Method for selective cleavage of C-SCF3 bonds and analogues

Abstract

The present invention relates to a method for preparing compound A-H by reacting compound A-X in the presence of a metal complex containing nickel, palladium or rhodium(I); a ligand, a hydride, and a solvent, A is selected from the group consisting of: (C6-C 10 ) aryl group, heteroaryl group, and vinyl compound, and X is selected from the group consisting of: YCF3, Y(O) n CF3, YCF2SO2Ph, Y(O) n CF2SO2Ph, Y(O) n CF2COOR, Y(O) n CF2CONR2, Y(O) n CF2CH2OH, Y(O) n CN, Y(O) n CHF2, Y(O) n CF2H, Y(O) n CF2C n F 2n+1 , Y(O) n CF2COR, where Y is S or Se, n is 1 or 2, and R is (C1-C6) alkyl.

Description

[Technical Field] 【0001】 The present invention relates to a method for selective cleavage of C-SCF3 bonds and analogues of such bonds. [Background technology] 【0002】 In a society concerned with the environment, land and water pollution, and a circular economy, the development of new technologies to achieve these objectives is a real challenge and a focus of attention across the entire chemical industry today. 【0003】 The field of organofluorine chemistry is unavoidable, with fluorine compounds accounting for a very high proportion in many fields, including materials science, pharmaceuticals, and the agricultural chemistry industry. Indeed, the incorporation of fluorine atoms or fluorinated units has the potential to significantly alter the physicochemical properties of organic molecules, demonstrating the scientific community's interest in this research area. However, the widespread use of these compounds raises questions about their fate and degradation. In recent years, there has been strong scientific and societal interest in chlorofluorocarbons (CFCs), hydrofluorocarbons (HFCs), and perfluoroalkyl and polyfluoroalkyl compounds (PFAs). Furthermore, it is important to consider the fate of emerging fluorinated groups, such as derivatives containing the SCF3 unit (e.g., toltrazuryl and fipronil), which have become indispensable. 【0004】 In this situation, developing tools that can enhance the value of these fluorinated derivatives, which are considered waste after a single use, by converting them into high-value compounds, would have a clear environmental impact and enable cost reduction. Therefore, it is essential to address this challenge and develop innovative tools to remove constraints in synthesis. 【0005】 Currently, (hetero)aromatic derivatives or C(sp) on the vinyl position 2 )-SRf bond or C(sp 3There is currently no technology that can selectively cleave )-SRf bonds, and any advancements would have significant impacts from both scientific and environmental perspectives. 【0006】 N. Barbero et al., Organic Letters, 2012, 14, pp. 796-799 (Supplementary Information, S1-S78), discuss the catalytic reductive cleavage of inactivated C-SMe bonds. As shown in the last paragraph of the left column on page 797, the SMe group, i.e., the electron-donating group on the sulfur atom, is reported to be the most efficient in the reductive cleavage of the CS bond. The optimization processes described in Tables 1-6 of the Supplementary Information (pp. S3-S5) were performed only for this particular thioether. Table 7 of this document (pp. S5) confirms that the SMe group yields the highest yield for CS bond cleavage, while electron-withdrawing groups such as Ac and CONMe2 are less efficient. 【0007】 Surprisingly, it has now been discovered that CS bonds and analogues of such bonds on organic molecules can be selectively cleaved in the presence of electron-withdrawing fluorinated groups such as CF3 or similar fluorine-containing groups. [Prior art documents] [Non-patent literature] 【0008】 [Non-Patent Document 1] N. Barbero et al., Organic Letters, 2012, 14, pp. 796-799 (Supplementary Information, S1-S78) [Overview of the project] [Problems that the invention aims to solve] 【0009】 Therefore, one object of the present invention is to provide a tool for defluorinating fluorinated compounds. 【0010】 One object of the present invention is to provide a method for defluorinating fluorinated compounds, for example, by cleaving a C-SCF3 bond or an analogue of such a bond. [Means for Solving the Problem] 【0011】 The present invention relates to a compound having the formula (I): A-H and a compound having the formula (II): in the presence of a metal complex containing nickel, palladium or rhodium (I), a ligand, a hydride, and a solvent, A-X by reacting them, which is a method for preparation, - A is as follows: - An aryl group of (C6-C ) (the aryl group is preferably halogen, (C1-C6) alkyl, (C1-C6) alkoxy, -CN, -CF3, -OCF3, -NR 10 ) aryl group R, -SiR a R b R a R b R c R, -BR a R b R, (C2-C6) alkenyl, (C2-C6) alkynyl, -C(=O)-NR a R b R, and -C(=O)-O(C1-C6) alkyl, and is optionally substituted with at least one substituent selected from the group consisting of; R a and R b are each independently H or a (C1-C6) alkyl group; R c is a (C1-C6) alkyl group); <00002​​​​​​​​​​​​​a R b , (C6~C 10 ) is optionally substituted with at least one substituent selected from aryl and -C(=O)-O(C1~C6)alkyl, R a , R b , and R c (As stipulated above) and; The following equation (III): 【0012】 [ka] 【0013】 Vinyl compounds having (R 1 These include halogens, (C1-C6) alkyls, (C1-C6) alkoxys, -CN, -CF3, -OCF3, and -NR. a R b , -Si(R c )3, -BR a R b (C2~C6) alkenyl, (C2~C6) alkynyl, -C(=O)-NR a R b Selected from the group consisting of -C(=O)-O(C1~C6)alkyl, R a , R b , and R c (as defined above) is selected from the group consisting of; - X is YCF3, YOCF3, YO2CF3, YCF2SO2Ph, YOCF2SO2Ph, YO2CF2SO2Ph, Y(O) n CF2COOR', Y(O) n CF2CONR'2, Y(O) n CF2CH2OH,Y(O) n CN, Y(O) n CHF2, Y(O) n CF2H, Y(O) n CF2C n F 2n+1 , Y(O) n Selected from the group consisting of CF2COR', Y is S or Se, and Y is preferably S. This relates to a method in which n is 1 or 2 and R' is an (C1-C6) alkyl group. 【0014】 Therefore, the present invention is based on formula (I): AH Compounds having the following characteristics: In the presence of nickel-containing metal complexes, ligands, hydrides, and solvents, Formula (II): AX A method for preparing a compound having the following characteristics by reacting them: - A is as follows: (C6~C 10 ) Aryl group (The aryl group is preferably a halogen, (C1-C6)alkyl, (C1-C6)alkoxy, -CN, -CF3, -OCF3, -NR) a R b , -SiR a R b R c ,-BR a R b (C2~C6) alkenyl, (C2~C6) alkynyl, -C(=O)-NR a R b , and are optionally substituted with at least one substituent selected from the group consisting of -C(=O)-O(C1~C6)alkyl groups; R a and R b These are, independently of each other, H or (C1-C6) alkyl groups; R c (is an alkyl group (C1-C6)); A heteroaryl group containing 5 to 10 atoms, including at least one heteroatom selected from O, N, and S. (The heteroaryl group is preferably a halogen, (C1-C6)alkyl, (C1-C6)alkoxy, -CN, -CF3, -OCF3, -NR) a R b , -Si(R c )3, -BR a R b (C2~C6) alkenyl, (C2~C6) alkynyl, -C(=O)-NR aR b is optionally substituted with at least one substituent selected from -C(=O)-O(C1-C6)alkyl, and R a , R b , and R c are as defined above); The following formula (III): 【0015】 [Chemical formula] 【0016】 A vinyl compound having (R 1 is halogen, (C1-C6)alkyl, (C1-C6)alkoxy, -CN, -CF3, -OCF3, -NR a R b , -Si(R c )3, -BR a R b , (C2-C6)alkenyl, (C2-C6)alkynyl, -C(=O)-NR a R b , and -C(=O)-O(C1-C6)alkyl, and R a , R b [[ID= 44]], and R c are as defined above) and is selected from the group consisting of; - X is YCF3, YOCF3, YO2CF3, YCF2SO2Ph, YOCF2SO2Ph, YO2CF2SO2Ph, Y(O) n CF2COOR, Y(O) n CF2CONR2, Y(O) n CF2CH2OH, Y(O) n CN, Y(O) n CHF2, Y(O) n CF2H, Y(O) n CF2C n F 2n+1 , Y(O) n CF2COR, and is selected from the group consisting of, Y is S or Se, and Y is preferably S; n is 1 or 2, and R is (C1-C6)alkyl, relating to a method. 【0017】 According to one embodiment, in the above formula (I) or (II), A is as follows: (C6 - C 10 ) aryl group (the aryl group is optionally substituted with at least one substituent selected from the group consisting of (C1 - C6) alkyl, (C1 - C6) alkoxy, and -C(=O)-O(C1 - C6) alkyl) and; a heteroaryl group containing 5 to 10 atoms and at least one heteroatom selected from O, N, and S (the heteroaryl group is optionally substituted with at least one substituent selected from halogen, (C1 - C6) alkyl, (C1 - C6) alkoxy, (C6 - C 10 ) aryl, and -C(=O)-O(C1 - C6) alkyl) and; the following formula (III): 【0018】 【Chemical formula】 【0019】 a vinyl compound having (R 1 is selected from the group consisting of (C1 - C6) alkyl, (C1 - C6) alkoxy, and -C(=O)-O(C1 - C6) alkyl)) and is selected from the group consisting of. 【0020】 According to one embodiment, in the above formula (II), X is SCF3, SOCF3, SO2CF3, SCF2SO2Ph, SOCF2SO2Ph, SO2CF2SO2Ph, S(O) n CF2COOR, S(O) n CF2CONR2, S(O) n CF2CH2OH, S(O) n CN, S(O) n CHF2, S(O) n CF2H, S(O) n CF2C n F 2n+1 、S(O)n Selected from the group consisting of CF2COR and all analogues in this list in the selenium series, where R and n are as defined above. 【0021】 According to one embodiment, in formula (II) above, X is SCF3, SOCF3, SO2CF3, SCF2SO2Ph, SOCF2SO2Ph, SO2CF2SO2Ph, S(O) n CF2COOR, S(O) n CF2CONR2, S(O) n CF2CH2OH, S(O) n CN, S(O) n CHF2, S(O) n CF2H, S(O) n CF2C n F 2n+1 , S(O) n The group is selected from CF2COR and SeCF3. 【0022】 According to one embodiment, in formula (II) above, X is selected from the group consisting of SCF3, SOCF3, SO2CF3, SCF2SO2Ph, SO2CF2SO2Ph, and SeCF3. [Modes for carrying out the invention] 【0023】 The following provisions are provided to illustrate and define the meanings and scopes of various terms used in this specification to describe the present invention. 【0024】 "C t ~C z The expression "C1-C3" refers to a carbon chain that can have t to z carbon atoms. For example, C1-C3 refers to a carbon chain that can have 1 to 3 carbon atoms. 【0025】 The term "alkyl group" means a linear or branched saturated hydrocarbon aliphatic group containing 1 to 12 carbon atoms, unless otherwise specified. Examples include the methyl group, ethyl group, n-propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, or pentyl group. 【0026】 The term "aryl group" refers to a cyclic aromatic group containing between 6 and 10 carbon atoms. Examples of aryl groups include the phenyl group and the naphthyl group. 【0027】 The term "heteroaryl group" refers to a 5-10 membered aromatic monocyclic or bicyclic group containing 1-4 heteroatoms selected from O, S, or N. Examples include imidazolyl, thiazolyl, oxazolyl, furanyl, thiophenyl, pyrazolyl, oxadiazolyl, tetrazolyl, pyridinyl, pyrazinyl, pyrimidinyl, pyridadinyl, indolyl, benzofuranyl, benzothiophenyl, benzoxazolyl, benzimidazolyl, indazolyl, benzothiazolyl, isobenzothiazolyl, benzotriazolyl, quinolinyl, and isoquinolinyl groups. 【0028】 As heteroaryl groups containing 5 to 6 atoms, including 1 to 4 nitrogen atoms, the following representative groups may be specifically mentioned: pyrrolyl group, pyrazolyl group, 1,2,3-triazolyl group, 1,2,4-triazolyl group, tetrazolyl group, and 1,2,3-triazinyl group. 【0029】 Examples of heteroaryl groups include thiophenyl, oxazolyl, flazanil, 1,2,4-thiadiazolyl, naphthilidinil, quinoxalinil, phthalazinil, imidazo[1,2-a]pyridine, imidazo[2,1-b]thiazolyl, sinnolinil, benzoflazanil, azaindol, benzimidazolyl, benzothiophenyl, thienopyridyl, thienopyrimidinil, pyrrolopyridyl, imidazopyridyl, benzoazaindole, 1,2,4-triazinil, indolidinil, isoxazolyl, isoquinolinil, isothiazolyl, purinyl, quinazolinil, quinolinil, isoquinolyl, 1,3,4-thiadiazolyl, thiazolyl, isothiazolyl, carbazolyl, and the corresponding groups resulting from their condensation or condensation with a phenyl nucleus. 【0030】 When an alkyl group is substituted with an aryl group, the terms "arylalkyl group" or "aralkyl group" are used. An "arylalkyl" group or "aralkyl" group is an arylalkyl group, and the aryl group and alkyl group are as defined above. Among arylalkyl groups, benzyl or phenethyl groups may be specifically mentioned. 【0031】 The term "halogen" refers to fluorine, chlorine, bromine, or iodine. 【0032】 The term "alkoxy group" means an -O-alkyl group, and alkyl groups are as previously defined. Examples include -O-(C1~C4) alkyl groups, particularly -O-methyl group, -O-ethyl group, -O-propyl group, -O-isopropyl group as -O-C3 alkyl groups, and -O-butyl group, -O-isobutyl group, or -O-tert-butyl group as -O-C4 alkyl groups. 【0033】 As used herein, the term "alkynyl" includes an unsaturated non-aromatic hydrocarbon group having 2 to 6 carbon atoms and containing at least one triple bond. Preferably, the alkynyl group is linear. Preferably, the alkynyl group is -(CH2) m -C ≡ CH group, and m is an integer from 1 to 4. 【0034】 As used herein, the term "alkenyl" includes an unsaturated non-aromatic hydrocarbon group having 2 to 6 carbon atoms and containing at least one double bond. Preferably, the alkenyl group is linear. Preferably, the alkenyl group is -(CH2) m -CH = 2 CH groups, and m is an integer from 1 to 4. 【0035】 The above-mentioned "alkyl," "aryl," and "heteroaryl" groups can be substituted with one or more substituents. Among these substituents, the following groups may be listed: amino, hydroxyl, thiol, oxo, halogen, alkyl, alkoxy, alkylthio, alkylamino, aryloxy, arylalkoxy, cyano, trifluoromethyl, carboxy, or carboxyalkyl. 【0036】 The term "alkylthio" means -S-alkyl group, and alkyl groups are defined as described above. 【0037】 The term "alkylamino" means -NH-alkyl group, and alkyl groups are defined as described above. 【0038】 The term "aryloxy" refers to an -O-aryl group, which is defined above. 【0039】 The term "arylalkoxy" refers to an aryl-alkoxy group, where the aryl and alkoxy groups are defined above. 【0040】 The term "carboxyalkyl" means HOOC-alkyl group, where the alkyl group is as defined above. Examples of carboxyalkyl groups include carboxymethyl and carboxyethyl. 【0041】 The term "haloalkyl group" refers to an alkyl group as defined above, in which one or more hydrogen atoms are replaced by halogen atoms. Examples include fluoroalkyl groups, particularly CF3 or CHF2. 【0042】 The term "carboxyl" refers to the COOH group. 【0043】 The term "oxo" means "=O". 【0044】 In one embodiment of the method according to the present invention, the hydride is of formula R 2 (R 3 )2SiH is a silane compound, R 2 and R 3 These are independently (C1-C6) alkyl groups, (C1-C6) alkoxy groups, and (C6-C 10 ) Selected from aryl groups, the aryl group is (C1-C6)alkyl, (C1-C6)alkoxy, -CN, -OCF3, -NR a R b , -Si(R c )3, -BR a R b (C2~C6) alkenyl, (C2~C6) alkynyl, -C(=O)-NR a R b R is optionally substituted with at least one substituent selected from -C(=O)-O(C1~C6)alkyl and CF3. a , R b , and R c This is as defined above. 【0045】 In particular, hydrides are of formula R 2 (R 3 )2SiH is a silane compound, R 2 and R 3 These are independently (C1-C6) alkyl groups, (C1-C6) alkoxy groups, and (C6-C 10 The aryl group is selected from aryl groups, and the aryl group is optionally substituted with at least one substituent selected from (C1-C6)alkyl, (C1-C6)alkoxy, and -C(=O)-O(C1-C6)alkyl, and CF3. 【0046】 In one embodiment of the method according to the present invention, the hydride is selected from the group consisting of EtMe2SiH, Me(OMe)2SiH, Me(OEt)2SiH, (OEt)3SiH, Et3SiH, tBuMe2SiH, Me2PhSiH, Me2BnSiH, MePh2SiH, Ph3SiH, Me2(p-CF3(C6H4))SiH, Me2(p-tBu(C6H4))SiH, and 1,1,3,3-tetramethyldisiloxane (TMDSO). In one embodiment, the hydride is Me2(p-CF3(C6H4))SiH or Me2BnSiH. 【0047】 According to one embodiment, in the method of the present invention, the ligand is selected from the group consisting of 1,5-cyclooctadiene (COD), 1,2-bis(dicyclohexylphosphino)ethane (dcype), 1,1'-bis(diphenylphosphino)ferrocene (dppf), 1,1'-bis(di-tert-butylphosphino)ferrocene (DTBPF), 4,5-bis(diphenyl-phosphino)-9,9-dimethylxanthene (XantPhos), triphenylarsine (AsPh3), and triphenylphosphan (PPh3). 【0048】 The term "ligand" refers to a chemical component that can bond with the metal in a metal complex. The initial state of a metal complex is the state in which the metal complex is used in the reaction medium. In the initial state of a metal complex, the ligand can bond with the metal. 【0049】 Alternatively, a ligand can be added to the reaction medium in addition to the metal complex. In such a case, the ligand binds to the metal in the reaction medium. 【0050】 According to one embodiment of the method, the ligand is bonded to the metal in the initial state of the metal complex. 【0051】 According to another embodiment of the method, a ligand is added to the reaction medium in addition to the metal complex. 【0052】 According to one embodiment of the method, at least one first ligand is bonded to the metal in the initial state of the metal complex, and at least one second ligand is added to the reaction medium in addition to the metal complex, wherein the first and second ligands are either identical or different. 【0053】 Preferably, the metal complex is a Ni(0) complex such as bis(1,5-cyclooctadiene)nickel (Ni[cod]2) or bis(triphenylphosphine)nickel (Ni[PPh3]2). 【0054】 In another embodiment, the metal complex may include nickel, palladium, or rhodium(I). For example, the metal complex may be a Pd(0) complex such as tris(dibenzylideneacetone)dipalladium(O) of formula Pd2dba3, or tetrakis(triphenylphosphine)palladium(O) of formula Pd(PPh3)4. In particular, the metal complex may be a Pd(II) complex such as [1,3-bis(2,6-diisopropylphenyl)imidazole-2-ylidene](3-chloropyridyl)palladium(II) dichloride (PEPSI Pd IPr, 905459-27-0), palladium(II) acetate of formula Pd(OAc)2, or allylpalladium(II) chloride dimer of formula [Pd(π-allyl)Cl]2. Alternatively, the metal complex may be an Rh(I) complex such as rhodium carbonyl chloride of formula [Rh(CO)2Cl]2, or hydroxy(cyclooctadiene)rhodium(I) dimer of formula [Rh(OH)COD]2. 【0055】 According to one embodiment, the solvent used in the method according to the present invention is selected from ordinary solvents used in the art. Preferably, the solvent in the method according to the present invention is toluene. 【0056】 In one embodiment of the method according to the present invention, the reaction is carried out at a temperature of 90°C to 140°C, and preferably, the reaction may be carried out at 90°C, 110°C, 120°C, and 140°C. 【0057】 The present invention also provides a method for preparing a compound having formula (I) from a compound having formula A-SCF3(II-1), A is a heteroaryl group comprising 5 to 10 atoms and at least one heteroatom selected from O, N, and S, wherein the heteroaryl group is a halogen, (C1-C6)alkyl, (C1-C6)alkoxy, (C6-C 10 The method described above is optionally substituted with at least one substituent selected from aryl and -C(=O)-O(C1~C6)alkyl groups. 【0058】 In particular, A is a heteroaryl group containing 5 to 10 atoms and at least one heteroatom selected from O, N, and S, wherein the heteroaryl group is optionally substituted with at least one substituent selected from halogens, (C1-C6)alkyl, (C1-C6)alkoxy, and -C(=O)-O(C1-C6)alkyl. 【0059】 The present invention also includes formula (I-2): 【0060】 [ka] 【0061】 Compounds having the following characteristics: Formula (II-2): 【0062】 [ka] 【0063】 A method for preparing a compound having the following characteristics: X1 is selected from the group consisting of SCF3, SOCF3, SO2CF3, SCF2SO2Ph, SOCF2SO2Ph, SO2CF2SO2Ph, and SeCF3, according to the method defined above. 【0064】 According to one embodiment of the method described above, the reaction is carried out in the presence of toluene using bis(1,5-cyclooctadiene)nickel and Me2(p-CF3(C6H4))SiH. 【0065】 The present invention also includes formula (I-3): 【0066】 [ka] 【0067】 Compounds having the following characteristics: Formula (II-3): 【0068】 [ka] 【0069】 A method for preparing a compound having the following characteristics: p is 0, 1, 2, or 3; R 4 The method described above is one in which the elements are identical or different and selected from the group consisting of (C1-C6)alkyl, (C1-C6)alkoxy, and -C(=O)-O(C1-C6)alkyl. 【0070】 The present invention also includes formula (I-4): 【0071】 [ka] 【0072】 Compounds having the following characteristics: Formula (II-4): 【0073】 [ka] 【0074】 A method for preparing a compound having the following characteristics: R 1This relates to the method specified above, which is selected from the group consisting of halogens, (C1-C6) alkyls, and -OC(=O)-(C1-C6) alkyls. 【0075】 According to one embodiment of the above method, the reaction is carried out using bis(1,5-cyclooctadiene)nickel and BnMe2SiH in the presence of toluene, a base, and a molecular sieve. 【0076】 Preferably, the base is K2HPO4. [Examples] 【0077】 General procedure for reductive cleavage General Procedure A: Ni(cod)2 (14 mg, 0.05 mmol, 10 mol%), (hetero)aryl-SCF3 derivatives 1a-1k or 3-7 (0.5 mmol, 1 equivalent), Me2(p-CF3(C6H4))SiH (408 mg, 2 mmol, 4 equivalents), and toluene (2 mL) were charged under argon. The resulting solution was stirred at 140°C for 48 hours. The mixture was cooled to 21°C. The solution was filtered through CHROMAFIL® XtraPTFE-45 / 25, and the solvent was evaporated under reduced pressure. The residue was purified by silica gel flash column chromatography to obtain the desired products 2a-2k. 【0078】 The same procedure can be performed using Ni(PPh3)2 (0.05 mmol, 10 mol%) instead of Ni(cod)2. 【0079】 The process, reactants, compound structures, and corresponding yields are shown in Scheme 1 below: - Compounds 2a to 2k are obtained by selective cleavage of the compound of formula (II)AX (where A is a heteroaryl group represented by (Het)Ar and X is SCF3) (Scheme 1A); Compounds 3-7 are compounds of formula (II)AX (where A is a heteroaryl group represented by (Het)Ar, and X is SOCF3, SO2CF3, SCF2SO2Ph, SO2CF2SO2Ph, and SeCF3). The yields shown next to the numbers 3-7 are the isolation yields of compound 2a obtained starting from compounds 3-7 (Scheme 1B). 【0080】 [ka] 【0081】 The results demonstrate the versatility of this method. In fact, we have successfully extended this method not only to the reduction of CS bonds or C-Se bonds in molecules supporting SCF3 or SeCF3 groups, but also to the cleavage of CS bonds in molecules supporting SCF2SO2Ph groups or other sulfonated groups with various oxidation states, including sulfoxides and sulfones of the corresponding fluorine group. 【0082】 General Procedure B: Ni(cod)2 (14 mg, 0.05 mmol, 10 mol%), aryl-SCF38 or vinyl-SCF310 derivative (0.5 mmol, 1 equivalent), K2HPO4 (174 mg, 1 mmol, 2 equivalents), Me2BnSiH (301 mg, 2 mmol, 4 equivalents), toluene (2 mL), and 4 Å MS (62 mg) were charged under argon. The resulting solution was stirred at 140 °C for 48 hours. The mixture was cooled to 21 °C. The solution was filtered through CHROMAFIL® Xtra PTFE-45 / 25, and the solvent was evaporated under reduced pressure. The residue was purified by silica gel flash column chromatography to obtain the desired product 9 or 11. 【0083】 [ka] 【0084】 [ka] 【0085】 General Procedure C: Ni(cod)2 (14 mg, 0.05 mmol, 10 mol%), 2-((trifluoromethyl)thio)benzo[d]thiazole 1a (118 mg, 0.5 mmol, 1 equivalent), Me2(p-CF3(C6H4))SiH (408 mg, 2 mmol, 4 equivalents), the corresponding ligand excluding C1 (0.05 mmol, 10 mol%), and toluene (0.25 M, 2 mL) were charged under argon. The resulting solution was stirred at 90°C for 16 hours. The mixture was cooled to 21°C. The solution was filtered through CHROMAFIL® Xtra PTFE-45 / 25, and the solvent was evaporated under reduced pressure. The residue was purified by silica gel flash column chromatography to obtain the desired product 2a. The yield was measured using 1,1,1,2-tetrachloroethane as an internal standard. 1 This was determined by 1H NMR. 【0086】 [ka] 【0087】 [Table 1] 【0088】 1,3,5-trimethoxybenzene as an internal standard. Yield in parentheses. 【0089】 The results indicate that reductive cleavage of 1a is achieved whether the ligand forms a complex with the metal in its initial form or whether the ligand is added to the reaction mixture in addition to the metal complex. 【0090】 General Procedure D: Reaction conditions are reported in Table 2: Ni(cod)2 (14 mg, 0.05 mmol, 10 mol%), 2-((trifluoromethyl)thio)benzo[d]thiazole 1a (118 mg, 0.5 mmol, 1 equivalent), silane compound (2 mmol, 4 equivalents) as a hydride, and toluene (0.25 M, 2 mL) were charged under argon in an oven-dried 10 mL tube equipped with a stirring bar. The resulting solution was stirred at various temperatures for 16 hours. The mixture was cooled to 21°C. The solution was filtered through CHROMAFIL® Xtra PTFE-45 / 25 and the solvent was evaporated under reduced pressure. The residue was purified by silica gel flash column chromatography, the sample was dried and loaded, and eluted in the following solvent system to obtain the desired product 2a. The yield was calculated using 1,1,1,2-tetrachloroethane as an internal standard. 1 This was determined by 1H NMR. 【0091】 [ka] 【0092】 The hydrides and their equivalent amounts, reaction temperature, and corresponding yields are reported in Table 2 below. 【0093】 [Table 2]

Claims

[Claim 1] Equation (I): AH Compounds having [a certain characteristic] are prepared in the presence of a metal complex, ligand, hydride, and solvent containing nickel, palladium, or rhodium(I). Formula (II): AX A method for preparing by reacting compounds having the following: A is as follows: (C 6 ~C 10 ) Aryl group (The aryl group is preferably halogen, (C 1 -C 6 )alkyl, (C 1 -C 6 )alkoxy, -CN, -CF 3 , -OCF 3 , -NR a R b , -SiR a R b R c , -BR a R b , (C 2 -C 6 )alkenyl, (C 2 -C 6 )alkynyl, -C(=O)-NR a R b , and -C(=O)-O(C 1 -C 6 )alkyl, and is optionally substituted with at least one substituent selected from the group consisting of; R a and R b These are H or (C) independent of each other. 1 ~C 6 ) is an alkyl group; R c is, (C 1 ~C 6 (It is an alkyl group) and; A heteroaryl group containing 5 to 10 atoms, including at least one heteroatom selected from O, N, and S. (The heteroaryl group is preferably a halogen, (C 1 ~C 6 ) alkyl, (C 1 ~C 6 ) Alkoxy, -CN, -CF 3 , -OCF 3 , -NR a R b , -Si(R c ) 3 ,-BR a R b , (C 2 ~C 6 ) Alkenil, (C 2 ~C 6 ) Alkinyl, (C 6 ~C 10 )aryl, -C(=O)-NR a R b , and -C(=O)-O(C 1 ~C 6 )Optionally substituted with at least one substituent selected from alkyl groups, R a , R b , and R c (As stipulated above) and; The following equation (III): 【Chemistry 1】 Vinyl compounds having (R 1 is halogen, (C 1 ~C 6 ) alkyl, (C 1 ~C 6 ) Alkoxy, -CN, -CF 3 , -OCF 3 , -NR a R b , -Si(R c ) 3 ,-BR a R b , (C 2 ~C 6 ) Alkenil, (C 2 ~C 6 ) Alkinyl, -C(=O)-NR a R b , and -C(=O)-O(C 1 ~C 6 ) Selected from the group consisting of alkyl groups, R a , R b , and R c (as defined above) is selected from the group consisting of; X is YCF 3 YOCF 3 YO 2 CF 3 YCF 2 SO 2 Ph, YOCF 2 SO 2 Ph, YO 2 CF 2 SO 2 Ph, Y(O) n CF 2 COOR, Y(O) n CF 2 CONR 2 Y(O) n CF 2 CH 2 OH, Y(O) n CN, Y(O) n CHF 2 Y(O) n CF 2 H, Y(O) n CF 2 C n F 2n+1 Y(O) n CF 2 selected from the group consisting of COR, and Y is S or Se, n is 1 or 2, and R is (C 1 ~C 6 ) an alkyl method. [Claim 2] The method according to claim 1, wherein the metal complex contains nickel. [Claim 3] The method according to claim 1 or 2, wherein the ligand is bonded to the metal in the initial state of the metal complex, and / or the ligand is added to the reaction medium in addition to the metal complex. [Claim 4] The aforementioned hydride is, Formula R 2 (R 3 ) 2 SiH is a silane compound, R 2 and R 3 They are independent of each other, (C 1 ~C 6 ) alkyl group, (C 1 ~C 6 )alkoxy group, and (C 6 ~C 10 ) Selected from aryl groups, the aryl group is (C 1 ~C 6 ) alkyl, (C 1 ~C 6 )alkoxy, -CN, -OCF 3 , -NR a R b , -Si(R c ) 3 ,-BR a R b , (C 2 ~C 6 ) Alkenil, (C 2 ~C 6 ) Alkinyl, -C(=O)-NR a R b , and -C(=O)-O(C 1 ~C 6 ) alkyl, and CF 3 It is optionally substituted with at least one substituent selected from R a , R b , and R c The method according to any one of claims 1 to 3, wherein the property is as defined in claim 1. [Claim 5] The hydride is EtMe 2 SiH, Me(OMe) 2 SiH, Me(OEt) 2 SiH, (OEt) 3 SiH, Et 3 SiH, tBuMe 2 SiH, Me 2 PhSiH, Me 2 BnSiH, MePh 2 SiH, Ph 3 SiH, Me 2 (p-CF 3 (C 6 H 4 ))SiH, Me 2 (p-tBu(C 6 H 4 The method according to any one of claims 1 to 4, selected from the group consisting of ))SiH and 1,1,3,3-tetramethyldisiloxane (TMDSO). [Claim 6] The aforementioned hydride is Me 2 (p-CF 3 (C 6 H 4 ))SiH or Me 2 The method according to any one of claims 1 to 5, wherein BnSiH. [Claim 7] The ligands are 1,5-cyclooctadiene (COD), 1,2-bis(dicyclohexylphosphino)ethane (dcype), 1,1'-bis(diphenylphosphino)ferrocene (dppf), 1,1'-bis(di-tert-butylphosphino)ferrocene (DTBPF), 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (XantPhos), and triphenylarsine (AsPh 3 ), and triphenylphosphan (PPh 3 The method according to any one of claims 1 to 6, selected from the group consisting of ). [Claim 8] The method according to any one of claims 1 to 7, wherein the solvent is toluene. [Claim 9] The method according to any one of claims 1 to 8, wherein the reaction is carried out at a temperature of 90°C to 140°C. [Claim 10] The method according to any one of claims 1 to 9, wherein the metal complex is a Ni(0) complex such as bis(1,5-cyclooctadiene)nickel. [Claim 11] Compounds having formula (I) are classified as formula A-SCF 3 A method for preparing a compound having (II-1), A is a heteroaryl group comprising 5 to 10 atoms and at least one heteroatom selected from O, N, and S, wherein the heteroaryl group is a halogen, (C 1 ~C 6 ) alkyl, (C 1 ~C 6 )alkoxy, (C 6 ~C 10 )aryl, and -C(=O)-O(C 1 ~C 6 The method according to any one of claims 1 to 10, wherein the molecule is optionally substituted with at least one substituent selected from alkyl groups. [Claim 12] Equation (I-2): 【Chemistry 2】 Compounds having the following characteristics: Formula (II-2): 【Transformation 3】 A method for preparing a compound having the following characteristics: X 1 SCF 3 SOCF 3 , SO 2 CF 3 SCF 2 SO 2 Ph, SOCF 2 SO 2 Ph, SO 2 CF 2 SO 2 Ph and SeCF 3 A method according to any one of claims 1 to 10, selected from the group consisting of the following. [Claim 13] The reaction occurred in the presence of toluene, involving bis(1,5-cyclooctadiene)nickel and Me 2 (p-CF 3 (C 6 H 4 The method according to claim 11 or 12, carried out using SiH. [Claim 14] Equation (I-3): 【Chemistry 4】 Compounds having the following characteristics: Formula (II-3): 【Transformation 5】 A method for preparing a compound having the following characteristics: p is 0, 1, 2, or 3; R 4 They are either the same or different, (C 1 ~C 6 ) alkyl, (C 1 ~C 6 )alkoxy, and -C(=O)-O(C 1 ~C 6 The method according to any one of claims 1 to 10, selected from the group consisting of alkyl groups. [Claim 15] Equation (I-4): 【Transformation 6】 Compounds having the following characteristics: Formula (II-4): 【Transformation 7】 A method for preparing a compound having the following characteristics: R 1 is halogen, (C 1 ~C 6 )alkyl, and -OC(=O)-(C 1 ~C 6 The method according to any one of claims 1 to 10, selected from the group consisting of alkyl groups. [Claim 16] The reaction proceeded in the presence of toluene, a base, and a molecular sieve, involving bis(1,5-cyclooctadiene)nickel and BnMe 2 The method according to claim 14 or 15, carried out using SiH. [Claim 17] The aforementioned base is K 2 Hpo 4 The method according to claim 16.

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