 2 bar. Next, this autoclave chamber was purged with ethylene under a pressure of 10 bar. A dynamic pressure of up to 10 bar was applied to this chamber for 20 minutes. At the end of this time, the autoclave was depressurized, opened, the NMR Young tube was taken out, the contents of the tube were shaken 4 times, and placed in the NMR apparatus at 40 °C (30 minutes after the first ethylene treatment). The spectrum was recorded at 40 °C over 8 hours. Degradation was measured based on the disappearance of the alkylidene signal compared to the signal from the standard (OMe group).

[0161] Summary [Technical Effect] It was observed that a catalyst having a bulky substituent having a quaternary carbon atom on a nitrogen atom in an aromatic ring and having at least one aromatic substituent on the C2 atom in the CAAC ligand results in a permanent steric configuration of the ruthenium complex in which the N-aromatic substituent is on the opposite side of the benzylidene substituent. This was confirmed using crystal analysis, and the inventors judged from the characteristic shift of the Ru=CH benzylidene signal at a low magnetic field near 18 ppm [not a shift near 16 ppm similar to that in the publication Organometallics 2023, 42, 6, 495 - 504] that the steric configuration of this CAAC ligand is retained in solution. In solution, 1In the ¹H NMR spectrum, a single signal from the alkylidene can be observed, indicating that the similar ligand configuration on the opposite side of the benzylidene ligand is maintained in solution. This spatial structure facilitates the coordination of the olefin substrate to the metal ruthenium center and can prevent the decomposition of the methylidene intermediate via C-H insertion, which can explain the observed high activity and stability of these catalysts. It is noteworthy that the confirmation of the structure in the crystal analysis and the permanent CAAC ligand configuration in solution are opposite to all the configurations recorded in the literature to date [see Angew. Chem. Int. Ed. 2007, 46, 7262 - 7265].

[0162] Example XI Obtaining the precursor of the novel CAAC ligand Imine synthesis General imine synthesis procedure

Chemical formula

[0163] N-(2-Ethyl-6-methylphenyl)-2-(4-isobutylphenyl)-2,4-dimethylpent-4-en-1-imine (9b)

Chemical formula

[0164] N-(2,6-Diethylphenyl)-2-(4-isobutylphenyl)-2,4-dimethylpent-4-en-1-imine (9c)

Chemical formula

[0165] N-(2,6-Diisopropylphenyl)-2-(4-isobutylphenyl)-2,4-dimethylpent-4-en-1-imine (9d)

Chemical formula

[0166] N-(2,5-Di-tert-butylphenyl)-2-(4-isobutylphenyl)-2,4-dimethylpent-4-en-1-imine (9e)

Chemical formula

[0167] Synthesis of the tetrafluoroborate precursor of CAAC [Chemical formula] General Salt Synthesis Procedure Under a protective argon atmosphere, in a round-bottom flask equipped with a magnetic stirring element, the imine (9a - e, 1.00 equivalent) was dissolved in anhydrous toluene (c = 0.5 M), followed by the addition of hydrochloric acid (c = 4.0 M, in dioxane, 2.50 equivalents) at 0 °C. The reaction mixture was stirred at 85 °C for 16 h, cooled to room temperature, and the solvent was evaporated under reduced pressure. The crude product was dissolved in a small amount of DCM, and NaBF4 (2.00 equivalents) dissolved in H2O (approx. 10 mL) was added, and the mixture was stirred at room temperature for 2 h. The reaction mixture was transferred to a separatory funnel, extracted 3 times with DCM, the organic layers were combined, dried over anhydrous MgSO4, and filtered through neutral celite on a Schott funnel. The solvent was evaporated under reduced pressure, the crude product was dissolved in a small amount of MeOH, followed by the addition of Et2O. The precipitate was allowed to precipitate, filtered, and dried in vacuo to afford the final products 10a - e.

[0168] 1-(2 - ethyl - 6 - methylphenyl)-4-(4 - isobutylphenyl)-2,2,4 - trimethyl - 3,4 - dihydro - 2H - pyrrol - 1 - ium tetrafluoroborate (10b) Salt 10b was synthesized according to the "General Salt Synthesis Procedure". Using 9b (1.85 g, 5.10 mmol), hydrochloric acid (3.20 mL, 4.0 M (in dioxane), 12.8 mmol), and sodium tetrafluoroborate (1.12 g, 10.2 mmol), the product was obtained as a colorless solid (1.22 g, 2.70 mmol, 52%). [Chemical formula] 1 1H NMR (400 MHz, CDCl3): δ 9.51 - 9.41 (m, 1H), 7.44 - 7.32 (m, 3H), 7.35 - 7.27 (m, 0.5×H), 7.27 - 7.18 (m, 3H), 7.21 - 7.13 (m, 0.5×1H), 3.15 (ddd, J = 14.0, 9.3, 0.9 Hz, 1H), 2.66 (dd, J = 14.0, 0.3 Hz, 1H), 2.63 - 2.52 (m, 1H), 2.50 - 2.42 (m, 2H), 2.41 - 2.28 (m, 2H), 2.24 - 2.03 (m, 2H), 1.99 - 1.91 (m, 3H), 1.91 - 1.78 m, 1H), 1.58 (d, J = 5.1 Hz, 3H), 1.38 (s, 3H), 1.33 - 1.23 (m, 0.5×3H), 1.11 - 1.01 (m, 0.5×3H), 0.92 - 0.85 (m, 6H); 13 13C NMR (101 MHz, CDCl3): δ 189.9, 42.4, 140.2, 139.6, 137.5, 137.4, 134.3, 133.2, 131.8, 131.7, 131.2, 130.8, 130.7, 130.2, 130.0, 127.9, 127.9, 125.6, 125.6, 83.9, 55.4, 55.3, 48.5, 48.4, 45.0, 45.0, 30.2, 30.2, 29.3, 28.9, 28.0, 27.5, 27.3, 26.9, 25.0, 24.8, 22.5, 22.4, 22.4, 22.4, 19.5, 19.2, 15.6, 14.8; HRMS - ESI (m / z): C 26 H 36 N + [M] + ) calculated: 362.2842, found: 362.2842; elemental analysis for C 26 H 36 BF4N calculated: C, 69.49; H, 8.08; N, 3.12; found: C, 69.59; H, 7.97; N, 3.24; IR: 3061, 2957, 2933, 2870, 643, 1513, 1465, 1384, 1349, 1269, 151, 1035, 797, 732, 701, 645, 573, 521.

[0169] 1-(2,6-Diethylphenyl)-4-(4-isobutylphenyl)-2,2,4-trimethyl-3,4-dihydro-2H-pyrrol-1-ium tetrafluoroborate (10c) Salt 10c was synthesized according to the "General Salt Synthesis Procedure". Using 9c (1.85 g, 4.90 mmol), hydrochloric acid (3.08 mL, 4.0 M in dioxane, 12.3 mmol), and sodium tetrafluoroborate (1.08 g, 9.90 mmol), the product was obtained as a colorless solid (1.30 g, 2.80 mmol, 57%). [Chemical Structure] 1 H NMR (400 MHz, CDCl3): δ 9.49 (s, 1H), 7.49 - 7.35 (m, 3H), 7.34 - 7.27 (m, 1H), 7.26 - 7.17 (m, 3H), 3.18 (d, J = 14.1 Hz, 1H), 2.64 (d, J = 14.0 Hz, 1H), 2.57 (q, J = 7.6 Hz, 2H), 2.49 - 2.44 (m, 2H), 2.32 (dq, J = 15.1, 7.6 Hz, 1H), 2.13 (dq, J = 14.6, 7.3 Hz, 1H), 1.93 (s, 3H), 1.91 - 1.78 (m, 1H), 1.54 (s, 3H), 1.33 (s, 3H), 1.28 (t, J = 7.5 Hz, 3H) 1.07 (t, J = 7.5 Hz, 3H), 0.88 (dd, J = 6.6, 2.0 Hz, 6H); 13 C NMR (101 MHz, CDCl3): δ 189.8, 142.4, 140.0, 139.5, 137.5, 131.4, 130.8, 130.7, 127.9, 127.8, 125.6, 83.7, 55.3, 48.2, 45.0, 30.2, 29.1, 27.5, 26.8, 25.1, 24.8, 22.4, 22.4, 15.6, 14.7; HRMS - ESI (m / z): C 27 H 38 N + ([M] + ) Calculated for: 376.2999, Found: 376.2998; Elemental analysis: C 27 H 38Calculated for BF4N: C, 69.98; H, 8.27; N, 3.02; Found: C, 69.85; H, 8.25; N, 3.19; IR: 3053, 2957, 2935, 2871, 1643, 1513, 1464, 1383, 1349, 1271, 1051, 1034, 798, 733, 701, 572, 520.

[0170] 1-(2,6-Diisopropylphenyl)-4-(4-isobutylphenyl)-2,2,4-trimethyl-3,4-dihydro-2H-pyrrol-1-ium tetrafluoroborate (10d) Salt 10d was synthesized according to the “General Salt Synthesis Procedure”. Using 9d (2.05 g, 5.10 mmol), hydrochloric acid (3.17 mL, 4.0 M (in dioxane), 12.7 mmol), and sodium tetrafluoroborate (1.12 g, 10.2 mmol), the product was obtained as a colorless solid (1.60 g, 3.30 mmol, 64%). [Chemical formula] 1 H NMR (400 MHz, CDCl3): δ 9.58 - 9.51 (m, 1H), 7.54 - 7.38 (m, 3H), 7.36 - 7.30 (m, 1H), 7.28 - 7.19 (m, 3H), 3.26 (dd, J = 14.1, 1.7 Hz, 1H), 2.76 - 2.60 (m, 2H), 2.53 - 2.40 (m, 2H), 2.24 (sept, J = 6.8 Hz, 1H), 1.94 - 1.77 (m, 4H), 1.55 (bs, J = 1.6 Hz, 3H), 1.38 - 1.34 (m, 3H), 1.31 (s, 3H), 1.23 - 1.17 (m, 3H), 1.13 - 1.09 (m, 3H), 1.06 - 1.01 (m, 3H), 0.91 - 0.86 (m, 6H); 13 C NMR (101 MHz, CDCl3): δ 189.9, 144.9, 144.4, 142.4, 137.3, 132.1, 130.7, 128.9, 125.7, 125.5, 83.5, 55.4, 47.7, 45.0, 30.3, 30.2, 29.2, 29.0, 7.5, 26.3, 26.2, 26.0, 22.4, 22.4, 22.3, 22.3.; HRMS - ESI (m / z): C 29H 42 N + ([M] + ) Calculated: 404.3312, Measured: 202.3314; Elemental analysis: C 29 H 42 For BF4N Calculated: C, 70.87; H, 8.61; N, 2.85; Measured: C, 70.68; H, 8.40; N, 2.85; IR: 3055, 2958, 2933, 2868, 1638, 1509, 1471, 1351, 1269, 1106, 1054, 1039, 880, 808, 735, 704, 581, 566, 520.

[0171] 1-(2,5-Di-tert-butylphenyl)-4-(4-isobutylphenyl)-2,2,4-trimethyl-3,4-dihydro-2H-pyrrol-1-ium tetrafluoroborate (10e) Salt 10e was synthesized according to the "General Salt Synthesis Procedure". Using 9e (2.25 g, 5.20 mmol), hydrochloric acid (3.26 mL, 4.0 M (in dioxane), 13.0 mmol), and sodium tetrafluoroborate (1.14 g, 10.4 mmol), the product was obtained as a colorless solid (1.30 g, 2.50 mmol, 48%).

Chemical Structure

[0172] Example XII Synthesis of Novel Ruthenium Complexes with CAAC General Procedure for Ruthenium Complex Synthesis In a dry Schlenk flask equipped with a magnetic stirring element, the salt (10a - e, 2.20 equiv) and the first-generation Hoveyda - Grubbs complex (Hov I) (1.00 equiv) were suspended in THF (c CAAC = 0.10 M), and simultaneously this mixture was stirred for 1 minute. Then, LiHMDS (2.20 equiv) was added, and the resulting mixture was stirred until complete consumption of the substrate. Next, this crude mixture was filtered through a short layer of neutral aluminum oxide (Al2O3, neutral, Brockman grade I) using Et2O or DCM as the eluent. The green fractions were collected and the solvent was evaporated under reduced pressure. Next, a small amount of n - pentane was added to the residue, and this mixture was placed in an ultrasonic bath. The precipitate was filtered and washed with cold n - pentane (Ru - e, Ru - g) or n - heptane, followed by diethyl ether (Ru - h). To purify the crude product to Ru - f and Ru - i, column chromatography (SiO2, 10% AcOEt in n - hexane) was carried out, and the resulting product was precipitated from n - pentane.

[0173] Synthesis of Ru - f Complex The Ru - f complex was synthesized according to the "General Synthetic Method for Ruthenium Complexes". Using Hov I (120 mg, 200 μmol), 10b (198 mg, 440 μmol), and LiHMDS (73.5 mg, 440 μmol), the product was obtained as a green powder (102 mg, 150 μmol, 74%). [Chemical formula] 11H NMR (400 MHz, CD2Cl2): δ 17.65 (s, 0.31×1H), 16.31 (s, 0.69×1H); 13 13C NMR (101 MHz, CD2Cl2): 300.8 (in addition to further assignments, the diagnostic signals of the benzylidene protons and carbons are only reported because of the presence of conformations and rotamers that result in a highly complex spectrum); HRMS-ESI (m / z): C 36 H 47 NOCl2Ru + ([M] + ) calculated: 81.2073, found: 681.2071; elemental analysis: C 36 H 47 Calculated for C6H6Cl2N2ORu: C, 3.42; H, 6.95; N, 2.05; found: C, 63.27; H, 6.95; N, 2.13; IR: 2981, 2945, 2869, 1588, 1576, 1516, 1476, 1456, 1374, 1315, 1298, 1242, 1226, 1160, 1140, 1117, 1096, 1040, 997, 932, 881, 844, 807, 778, 755, 690, 569, 544.

[0174] Synthesis of Ru-i complex The Ru-i complex was synthesized according to the "General Synthetic Method for Ruthenium Complexes". Using Hov I (150 mg, 150 μmol), 10c (255 mg, 549 μmol), and LiHMDS (91.9 mg, 549 μmol), the product was obtained as a green powder (125 mg, 180 μmol, 71%).

Chemical formula

[0175] Ru-g complex The Ru-g complex was synthesized according to the "General Synthetic Method for Ruthenium Complexes". Using Hov I (170 mg, 250 μmol), 10d (270 mg, 549 μmol), and LiHMDS (91.9 mg, 549 μmol), the product was obtained as a green powder (131 mg, 181 μmol, 72%).

Chemical formula

[0176] Ru-h complex The Ru-h complex was synthesized according to the “General Synthetic Method for Ruthenium Complexes”. Using Hov I (300 mg, 499 μmol), 103 (571 mg, 1.10 mmol), and LiHMDS (184 mg, 1.10 mmol), the product was obtained as a green powder (328 mg, 436 μmol, 87%).

Chemical formula

[0177] Example XIII General ethenolysis procedure Under a protective argon atmosphere, (Ru16, Ru-e~i, approximately 5 mg) was placed in a Schlenk flask, dissolved in 5 mL of anhydrous toluene to prepare a basic solution. Methyl oleate was filtered through aluminum oxide into a Schlenk flask equipped with a magnetic stirring element and degassed under reduced pressure (p approximately 1×10 -2 )). An amount of the basic solution containing 3 or 1 ppm of the Ru complex was added to methyl oleate under an argon atmosphere. This mixture was immediately transferred to an autoclave containing a glass vessel equipped with a magnetic stirring element. The autoclave was then filled with 3.5 or 4.5 ethylene (10 bar), and the reaction mixture was stirred at 40 °C for 6 hours. After this time, the pressure was equalized, the autoclave was removed, SnatchCat solution (in DCM) was added, samples were collected, and GC analysis was performed.

[0178] GC method result analysis procedure Before the reaction, reaction coefficients (RF) for GC were determined using samples of methyl oleate and the ethenolysis product. Substrates and products of known mass were added to GC vials, dissolved in toluene, and analyzed 4 times using GC. [Chemical formula] Conversion = 100×[1-(A 11 ×A 0IS ) / (A 0 11 ×A IS )]; Selectivity = 100×(n 12 + n 13 ) / [(n 12 + n 13 ) + 2×(n 14 + n 15 )]; Yield = (Conversion × Selectivity) / 100; TON = Yield × [(n 0 11 / n 0 [Ru] )] / 100; A 11 、A IS = Methyl oleate and internal standard GC peak area at the end of the reaction; A 0 11 、A 0 IS = GC peak area of methyl oleate and internal standard before the reaction; n 0 11 、n 0 [Ru] = Initial number of moles of methyl oleate and catalyst used; IS = Internal standard (methyl stearate).

[0179]

Table 9

[0180] Example XIV RCM ring - closing reaction of diethyl 2,2 - diallylmalonate (DEDAM)

Chemical formula

[0181]

Table 10

[0182]

Table 11

[0183] Example XV RCM Reaction for N-Allyl-4-methyl-N-(2-methylallyl)benzenesulfonamide

Chem.

[0184]

Table 12

[0185]

Table 13

[0186] Example XVI Self-CM cross reaction of methyl oleate General procedure for Self-CM 11 Methyl oleate was placed in vacuo (p approximately 1×10 -2) Degassed and transferred to a Schlenk flask (1 equivalent) using a glass syringe filter under a protective argon atmosphere. The substrate (containing internal standard - methyl stearate) was transferred to six vials (catalyst loading 1.0 ppm) or a Schlenk flask (catalyst loading 2.5 ppm). In a protective argon atmosphere, (Ru16, Ru - e~i, approximately 5 mg) was placed in another Schlenk flask and dissolved in 5 mL of anhydrous toluene. An appropriate amount of the basic catalyst solution was added to this mixture under argon. The solution was stirred at 55 °C for 4 hours (1 ppm) or 24 hours (2.5 ppm). During the reaction, samples (each approximately 0.1 mL) for GC analysis were collected in 1.5 mL vials containing approximately 1 mL of toluene and two drops of SnatchCat solution (in DCM).

[0187]

Table 14

[0188]

Table 15

[0189] Example XVII Cross - CM reaction of allylbenzene with (Z)-but - 2 - ene - 1,4 - dioctane

Chem.

[0190] Results: a. Using Ru16 (92 μg, 0.1 μmol), the expected product (78 mg, 0.41 mmol, 72%) was obtained; b. Using Ru-e (100 μg, 0.1 μmol), the expected product (80 mg, 0.42 mmol, 74%) was obtained; c. Using Ru-f (98 μg, 0.1 μmol), the expected product (80 mg, 0.42 mmol, 74%) was obtained; d. Using Ru-I (100 μg, 0.1 μmol), the expected product (80 mg, 0.42 mmol, 74%) was obtained; e. Using Ru-g (145 μg, 0.2 μmol), the expected product (60 mg, 0.32 mmol, 55%) was obtained; f. Using Ru-h (108 μg, 0.1 μmol), the expected product (82 mg, 0.43 mmol, 75%) was obtained.

Chemical formula

[0191] Example XVIII Cross-CM reaction of undec-10-en-1-yl acetate and acrylonitrile [Chemical formula] Under a protective argon atmosphere, in a Schlenk flask equipped with a magnetic stirring element, undec-10-en-1-yl acetate (175 mg, 0.82 mmol) and acrylonitrile (88 mg, 1.65 mmol) were dissolved in anhydrous PhMe (c = 0.1 M). A 300 ppm Ru catalyst (as a basic solution in anhydrous PhMe) was added to this reaction mixture, and the reaction mixture was stirred for 4 hours. At the end of the reaction, the solvent was evaporated under reduced pressure, and the product (25) was purified using quick column chromatography (2% → 5% EtOAc in n-hexane).

[0192] Results: a. Using Ru16 (158 μg, 0.24 μmol), the expected product (100 mg, 0.42 mmol, 51%) was obtained as a colorless oil; b. Using Ru-f (169 μg, 0.24 μmol), the expected product (140 mg, 0.59 mmol, 72%) was obtained as a colorless oil; c. Using Ru-i (172 μg, 0.24 μmol), the expected product (162 mg, 0.68 mmol, 83%) was obtained as a colorless oil; d. Using Ru28 (169 μg, 0.24 μmol), the expected product (120 mg, 0.51 mmol, 61%) was obtained as a colorless oil.

Chemical formula

Claims

1. Precursor of cyclic alkylamine carbene (CAAC) having the formula CAAC-1 【Chemical 1】 (wherein X represents an anion selected from the group consisting of a halogen anion, BF ４ － , PF ６ － , ClO ４ － , CF ３ SO ２ O － ; R １ 、R ２ 、R ３ 、R ４ 、and R ５ are, independently, a hydrogen atom, a C １ -C １２ alkyl group, a C ３ -C １２ cycloalkyl group, a C ５ -C ２０ aryl group or a C ５ -C ２０ heteroaryl group, a C ５ -C ２５ aralkyl group, and these are a hydrogen atom, a halogen atom, a C １ -C １２ alkyl group, a C １ -C １２ perfluoroalkyl group, a C ５ -C ２０ aryl group, a C ５ -C ２０ perfluoroaryl group, a C ５ -C ２０ heteroaryl group, a C １ -C １２ alkoxy group, a C ５ -C ２４ aryloxy group, a C ５ -C ２０ heteroaryloxy group, a sulfide group (-SR''), an amine group (-NR'' ２ ), and may be independently substituted with one and / or more substituents selected from the group consisting of, where the R'' group is independently a hydrogen atom, a C １ -C ５ alkyl, a C ６ -C ２４ aryl, a C ７ -C ２４ aralkyl, or R １ 、R ２ 、R ３ 、R ４ 、and R ５ are linked to form a C ５ -C ２５ ring, In the formula, at least one substituent R １ , R ２ , and R ５ has an alkyl substituent having at least one secondary, tertiary, or quaternary carbon atom, and preferably, at least one substituent R １ , R ２ , and R ５ has an alkyl substituent having at least two secondary, tertiary, or quaternary carbon atoms, more preferably, at least one substituent R １ , R ２ , and R ５ has an alkyl substituent having at least three secondary, tertiary, or quaternary carbon atoms, and most preferably, at least one substituent R １ , R ２ , and R ５ has an alkyl substituent having at least four secondary, tertiary, or quaternary carbon atoms, Each substituent R ６ , R ７ , R ８ , and R ９ represents a hydrogen atom, a halogen atom, a C １ -C １２ alkyl group, or a C ５ -C ２０ aryl group, and these are hydrogen, a C １ -C １２ alkyl group, a C １ -C １２ perfluoroalkyl group, a C ５ -C ２０ aryl group, a C ５ -C ２０ perfluoroaryl group, a C ５ -C ２０ heteroaryl group, a C １ -C １２ alkoxy group, a C ５ -C ２４ aryloxy group, a C ５ -C ２０ heteroaryloxy group or a halogen atom, a sulfide group (-SR''), an amine group (-NR'' ２ ), and may be independently substituted with one and / or more substituents selected from the group consisting of, where the R'' group is independently a hydrogen atom, a C １ -C ５ alkyl, a C ６ -C ２４ aryl, a C ７ -C ２４ aralkyl, or R ６ and R ７ and / or R ８ and R ９ are linked to form a C ５ -C ２５ ring group).

2. The precursor according to claim 1, having the formula CAAC-2 or CAAC-3 or CAAC-4 【Chemical 2】 (wherein the substituent R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , and R ９ have the meanings defined above, R １０ 、R １１ 、R １２ 、R １３ 、and R １４ The substituents are independently a hydrogen atom, C １ -C １２ alkyl group, C ３ -C １２ cycloalkyl group, C ５ -C ２０ aryl group or C ５ -C ２０ heteroaryl group, C ５ -C ２５ aralkyl group, and these are a hydrogen atom, a 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 alkoxy group, C ５ -C ２４ aryloxy group, C ５ -C ２０ heteroaryloxy group, sulfide group (-SR''), amine group (-NR'' ２ ), and may be independently substituted by one and / or more substituents selected from the group containing them, where the R'' group is independently a hydrogen atom, C １ -C ５ alkyl, C ６ -C ２４ aryl, C ７ -C ２４ aralkyl, or R １ 、R ２ 、R ３ 、R １３ 、and R ５ are linked to form a C ５ -C ２５ ring).

3. The precursor according to claim 1 or 2, having the formula CAAC-5 or CAAC-6 or CAAC-7 [Chemical Formula 3] (X represents an anion selected from the group including halogen anions, BF ４ － , PF ６ － , ClO ４ － , CF ３ SO ２ O － ;) In the formula, the substituent R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , R １０ , R １１ , R １２ , R １３ , and R １４ have the meanings defined above R １５ independently represents a hydrogen atom, C １ -C １２ alkyl group, C ３ -C １２ cycloalkyl group, C ５ -C ２０ aryl or C ５ -C ２０ heteroaryl group, C ５ -C ２５ aralkyl group, and these may be independently substituted by one and / or more substituents selected from the group consisting of a hydrogen atom, a 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 alkoxy group, C ５ -C ２４ aryloxy group, C ５ -C ２０ heteroaryloxy group, alkoxy group (-OR''), sulfide group (-SR''), amine group (-NR'' ２ ), and here, the R'' group independently represents a hydrogen atom, C １ -C ５ alkyl, C ６ -C ２４ aryl, C ７ -C ２４ aralkyl).

4. The precursor according to claim 1 or 2 or 3, having the formula CAAC-a, CAAC-b, CAAC-c, CAAC-d, CAAC-e, CAAC-f, CAAC-g, CAAC-h, CAAC-i, CAAC-j, CAAC-k, or CAAC-l 【Chemical Formula 4】

5. A method for synthesizing a cyclic precursor of alkylamine carbene (CAAC) having the formula CAAC-2 or CAAC-3 defined in claim 2 [Chemical Formula 5] comprising, in a first stage, a compound having the formula 2a or 3a undergoing an aza-Claisen type thermal rearrangement reaction in the presence of a Lewis acid to obtain a compound having the formula 2b or 3b 【Chemical Formula 6】 (wherein the substituent R ２ , R ３ , R ４ , R ５ , R １０ , R １１ , R １２ , R １３ , and R １４ have the meanings defined above) which is then subjected, in a second reaction stage, to reduction of the double bond using a transition metal catalyst attached to activated carbon in the presence of hydrogen gas to form a compound having the formula 2c or 3c 【Chemical Formula 7】 (wherein the substituents R ２ , R ３ , R ４ , R １０ , R １１ , R １２ , R １３ , and R １４ have the meanings defined above) which is then subjected, in a third stage, to reaction with a compound having the formula 4 [Chemical 8] (wherein the substituent R ２ , R ３ , R ４ , R １０ , R １１ , R １２ , R １３ , and R １４ have the meanings defined above) in the presence of a Brønsted acid to form a compound having the formula 2d or 3d

6. 【Chemical Formula 9】 (wherein, R ６ , R ７ , R ８ , and R ９ have the meanings defined above) In the second step, the reduction reaction is carried out in the presence of a catalyst selected from Pd, Pt, Rh, Ru, Ag, Au; 【Chemical Formula 10】 (wherein, R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , R １０ , R １１ , R １２ , R １３ , and R １４ substituents have the meanings defined above). In the third step, the reaction is carried out in the presence of a Brønsted acid selected from para-toluenesulfonic acid, sulfuric acid, hydrochloric acid, trifluoroacetic acid, trifluoromethanesulfonic acid, fluorosulfuric acid, Subsequently, this is subjected to a reaction with hydrochloric acid at high temperature, followed by an anion exchange reaction using an anion selected from the group consisting of halogen anions, BF ４ － , PF ６ － , ClO ４ － , CF ３ SO ２ O － to form the corresponding precursor of cyclic alkylamine carbene (CAAC) having the formula CAAC-2 or CAAC-3. The method according to claim 5 In the first step, BF ３ , B(OR) ３ , AlCl ３ , MgCl ２ , TiCl ４ , Ti(OR) ４ is used;

7. A ruthenium complex having the formula 1-Ru (wherein: G is selected from entities such as the following - a ligand having the formula CAAC-5 or CAAC-6 or CAAC-7 【Chemical Formula 11】 or X １ and X ２ are, independently of each other, anionic ligands selected from the group consisting of a halogen anion, -CN, -SCN, -OR ａ , -SR ａ , -O(C=O)R ａ , -O(SO ２ )R ａ , and -OSi(R ａ ) ３ groups, where R ａ is 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 heteroaryloxyl, or C １ -C １２ alkyl, C ３ -C １２ cycloalkyl, C ２ -C １２ alkenyl, or C ５ -C ２０ aryl, optionally substituted with a halogen atom; R １ 、R ２ 、R ３ 、R ４ 、and R ５ are, independently, a hydrogen atom, a C １ -C １２ alkyl group, a C ３ -C １２ cycloalkyl group, a C ５ -C ２０ aryl group or a C ５ -C ２０ heteroaryl group, a C ５ -C ２５ aralkyl group, and these are a hydrogen atom, a halogen atom, a C １ -C １２ alkyl group, a C １ -C １２ perfluoroalkyl group, a C ５ -C ２０ aryl group, a C ５ -C ２０ perfluoroaryl group, a C ５ -C ２０ heteroaryl group, a C １ -C １２ alkoxy group, a C ５ -C ２４ aryloxy group, a C ５ -C ２０ heteroaryloxy group, a sulfide group (-SR''), an amine group (-NR'' ２ ), and may be independently substituted by one and / or more substituents selected from the group consisting of, where the R'' group is independently a hydrogen atom, a C １ -C ５ alkyl, a C ６ -C ２４ aryl, a C ７ -C ２４ aralkyl, or R １ 、R ２ 、R ３ 、R ４ 、and R ５ are linked to form a C ５ -C ２５ ring, In the formula, at least one substituent R １ , R ２ , and R ５ has an alkyl substituent having at least one secondary, tertiary, or quaternary carbon atom, and preferably, at least one substituent R １ , R ２ , and R ５ has an alkyl substituent having at least two secondary, tertiary, or quaternary carbon atoms, more preferably, at least one substituent R １ , R ２ , and R ５ has an alkyl substituent having at least three secondary, tertiary, or quaternary carbon atoms, and most preferably, at least one substituent R １ , R ２ , and R ５ has an alkyl substituent having at least four secondary, tertiary, or quaternary carbon atoms, Each substituent R ６ , R ７ , R ８ , and R ９ represents a hydrogen atom, a halogen atom, a C １ -C １２ alkyl group, or a C ５ -C ２０ aryl group, and these are hydrogen, 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 alkoxy group, C ５ -C ２４ aryloxy group, C ５ -C ２０ heteroaryloxy group or a halogen atom, a sulfide group (-SR''), an amine group (-NR'' ２ ), and may be independently substituted with one and / or more substituents selected from the group consisting of, where the R'' group is independently a hydrogen atom, C １ -C ５ alkyl, C ６ -C ２４ aryl, C ７ -C ２４ aralkyl, or R ６ and R ７ and / or R ８ and R ９ are linked to form a C ５ -C ２５ ring group, R １６ and R １７ each independently represents a hydrogen atom, a halogen atom, an optionally substituted C １ to C ２５ alkyl, an optionally substituted C ３ to C ２５ cycloalkyl, an optionally substituted C １ to C １２ perfluoroalkyl, an optionally substituted C ２ to C ２５ alkene, an optionally substituted C ２ to C ２５ alkenyl, an optionally substituted C ３ to C ２５ cycloalkenyl, an optionally substituted C ２ to C ２５ alkynyl, an optionally substituted C ３ to C ２５ cycloalkynyl, an optionally substituted C １ to C ２５ alkoxyl, an optionally substituted C ５ to C ２５ aryl, an optionally substituted C ５ to C ２５ aryloxyl, an optionally substituted C ６ to C ２５ arylalkyl, an optionally substituted C ５ to C ２５ heteroaryl, an optionally substituted C ５ to C ２５ heteroaryloxyl, an optionally substituted C ５ to C ２５ perfluoroaryl; represents an optionally substituted 3- to 12-membered heterocyclic ring containing a sulfur, oxygen, nitrogen, selenium, or phosphorus atom, Here, R １６ and R １７ substituents may be linked to form a ring selected from the group consisting of C ３ to C ２５ cycloalkyl, C ３ to C ２５ cycloalkenyl, C ３ to C ２５ cycloalkynyl, C ５ to C ２５ aryl, C ５ to C ２５ heteroaryl, C ５ to C ２５ perfluoroaryl; they may independently be substituted with one and / or more substituents selected from the group including a 3- to 12-membered heterocycle containing a sulfur, oxygen, nitrogen, selenium, or phosphorus atom, and these substituents may be a hydrogen atom, a halogen atom, C １ to C ２５ alkyl, C ３ to C ２５ cycloalkyl, C １ to C １２ perfluoroalkyl, C ２ to C ２５ alkene, C ２ to C ２５ alkenyl, C ３ to C ２５ cycloalkenyl, C ２ to C ２５ alkynyl, C ３ to C ２５ cycloalkynyl, C １ to C ２５ alkoxyl, C ５ to C ２５ aryl, C ５ to C ２５ aryloxyl, C ６ to C ２５ arylalkyl, C ５ to C ２５ heteroaryl, C ５ to C ２５ heteroaryloxyl, C ５ to C ２５ perfluoroaryl, and may independently be substituted with one and / or more substituents selected from the group including a 3- to 12-membered heterocycle; Here, the substituent R １６ and R １７ are independently and preferably a hydrogen atom and / or a C ５ to C ２５ aryl, a halogen atom, a C １ to C ２５ alkyl group, a C ２ to C ２５ alkenyl group, an alkoxy group (—OR″), a sulfide group (—SR″), a sulfoxide group (—S(O)R″), a sulfonium group (—S ＋ R″ ２ ), a sulfone group (—SO ２ R″), a sulfonamide group (—SO ２ NR″ ２ ), an amine group (—NR″ ２ ), an ammonium group (—N ＋ R″ ３ ), a nitro group (—NO ２ ), a cyanide group (—CN), a phosphonic acid group (—P(O)(OR″) ２ ), a phosphinic acid group (—P(O)R″(OR″)), a phosphonine group (—P(OR″) ２ ), a phosphine group (—PR″ ２ ), a phosphine oxide group (—P(O)R″ ２ ), a phosphonium group (—P ＋ R″ ３ ), a carboxy 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″), a dithioester group (—CS ２ R″), and represent Here, the R'' groups are independently a hydrogen atom, C １ -C ５ alkyl, C １ -C ５ perfluoroalkyl, C ６ -C ２４ aryl, C ７ -C ２４ aralkyl, C ５ -C ２４ perfluoroaryl, and two R'' groups may be linked to form a C １ -C １２ alkyl group optionally further substituted with a C ３ -C １２ cycloalkyl or C ３ -C ２５ heterocycloalkyl ring, or R'' represents a ketone group (-COR ｃ ), where R ｃ is a C １ -C １２ perfluoroalkyl or alkoxy group (-OR ｄ ), where R ｄ contains a nitrogen atom, an oxygen atom, or a sulfur atom and is optionally further substituted with a C １ -C １２ alkyl group to form a C １ -C １２ alkyl or C ３ -C １２ heterocycloalkyl; - heteroatom 1 - heteroatom 2 【Chemical Formula 12】 (wherein X and substituents R １ ~R １５ have the meanings defined above) - heteroatom 3

8. For example, a hydrogen atom, a halogen atom, an oxygen atom, C １ -C ２５ alkyl, C １ -C ２５ perfluoroalkyl, C ３ -C ２５ cycloalkyl, C ５ -C ２０ alkoxyl, C ５ -C ２０ aryl, C ５ -C ２０ perfluoroaryl, C ７ -C ２０ aralkyl, C ５ -C ２４ aryloxyl, C ２ -C １２ alkenyl, C ６ -C ２０ heteroaryl, or C ５ -C ２４ heteroaryloxyl, a 3- to 12-membered heterocycle (acyl (-COR'), cyano (-CN), carboxy (-COOH), ester (-COOR'), ester (-CH ２ COOR'), ester (-CHR'COOR'), ester (-C(R') ２ COOR'), amide (-CONR' ２ ), Weinreb-type amide (-CON(R')(OR')), sulfone (-SO ２ R'), formyl (-COH), sulfonamide (-SO ２ NR' ２ ), ketone (-COR'), thioamide (-CSNR' ２ ), thioketone (-CSR'), thionoester (-CSOR'), thioester (-COSOR'), dithioester (-CS ２ R') group optionally substituted with a group selected from the group consisting of an oxygen, sulfur, selenium atom (wherein the R' group is independently C １ -C ２５ alkyl, C １ -C ２５ perfluoroalkyl, C ３ -C ２５ cycloalkyl, C ５ -C ２０ alkoxyl, C ５ ~C ２０ aryl, C ５ ~C ２０ perfluoroaryl, C ７ ~C ２０ aralkyl, C ５ ~C ２４ aryloxyl, C ２ ~C １２ alkenyl, C ６ ~C ２０ heteroaryl, C ５ ~C ２４ represents heteroaryloxyl, and then the dashed line represents a direct bond between the heteroatom and the R １７ substituent, or a methylene bridge -CH ２ -, -CHR'-, or -CR' ２ -mediated bond between the R １７ substituent and the heteroatom, where the R １４ substituent is a hydrogen atom, a halogen atom, C １ ~C ２５ alkyl, C ３ ~C ２５ cycloalkyl, C ２ ~C ２５ alkenyl, C ３ ~C ２５ cycloalkenyl, C ２ ~C ２５ alkynyl, C ３ ~C ２５ cycloalkynyl, C １ ~C ２５ perfluoroalkyl, C ５ ~C ２０ alkoxyl, C ５ ~C ２０ aryl, C ５ ~C ２０ perfluoroaryl, C ７ ~C ２０ aralkyl, C ５ ~C ２４ aryloxyl, C ６ ~C ２０ heteroaryl or C ５ ~C ２４ Heteroaryloxy, a 3- to 12-membered heterocycle, an alkoxy group (—O’’’’), a sulfide group (—S’’’’), a sulfoxide group (—S(O)’’’’), a sulfonium group (—S ＋ ’’’’ ２ ), a sulfone group (—SO ２ ’’’’), a sulfonamide group (—SO ２ N’’’’ ２ ), an amine group (—N’’’’ ２ ), an ammonium group (—N ＋ ’’’’ ３ ), a nitro group (—NO ２ ), a cyanide group (—CN), a phosphonic acid group (—P(O)(O’’’’) ２ ), a phosphinic acid group (—P(O)’’’’(O’’’’)), a phosphonine group (—P(O’’’’) ２ ), a phosphine group (—P’’’’ ２ ), a phosphine oxide group (—P(O)’’’’ ２ ), a phosphonium group (—P ＋ ’’’’ ３ ), a carboxy group (—COOH), an ester group (—COO’’’’), an amide group (—CON’’’’ ２ ), an amide group (—N’’’’C(O)’’’’), a formyl group (—CHO), a ketone group (—CO’’’’), a thioamide group (—CSN’’’’ ２ ), a thioketone group (—CS’’’’), a thionoester group (—CSO’’’’), a thioester group (—COS’’), a dithioester group (—CS ２ ’’’’) and is optionally substituted with 1 to 4 substituents independently selected from the group consisting of C ５ to C １５ aryl, where the ’’’’ group represents C １ to C ５ alkyl, C １ to C ５ perfluoroalkyl, C ６ to C ２４ aryl, C ７ to C ２４ aralkyl, C ５ to C ２４ perfluoroaryl); or The ruthenium complex according to claim 7, represented by the formula 1a-Ru A hydrogen atom, methylidene optionally substituted with an R' substituent, C １ -C ２５ alkyl, C １ -C ２５ perfluoroalkyl, C ３ -C ２５ cycloalkyl, C ５ -C ２０ alkoxyl, C ５ -C ２０ aryl, C ５ -C ２０ perfluoroaryl, C ７ -C ２０ aralkyl, C ５ -C ２４ aryloxyl, C ２ -C １２ alkenyl, C ６ -C ２０ alkenyl or C ５ -C ２４ heteroaryloxyl, a 3- to 12-membered heterocyclic ring, an acyl group (-COR'), an ester group (-COOR'), a tert-butylcarboxycarbon group (t-Boc), or a 9-fluorenylmethoxycarbonyl group (Fmoc), a carbamine group (-CONR' ２ ), a sulfone group (-SO ２ R'), a formyl group (-COH), etc., a group selected from the group consisting of a nitrogen atom or a phosphorus atom substituted with a group selected from the group consisting of (wherein the R' group is an acyl group (-COR'), a cyano group (-CN), a carboxy group (-COOH), an ester group (-COOR'), an ester group (-CH ２ COOR'), an ester group (-CHR'COOR'), an ester group (-C(R') ２ COOR'), an amide group (-CONR' ２ ), a sulfone group (-SO ２ R'), a formyl group (-COH), a sulfonamide group (-SO ２ NR' ２ ), a ketone group (-COR'), a thioamide group (-CSNR' ２ ), a thioketone group (-CSR'), a thionoester group (-CSOR'), a thioester group (-COSOR'), a dithioester group (-CS ２ R') (wherein the R' group is C １ to C ２５ alkyl, C １ to C ２５ perfluoroalkyl, C ３ to C ２５ cycloalkyl, C ５ to C ２０ alkoxyl, C ５ to C ２０ aryl, C ５ to C ２０ perfluoroaryl, C ７ to C ２０ aralkyl, C ５ to C ２４ aryloxyl, C ２ to C １２ alkenyl, C ６ to C ２０ heteroaryl, or C ５ to C ２４ heteroaryloxyl), optionally substituted with C １ to C ２５ alkyl, C １ to C ２５ perfluoroalkyl, C ３ to C ２５ cycloalkyl, C ５ to C ２０ alkoxyl, C ５ to C ２０ aryl, C ５ to C ２０ perfluoroaryl, C ７ to C ２０ aralkyl, C ５ to C ２４ aryloxyl, C ２ to C １２ alkenyl, C ６ to C ２０ heteroaryl, or C ５ to C ２４ heteroaryloxyl, and then the dashed line represents a direct bond between the heteroatom and the R １４ substituent, or a methylene bridge (CH ２ ), -(CHR'), or (CR' ２ ) - represents the bond between the R １７ substituent and the heteroatom; wherein R １７ is a hydrogen atom, a halogen atom, C １ to C ２５ alkyl, C ３ to C ２５ cycloalkyl, C ２ to C ２５ alkenyl, C ３ to C ２５ cycloalkenyl, C ２ to C ２５ alkynyl, C ３ to C ２５ cycloalkynyl, C １ to C ２５ perfluoroalkyl, C ５ to C ２０ alkoxyl, C ５ to C ２０ aryl, C ５ to C ２０ perfluoroaryl, C ７ to C ２０ aralkyl, C ５ to C ２４ aryloxyl, C ６ to C ２０ heteroaryl or C ５ to C ２４ heteroaryloxyl, a 3- to 12-membered heterocyclic ring, an alkoxy group (-OR''), a sulfide group (-SR''), a sulfoxide group (-S(O)R''), a sulfonium group (-S ＋ R'' ２ ), a sulfone group (-SO ２ R''), a sulfonamide group (-SO ２ NR'' ２ ), an amine group (-NR'' ２ ), an ammonium group (-N ＋ R'' ３ ), a nitro group (-NO ２ ), a cyano group (-CN), a phosphinous group (-P(O)(OR'')) ２ ), a phosphinic group (-P(O)R''(OR'')), a phosphonin group (-P(OR'') ２ ), a phosphine group (-PR'' ２ ), a phosphine oxide group (-P(O)R'') ２ ), a phosphonium group (-P ＋ R'' ３ ), a carboxy 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 (-COSOR''), a dithioester group (-CS ２ R''), and is optionally substituted with 1 to 4 substituents independently selected from the group consisting of C ５ -C １５ aryl, where the R'' group is C １ -C ５ alkyl, C １ -C ５ perfluoroalkyl, C ６ -C ２４ aryl, C ７ -C ２４ aralkyl, C ５ -C ２４ perfluoroaryl) or “n” means 1 or 0 Those selected from the group containing a halogen atom (next, the dashed line represents a direct bond between the hetero atom and the R １７ substituent, and in the formula, R １７ substituent is a hydrogen atom, a halogen atom, C １ to C ２５ alkyl, C ３ to C ２５ cycloalkyl, C ２ to C ２５ alkenyl, C ３ to C ２５ cycloalkenyl, C ２ to C ２５ alkynyl, C ３ to C ２５ cycloalkynyl, C １ to C ２５ perfluoroalkyl, C ５ to C ２０ alkoxyl, C ５ to C ２０ aryl, C ５ to C ２０ perfluoroaryl, C ７ to C ２０ aralkyl, C ５ to C ２４ aryloxyl, C ６ to C ２０ heteroaryl or C ５ to C ２４ heteroaryloxyl, a 3- to 12-membered heterocyclic ring, an alkoxy group (-OR''), a sulfide group (-SR''), a sulfoxide group (-S(O)R''), a sulfonium group (-S ＋ R'' ２ ), a sulfone group (-SO ２ R''), a sulfonamide group (-SO ２ NR'' ２ ), an amine group (-NR'' ２ ), an ammonium group (-N ＋ R'' ３ ), a nitro group (-NO ２ ), a cyano group (-CN), a phosphonous group (-P(O)(OR'')) ２ ), a phosphinic acid group (-P(O)R''(OR'')), a phosphonin group (-P(OR'') ２ ), a phosphine group (—PR″ ２ ), a phosphine oxide group (—P(O)R″ ２ ), a phosphonium group (—P ＋ R″ ３ ), a carboxy 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″), a dithioester group (—CS ２ R″), optionally substituted with 1 to 4 substituents independently selected from the group consisting of, C ５ ~C １５ aryl, or C ５ ~C ２５ polyaryl, wherein the R″ group is C １ ~C ５ alkyl, C １ ~C ５ perfluoroalkyl, C ６ ~C ２４ aryl, C ７ ~C ２４ aralkyl, C ５ ~C ２４ perfluoroaryl))).

9. The ruthenium complex according to claim 7 or 8, having the formula 1b-Ru 【Chemical 13】 (wherein X １ and X ２ , and R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ substituents have the meanings defined above;

10. Z is selected from the group containing a halogen atom, an O atom, an S atom, a Se atom, or an NR''' group, where R''' is methylidene, C １ -C ２５ alkyl, C １ -C ２５ perfluoroalkyl, C ３ -C ２５ cycloalkyl, C ５ -C ２０ alkoxyl, C ５ -C ２０ aryl, C ５ -C ２０ perfluoroaryl, C ７ -C ２０ aralkyl, C ５ -C ２４ aryloxyl, C ２ -C １２ alkenyl, C ６ -C ２０ heteroaryl or C ５ -C ２４ heteroaryloxyl, a 3- to 12-membered heterocyclic ring, an acyl group (-COR'), an ester group (-COOR'), a tert-butyl carboxy carbon group (t-Boc) or a 9-fluorenylmethoxycarbonyl group (Fmoc), a carbamine group (-CONR' ２ ), a sulfone group (-SO ２ R'), a formyl group (-COH), where the R' group is C １ -C ２５ alkyl, C １ -C ２５ perfluoroalkyl, C ３ -C ２５ cycloalkyl, C ５ -C ２０ alkoxyl, C ５ -C ２０ aryl, C ５ -C ２０ perfluoroaryl, C ７ -C ２０ aralkyl, C ５ -C ２４ aryloxyl, C ２ -C １２ alkenyl, C ６ -C ２０ heteroaryl or C ５ ~C ２４ represents heteroaryloxyl or a halogen atom, and in the formula, if Z represents a halogen atom, then R １８ is absent; R １８ independently represents a hydrogen atom, C １ to C ２５ alkyl, C １ to C ２５ cycloalkyl, C ５ to C ２０ alkoxyl, C ５ to C ２０ aryl, C ５ to C ２４ aryloxyl, -COOR''', -CH ２ COOR''', -CONR''' ２ group, -CH ２ CONR''' ２ group, -COR''', -CH ２ COR''', -CON(OR'')(R'''), -CH ２ CON(OR'')(R''') group, or a halogen atom, where ''' represents C １ to C １２ alkyl, C ３ to C １２ cycloalkyl, C ２ to C １２ alkenyl, C ６ to C ２０ aryl, which are optionally substituted with at least one C １ to C １２ alkyl, C １ to C １２ perfluoroalkyl, C １ to C １２ alkoxyl, C ６ to C ２４ aryloxyl, or a halogen atom; R １９ 、 R ２０ 、 R ２１ 、 and R ２２ are, independently, a hydrogen atom, a halogen atom, C １ - C ２５ alkyl group, C ２ - C ２５ alkenyl group, C ５ - C ２５ aryl group, (-OR'') alkoxy group, sulfide group (-SR''), sulfoxide (-S(O)R''), sulfonium group (-S ＋ R'' ２ ), sulfone group (-SO ２ R''), sulfonamide group (-SO ２ NR'' ２ ), amine group (-NR'' ２ ), ammonium group (-N ＋ R'' ３ ), nitro group (-NO ２ ), cyano group (-CN), phosphate group (-P(O)(OR'')) ２ ), phosphorus 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 ), carboxy 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 (-COSOR''), dithioester group (-CS ２ R''), where the R'' group is C １ - C ５ alkyl, C １ - C ５ perfluoroalkyl, C ６ - C ２４ aryl, C ７ - C ２４ Aralkyl, C ５ ~C ２４ represents perfluoroaryl, where R １６ , R １７ , R １８ , and R １９ substituents are linked and may form a substituted or unsubstituted ring system C ４ ~C １０ or a polycyclic system C ４ ~C １２ ). The ruthenium complex according to any one of claims 7 to 9, having the formula 1c-Ru or 1d-Ru or 1e-Ru

11. 【Chemical Formula 14】 (wherein X １ and X ２ , and R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ substituents have the meanings defined above; R １６ and R １７ each independently represents a hydrogen atom, a halogen atom, an optionally substituted C １ -C ２５ alkyl, an optionally substituted C ３ -C ２５ cycloalkyl, an optionally substituted C １ -C １２ perfluoroalkyl, an optionally substituted C ２ -C ２５ alkene, an optionally substituted C ２ -C ２５ alkenyl, an optionally substituted C ３ -C ２５ cycloalkenyl, an optionally substituted C ２ -C ２５ alkynyl, an optionally substituted C ３ -C ２５ cycloalkynyl, an optionally substituted C １ -C ２５ alkoxyl, an optionally substituted C ５ -C ２５ aryl, an optionally substituted C ５ -C ２５ aryloxyl, an optionally substituted C ６ -C ２５ arylalkyl, an optionally substituted C ５ -C ２５ heteroaryl, an optionally substituted C ５ -C ２５ heteroaryloxyl, an optionally substituted C ５ -C ２５ perfluoroaryl; represents an optionally substituted 3- to 12-membered heterocyclic ring containing a sulfur, oxygen, nitrogen, selenium, or phosphorus atom; Here, R １６ and R １７ substituents may be linked to form a ring selected from the group consisting of C ３ to C ２５ cycloalkyl, C ３ to C ２５ cycloalkenyl, C ３ to C ２５ cycloalkynyl, C ５ to C ２５ aryl, C ５ to C ２５ heteroaryl, C ５ to C ２５ perfluoroaryl; and may independently be substituted with one and / or more substituents selected from the group containing a 3- to 12-membered heterocyclic ring containing a sulfur, oxygen, nitrogen, selenium, or phosphorus atom, and these substituents may be a hydrogen atom, a halogen atom, C １ to C ２５ alkyl, C ３ to C ２５ cycloalkyl, C １ to C １２ perfluoroalkyl, C ２ to C ２５ alkene, C ２ to C ２５ alkenyl, C ３ to C ２５ cycloalkenyl, C ２ to C ２５ alkynyl, C ３ to C ２５ cycloalkynyl, C １ to C ２５ alkoxyl, C ５ to C ２５ aryl, C ５ to C ２５ aryloxyl, C ６ to C ２５ arylalkyl, C ５ to C ２５ heteroaryl, C ５ to C ２５ heteroaryloxyl, C ５ to C ２５ perfluoroaryl, and may independently be substituted with one and / or more substituents selected from the group containing a 3- to 12-membered heterocyclic ring). ​ ​ 【Chemical Formula 15】 (wherein X １ and X ２ , and R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R １０ , R １１ , R １２ , R １３ , R １４ , R １５ , R ２３ , R ２４ substituents have the meanings defined above). ​ Complexes represented by the formulas Ru-a, Ru-b, Ru-c, Ru-d, Ru-e, Ru-f, Ru-g, Ru-h, Ru-i, Ru-j, Ru-k, Ru-l 【Chemical 16】 The ruthenium complex according to any one of claims 7 to 10, selected from the complexes represented by the formula.

12. Use of a compound having the formula 1-Ru defined in any one of claims 7 to 11 as a pre-catalyst and / or catalyst in olefin metathesis reactions, in particular in the metathetic reaction of diastereoselective ring rearrangement (DRRM), the "alkene-alkyne" (en-yn) type metathesis, or the ring-closing metathesis (RCM) reaction, cross-metathesis (CM), homometathesis (cross-metathesis between two molecules of the same olefin), ethenolysis, isomerization in the ROMP or ADMET type polymerization reaction.

13. The use according to claim 12, wherein the reaction is carried out in an organic solvent such as toluene, mesitylene, hexane, cyclohexane, ethyl acetate, methyl acetate, methyl carbonate, ethyl carbonate, tert-butyl-methyl ether, cyclopentyl-methyl ether, diethyl ether, THF, 2-Me-THF, 4-Me-THP, dioxane, DME, PAO, PEG, paraffin, esters of saturated fatty acids.

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

15. The use according to any one of claims 1 to 14, wherein the reaction is carried out at 20 to 200 °C.

16. The use according to any one of claims 1 to 15, wherein the reaction is carried out for 5 minutes to 48 hours.

17. The use according to any one of claims 1 to 16, wherein the 1-Ru compound is used in an amount of 10 mol% or less.

18. The use according to any one of claims 1 to 17, wherein the 1-Ru compound is used in an amount of 0.1 mol% or less.

19. The use according to any one of claims 1 to 18, wherein the 1-Ru compound is added to the reaction mixture in portions several times as a solid and / or continuously using a pump as a solution in an organic solvent.

20. The use according to any one of claims 1 to 19, wherein the gaseous by-products of the reaction, selected from ethylene, propylene, and butylene, are actively removed from the reaction mixture using an inert gas barbottage or under reduced pressure.

21. A ruthenium complex having the formula 1aa-Ru 【Chemical 17】 (wherein X １ and X ２ each independently represent an anionic ligand selected from the group consisting of a halogen anion, -CN, -SCN, -OR ａ , -SR ａ , -O(C=O)R ａ , -O(SO ２ )R ａ , and -OSi(R ａ ) ３ group, where R ａ represents 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 heteroaryloxyl, or C optionally substituted with a halogen atom １ -C １２ alkyl, C ３ -C １２ cycloalkyl, C ２ -C １２ alkenyl, or C ５ -C ２０ aryl; R １ 、R ２ 、R ３ 、R ４ 、and R ５ each independently represents a hydrogen atom, a C １ -C １２ alkyl group, a C ３ -C １２ cycloalkyl group, a C ５ -C ２０ aryl group or a C ５ -C ２０ heteroaryl group, a C ５ -C ２５ aralkyl group, and these may be independently substituted by one and / or more substituents selected from the group consisting of a hydrogen atom, a halogen atom, a C １ -C １２ alkyl group, a C １ -C １２ perfluoroalkyl group, a C ５ -C ２０ aryl group, a C ５ -C ２０ perfluoroaryl group, a C ５ -C ２０ heteroaryl group, a C １ -C １２ alkoxy group, a C ５ -C ２４ aryloxy group, a C ５ -C ２０ heteroaryloxy group, a sulfide group (-SR''), an amine group (-NR'' ２ ), and R'' groups each independently represent a hydrogen atom, a C １ -C ５ alkyl, a C ６ -C ２４ aryl, a C ７ -C ２４ aralkyl, or R １ 、R ２ 、R ３ 、R ４ 、and R ５ are linked to form a C ５ -C ２５ ring, In the formula, at least one substituent R １ R ２ R ３ R ４ and R ５ has an alkyl substituent having at least one quaternary carbon atom, preferably, at least one substituent R １ R ４ and R ５ has an alkyl substituent having at least two quaternary carbon atoms, more preferably, at least one substituent R １ R ４ and R ５ has an alkyl substituent having at least three quaternary carbon atoms; Each substituent R ６ and R ７ is a hydrogen atom, a halogen atom, C １ to C １２ alkyl group or C ５ to C ２０ aryl group, and these are hydrogen, C １ to C １２ alkyl group, C １ to C １２ perfluoroalkyl group, C ５ to C ２０ aryl group, C ５ to C ２０ perfluoroaryl group, C ５ to C ２０ heteroaryl group, C １ to C １２ alkoxy group, C ５ to C ２４ aryloxy group, C ５ to C ２０ heteroaryloxy group or a halogen atom, a sulfide group (—SR''), an amine group (—NR'' ２ ), and may be independently substituted by one and / or a plurality of substituents selected from the group consisting of, wherein the R'' group is independently a hydrogen atom, C １ to C ５ alkyl, C ６ to C ２４ aryl, C ７ to C ２４ aralkyl, or R ６ and R ７ and / or R ８ and R ９ are linked to form a C ５ to C ２５ ring group; R ８ The substituent is C ５ to C ２０ aryl group, which represents hydrogen, C １ to C １２ alkyl group, C １ to C １２ perfluoroalkyl group, C ５ to C ２０ aryl group, C ５ to C ２０ perfluoroaryl group, C ５ to C ２０ heteroaryl group, C １ to C １２ alkoxy group, C ５ to C ２４ aryloxy group, C ５ to C ２０ heteroaryloxy group or halogen atom, sulfide group (–SR''), amine group (–NR'' ２ ), and may be independently substituted with one and / or more substituents selected from the group consisting of, where the R'' group is independently a hydrogen atom, C １ to C ５ alkyl, C ６ to C ２４ aryl, C ７ to C ２４ aralkyl, R ９ The substituent is a hydrogen atom, a halogen atom, C １ to C １２ alkyl group, and these are hydrogen, C １ to C １２ alkyl group, C １ to C １２ perfluoroalkyl group, C ５ to C ２０ aryl group, C ５ to C ２０ perfluoroaryl group, C ５ to C ２０ heteroaryl group, C １ to C １２ alkoxy group, C ５ to C ２４ aryloxy group, C ５ to C ２０ heteroaryloxy group or a halogen atom, a sulfide group (—SR″), an amine group (—NR″ ２ ), and may be independently substituted with one and / or more substituents selected from the group consisting of, where the R″ group is independently a hydrogen atom, C １ to C ５ alkyl, C ６ to C ２４ aryl, C ７ to C ２４ represents aralkyl, Alternatively, R ８ and R ９ are linked to form a group of C ５ to C ２５ rings. "n" means 1 or 0; Z is selected from the group consisting of a halogen atom, an O atom, an S atom, a Se atom, or an NR''' group, where R''' is methylidene, C １ -C ２５ alkyl, C １ -C ２５ perfluoroalkyl, C ３ -C ２５ cycloalkyl, C ５ -C ２０ alkoxyl, C ５ -C ２０ aryl, C ５ -C ２０ perfluoroaryl, C ７ -C ２０ aralkyl, C ５ -C ２４ aryloxyl, C ２ -C １２ alkenyl, C ６ -C ２０ heteroaryl or C ５ -C ２４ heteroaryloxyl, a 3- to 12-membered heterocyclic ring, an acyl group (-COR'), an ester group (-COOR'), a tert-butyl carboxycarbonyl group (t-Boc) or a 9-fluorenylmethoxycarbonyl group (Fmoc), a carbamine group (-CONR' ２ )), a sulfone group (-SO ２ R'), a formyl group (-COH), where the R' group is C １ -C ２５ alkyl, C １ -C ２５ perfluoroalkyl, C ３ -C ２５ cycloalkyl, C ５ -C ２０ alkoxyl, C ５ -C ２０ aryl, C ５ -C ２０ perfluoroaryl, C ７ -C ２０ aralkyl, C ５ -C ２４ aryloxyl, C ２ -C １２ alkenyl, C ６ -C ２０ heteroaryl or C ５ ~C ２４ represents heteroaryloxy or a halogen atom, and in the formula, if Z represents a halogen atom, then R １８ is absent; R １８ is independently a halogen atom, C １ to C ２５ alkyl, C １ to C ２５ cycloalkyl, C ５ to C ２０ alkoxyl, C ５ to C ２０ aryl, C ５ to C ２４ aryloxyl, -COOR''', -CH ２ COOR''', -CONR''' ２ group, -CH ２ CONR''' ２ group, -COR''', -CH ２ COR''', -CON(OR'')(R'''), -CH ２ CON(OR'')(R''') group, or a halogen atom, where R''' is C １ to C １２ alkyl, C ３ to C １２ cycloalkyl, C ２ to C １２ alkenyl, C ６ to C ２０ aryl, which are optionally substituted with at least C １ to C １２ alkyl, C １ to C １２ perfluoroalkyl, C １ to C １２ alkoxyl, C ６ to C ２４ aryloxyl, or a halogen atom; R １９ 、 R ２０ 、 R ２１ 、 and R ２２ are, independently, a hydrogen atom, a halogen atom, C １ - C ２５ alkyl group, C ２ - C ２５ alkenyl group, C ５ - C ２５ aryl group, an alkoxy group (-OR''), a sulfide group (-SR''), a sulfoxide (-S(O)R''), a sulfonium group (-S ＋ R'' ２ ), a sulfone group (-SO ２ R''), a sulfonamide group (-SO ２ NR'' ２ ), an amine group (-NR'' ２ ), an ammonium group (-N ＋ R'' ３ ), a nitro group (-NO ２ ), a cyano group (-CN), a phosphonous acid group (-P(O)(OR'') ２ ), a phosphinous acid group (-P(O)R''(OR'')), a phosphonin group (-P(OR'') ２ ), a phosphine group (-PR'' ２ ), a phosphine oxide group (-P(O)R'' ２ ), a phosphonium group (-P ＋ R'' ３ ), a carboxy 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 (-COSOR''), a dithioester group (-CS ２ R''), where the R'' group is C １ - C ５ alkyl, C １ - C ５ perfluoroalkyl, C ６ - C ２４ aryl, C ７ - C ２４ aralkyl, C ５ ~C ２４ represents a perfluoroaryl, where R １６ , R １７ , R １８ , and R １９ substituents are linked and thus form a substituted or unsubstituted C ４ ~C １０ cyclic or C ４ ~C １２ polycyclic system (there is a possibility of forming). **Claim 22** The ruthenium complex according to claim 21, represented by the formula 1aaa-Ru 【Chemical Formula 18】 wherein X １ and X ２ , and R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ The substituents have the meanings defined in claim 21 above; Z is selected from the group including a halogen atom, an O atom, an S atom, and a Se atom). **Claim 23** The ruthenium complex according to claim 21 or 22, having the formula 1aaaa-Ru 【Chemical Formula 19】 (wherein X １ and X ２ , and R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ the substituents have the meanings defined in claim 21 above; Ar is C ６ ~C ２０ represents an aryl group, which is hydrogen, 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 alkoxy group, C ５ ~C ２４ aryloxy group, C ５ ~C ２０ heteroaryloxy group or a halogen atom, a sulfide group (-SR''), an amine group (-NR'' ２ ), and may be independently substituted by one and / or more substituents selected from the group consisting of, where the R'' group is independently a hydrogen atom, C １ ~C ５ alkyl, C ６ ~C ２４ aryl, C ７ ~C ２４ represents aralkyl). **Claim 24** R １ 、R ２ 、R ３ 、R ４ 、R ５ The ruthenium complex according to any one of claims 21 to 23, wherein at least one of the substituents of R **Claim 25** The ruthenium complex having the formula 1a-Ru, as defined in claim 7 【Chemical 20】 A method for synthesizing a ruthenium complex having An alkylidene ruthenium complex having the formula 10 【Chemical 21】 (wherein: L １ represents a neutral ligand selected from the group consisting of pyridine or substituted pyridine, P(''), ３ P(O''), ３ O(''), ２ N(''), ３ where each '' independently represents C １ to C １２ alkyl, C ３ to C １２ cycloalkyl, C ５ to C ２０ aryl, C ７ to C ２４ aralkyl, C ５ to C ２４ perfluoroaryl, 5- to 12-membered heteroaryl; N, Z, X １ , X ２ , and substituent R １８ , R １９ , R ２０ , R ２１ , and R ２２ have the meanings defined above) is subjected to a reaction with a carbene having the formula 8 【Chemical 22】 (wherein the substituents R １ to R ９ have the meanings defined above) characterized by the method.

Images