Salicylaldehyde-containing diamine oxazoline compound and metal complex thereof as well as preparation method and application of salicylaldehyde-containing diamine oxazoline compound and metal complex

Abstract

The invention discloses a chiral salicylaldehyde-containing diamine oxazoline compound of which the structural formula is shown in the following formula (1), and discloses a preparation method of the chiral salicylaldehyde-containing diamine oxazoline compound and a metal complex of the chiral salicylaldehyde-containing diamine oxazoline compound prepared by the chiral salicylaldehyde-containing diamine oxazoline compound. The metal complex of the chiral salicylaldehyde diamine oxazoline compound can be used for catalyzing a sulfoxide compound to be subjected to a deoxidation reduction reaction to generate a thioether compound, and especially can be used for preparing a thioether product with large steric hindrance, and the product yield can reach 90% or above. The metal complex can also catalyze the epoxidation reaction of olefin compounds, the catalytic activity is higher, and the dosage of the catalyst is smaller. # imgabs0 #

Description

Technical Field

[0001] The invention relates to a salicylaldehyde diamine oxazoline compound and a preparation method thereof, a metal complex containing the salicylaldehyde diamine oxazoline compound and use of the metal complex as a catalyst. Background Art

[0002] In the field of redox reaction research, the methodology of transition metal complex catalysis has attracted extensive attention from academia and industry worldwide, and the research on ligands connected to central metals is also very extensive. Among them, the salen ligand obtained by condensation of alkyl diamine or aryl diamine with salicylaldehyde is a very classic ligand, which can form complexes with many metals to catalyze many types of reactions [(a) W. Liu, JT Groves. Acc. Chem. Res. 2015, 48, 1727–1735. (b) X. Han, C. Yuan, B. Hou, L, -J. Liu. H.–Y. Li, Y. Liu, Y. Cui. Che m.Soc.Rev.,2020,49,6248-6272.(c)MAMalik,OADaR,P.Gull,MYWani.AAHashmi.Med.Chem.Commun.,2018,9,409-436]; In 2016, Gao Shuang et al. first reported the phenylenediamine bisoxazoline ligand and characterized its structure [W.Dai,J.Li,G.-S.Li,H.Yang L.-Y.Wang,S.Gao.Org.Lett.,2013,15,4138-4141]; It is mainly coordinated with cheap metals (Fe, Co, Ni) to form catalysts, which are widely used in asymmetric epoxidation and asymmetric dihydroxylation of olefins. Complexes of other transition metals have also been synthesized and used to catalyze organic reactions. The inventors synthesized a salicylaldehyde diamine oxazoline compound, which is of great significance in the field of transition metal catalysis.

[0003] Sulfide compounds are vital components of various commercial drugs (such as antibiotics) and chemicals (such as fuel additives), and they occupy a very important position in organic synthesis [(a) McGarrigle, EM; Myers, EL; Illa, O.; Shaw, MA; Riches, SL; Aggarwal, VK Chem. Rev. 2007, 107, 5841. (b) Rickard, D.; Luther III, GW Chem. Rev. 2007, 107, 514.]. Among them, the deoxygenation reduction reaction of sulfoxides, as an important type of transformation, has considerable practicality in organic synthesis (especially asymmetric synthesis reactions). For example, in asymmetric synthesis reactions, after stereoselective induction, the chiral sulfinyl group can be removed by reducing the sulfoxide to a sulfide. However, the reduction of sulfoxides involves chemical selectivity issues, and the production of byproduct thiols also limits the application of early methodologies. With the development of metal organics, various metals and their complexes or Lewis acids are added as catalysts in the sulfoxide reduction system to accelerate the reduction reaction. It is of great significance to develop more sulfoxide reduction systems that are simple to operate, mild in conditions and practical and effective. Sulfoxide compounds have been widely used in the pharmaceutical industry [Chen, C.; Li, Y.; Xiao, Y.; Zhu, L.; Cheng, C.; Liu, Y. Chin. J. Org. Chem. 2011, 31, 925]. However, the sulfoxide reduction system in the prior art often faces limitations such as side reactions, low yields, difficult post-treatment or harsh reaction conditions [(a) Kukushkin, VY Coord. Chem. Rev. 1995, 139, 375. (b) Firouzabadia, H.; Jamalianni, AJ Sulfur Chem. 2008, 29, 53. (b) Shiri, L.; Kazemi, M. Res. Chem. Intermed. 2017, 43, 6007.]. For sulfoxide reduction products with large steric hindrance, the yield is very low. Therefore, it is of great significance to develop inexpensive metal-catalyzed reduction reactions of sulfoxides with high efficiency, high yield and high chemical selectivity. Summary of the invention

[0004] The invention discloses a salicylaldehyde diamine oxazoline compound and a preparation method thereof, wherein the compound is prepared by connecting the SP2 carbon atom in the oxazoline ring with the 2-position of bromobenzene, and connecting the imine group after the unilateral condensation of salicylaldehyde and diamine with the 1-position of bromobenzene. The invention also discloses a metal complex of the salicylaldehyde diamine oxazoline compound; and relates to the metal complex having a catalytic effect as a catalyst in a reduction reaction, particularly in the deoxygenation reduction of a sulfoxide group.

[0005] The present invention is achieved through the following technical solutions:

[0006] A salicylaldehyde diamine oxazoline compound, the structural formula of which is shown in the following formula (1):

[0007]

[0008] R 1 , R 2 Each independently represents H, one of the following groups which are unsubstituted or substituted by one or more substituents A: C1-C12 alkyl, C5-C12 cycloalkyl, C6-C12 aryl; the substituent A is one or more of C1-C5 alkyl, C1-C5 alkoxy, phenyl, C1-C5 fluoroalkyl, C1-C5 fluoroalkoxy, hydroxyl, and halogen;

[0009] R 1 , R 2 When R is a different substituent, 1 , R 2 The connected carbon atom is a chiral carbon atom, and the compound represented by formula (1) is a chiral salicylaldehyde diamine-containing oxazoline compound.

[0010] Preferred R 1 is C1-C12 alkyl, phenyl or benzyl, more preferably methyl, isopropyl, tert-butyl, phenyl or benzyl;

[0011] Preferred R 2 It is H or C1-C12 alkyl, more preferably H or methyl.

[0012] R 3 , R 4 Each of the following groups is independently H, unsubstituted or substituted by one or more substituents A: C1-C12 alkyl, C5-C12 cycloalkyl, C6-C12 aryl; the substituent A is one or more of C1-C5 alkyl, C1-C5 alkoxy, phenyl, C1-C5 fluoroalkyl, C1-C5 fluoroalkoxy, hydroxyl, halogen;

[0013] Preferred R 3 , R 4 Each is independently H, unsubstituted or C1-C12 alkyl substituted with 1-2 C1-C5 alkoxy groups, more preferably R 3 , R 4 Each is independently H, methyl, ethyl, isopropyl or tert-butyl.

[0014] R 5 , R 6 , R 7 , R 8Each is independently H, C1-C4 fluoroalkoxy, F, Cl, nitro, or C1-C12 alkyl which is unsubstituted or substituted with 1-2 C1-C4 alkoxy groups, more preferably R 5 , R 6 , R 7 , R 8 Each is independently H or C1-C12 alkyl; more preferably R 5 , R 6 , R 7 , R 8 is H, methyl, ethyl, isopropyl or tert-butyl.

[0015] R 9 , R 10 Each is independently H, C1-C12 alkyl, C1-C4 fluoroalkoxy, F, Cl, nitro, C5-C12 cycloalkyl, C6-C12 aryl;

[0016] or R 9 , R 10 and the two carbon atoms connected thereto are connected to form a ring to form a C5-C12 cycloalkyl, a C6-C12 aryl or a C5-C12 heterocyclic aromatic group; the H on the C5-C12 cycloalkyl, the C6-C12 aryl or the C5-C12 heterocyclic aromatic group is not substituted or is substituted by a substituent B, and the substituent B is a C1-C5 alkyl, a C1-C5 alkoxy, a phenyl, a hydroxyl, a nitro or a halogen;

[0017] Preferred R 9 , R 10 Each is independently H, C1-C12 alkyl, C6-C12 aryl or R 9 , R 10 And the two carbon atoms connected to it are connected to form a ring to form a phenyl or naphthyl group.

[0018] R 11 is H, one of the following groups which is unsubstituted or substituted by one or more substituents A: C1-C12 alkyl, C5-C12 cycloalkyl, C6-C12 aryl; the substituent A is C1-C5 alkyl, C1-C5 alkoxy, phenyl, C1-C5 fluoroalkyl, C1-C5 fluoroalkoxy, hydroxyl or halogen; preferably R 10 is H or C1-C12 alkyl; more preferably R 11 is H, methyl, ethyl, isopropyl or tert-butyl.

[0019] R 12 , R 13 , R 14 , R 15Each is independently H, C1-C12 alkyl which is unsubstituted or substituted by 1-2 C1-C4 alkoxy groups, C1-C4 fluoroalkoxy group, F, Cl, Br, nitro, or C5-C12 cycloalkyl which is unsubstituted or substituted by 1-3 substituents C, wherein the substituent C is C1-C4 alkyl or C1-C4 alkoxy group;

[0020] Preferred R 12 , R 13 , R 14 , R 15 Each is independently H, C1-C12 alkyl, F, Cl or Br; more preferably R 12 , R 14 H; R 13 , R 15 Each is independently H, C1-C12 alkyl or Br, more preferably H, Br, methyl, ethyl, isopropyl or tert-butyl.

[0021] R 9 , R 10 When the two carbon atoms connected to it are connected to form a ring to form a phenyl group, the chemical formula is as follows (1-1):

[0022]

[0023] R 1 , R 2 When the substituents are different, the chiral salicylaldehyde diamine-containing oxazoline compound is highly optically pure, and the highly optically pure compound means having an enantiomeric selectivity of more than 90%, preferably more than 95%, and more preferably more than 99%.

[0024] The present invention also discloses a method for preparing a salicylaldehyde diamine oxazoline compound represented by formula (1), wherein the method comprises the following steps:

[0025] (a) Under nitrogen protection, the 2-oxazolinyl bromobenzene compound represented by formula (2) and the diamine compound represented by formula (3) are subjected to a coupling reaction in the presence of a catalyst to obtain a compound represented by formula (4);

[0026] (b) Under nitrogen protection, the compound represented by formula (4) and the salicylaldehyde compound represented by formula (5) undergo condensation reaction to obtain the salicylaldehyde-containing diamine oxazoline compound represented by formula (1).

[0027]

[0028]

[0029] R 1 ~R 15 The definition of is as mentioned above.

[0030] The catalyst in step (a) is a transition metal salt, an organic phosphine ligand, and an inorganic base.

[0031] Further, the transition metal salt is a metal salt of Ru, Rh, Pd, or Ir, preferably dichlorobistriphenylphosphine palladium;

[0032] The inorganic base may be sodium tert-butoxide or potassium tert-butoxide, preferably sodium tert-butoxide;

[0033] The organic phosphine ligand may be triphenylphosphine, tricyclohexylphosphine, 1,2-bis(diphenylphosphino)ethane or 1,1′-bis(diphenylphosphino)ferrocene, preferably 1,1′-bis(diphenylphosphino)ferrocene.

[0034] The reaction in step (a) is preferably carried out in an organic solvent, and the organic solvent is any one of benzene, carbon tetrachloride, petroleum ether, tetrahydrofuran, dimethylformamide, ethyl ether, dichloromethane, chloroform, toluene, xylene, cyclohexane, n-hexane, n-heptane, dioxane, and acetonitrile, preferably toluene.

[0035] The volume amount of the organic solvent in step (a) is 2 to 10 mL / mmol based on the amount of the compound represented by formula (2).

[0036] As a further improvement, the reaction temperature of the coupling reaction in step (a) is -0°C to 150°C, preferably heated to reflux for reaction, and the reaction time is 1 hour to 48 hours.

[0037] As a further improvement, in step (a) of the present invention, the molar ratio of the 2-oxazolinyl bromobenzene compound shown in formula (2), the diamine compound shown in formula (3), the transition metal inorganic salt, the organic phosphine ligand, and the inorganic base is 1:1-5:0.01-1:0.02-2:2-10, preferably 1:1-3:0.01-0.1:0.02-0.1:2-4.

[0038] In the step (a), after the reaction is completed, the reaction solution is post-treated to obtain the compound shown in formula (4), and the post-treatment method is: the reaction solution is cooled to room temperature, filtered, washed with dichloromethane, concentrated and separated by column chromatography to obtain the compound shown in formula (4). The eluent used for column chromatography is a mixed solvent of petroleum ether and ethyl acetate.

[0039] In the step (b), the molar ratio of the compound represented by formula (4) to the salicylaldehyde compound represented by formula (5) is 1:1-10, preferably 1:1-5, and more preferably 1:1-2.

[0040] The step (b) may or may not include the addition of a catalyst. When a catalyst is added, the catalyst may be a protonic acid or a molecular sieve. The amount of the catalyst is 1 to 5% of the amount of the compound represented by formula (4).

[0041] Preferably, step (b) is carried out without adding a catalyst.

[0042] The reaction solvent of step (b) is an organic solvent, preferably methanol or ethanol, more preferably ethanol. The volume amount of the reaction solvent of step (b) is 2 to 10 mL / mmol based on the amount of the compound represented by formula (4).

[0043] The reaction temperature of step (b) is heated to reflux, and the reaction time is 15 to 30 hours.

[0044] After the reaction of step (b) is completed, the reaction solution is post-treated to obtain the salicylaldehyde diamine-containing oxazoline compound shown in formula (1). The post-treatment method is: the reaction solution is cooled to room temperature, filtered, the filtrate is washed and concentrated, and then column chromatography is performed to obtain the salicylaldehyde diamine-containing oxazoline compound shown in formula (1).

[0045] The present invention also discloses a metal complex containing salicylaldehyde diamine oxazoline compounds, wherein the metal complex is a transition metal salt ME of a subgroup element of the periodic table. n The general formula of the metal complex containing salicylaldehyde diamine oxazoline compound obtained by complexation reaction is as shown in the following formula (6):

[0046]

[0047] In formula (6), R 1 -R 15 As mentioned before;

[0048] In formula (6), M is a transition metal such as Fe, Co, Ni, Cu, Ag, Au, Ru, Rh, Pd, Os or Ir;

[0049] E is any one of a halide (F, Cl, Br, I), a pseudohalide (cyanide, cyanate, tetrafluoroborate, isocyanate), a carboxylic acid, a sulfonic acid, and an anion of a phosphonic acid (carbonate, formate, acetate, propionate, methanesulfonate, trichloromethanesulfonate, phenylsulfonate, toluenesulfonate, phosphate, and hexafluorophosphate);

[0050] n is the number of E, which is 0, 1, 2 or 3. When n=0, it means that M is not connected to E. Generally speaking, when M is a divalent metal cation, the valence of the oxygen anion and the N anion is balanced with the divalent metal cation, and no connection to E is required.

[0051] R 1 , R 2 When R is a different substituent, 1 , R 2 The connected carbon atom is a chiral carbon atom. The compound shown in formula (6) is a metal complex of a chiral salicylaldehyde diamine oxazoline compound and can be used for chiral catalytic reactions.

[0052] The metal complex containing salicylaldehyde diamine oxazoline compound is prepared by the following method:

[0053] Under nitrogen protection, the salicylaldehyde diamine oxazoline compound represented by formula (1) and the transition metal salt ME n The reaction is carried out in an organic solvent for 1 to 20 hours to obtain a metal complex containing a salicylaldehyde diamine oxazoline compound represented by formula (6); the organic solvent is ethanol.

[0054] The salicylaldehyde diamine oxazoline compound represented by formula (1) and the transition metal salt ME n The amount ratio of the substance is 0.9 to 2.2:1, preferably 0.9 to 1.1:1, and more preferably 1 to 1.1:1.

[0055] The synthesis of the metal complex containing salicylaldehyde diamine oxazoline compounds can be carried out at a low or high temperature, for example, at a temperature of -20 to 150°C, preferably at room temperature to reflux temperature.

[0056] The reaction time is preferably 10 to 15 hours.

[0057] After the reaction is completed, the solvent is evaporated from the reaction solution, and the solution is washed with ethanol, filtered and dried to obtain a metal complex containing salicylaldehyde diamine oxazoline compounds.

[0058] The present invention also provides the use of a metal complex containing a salicylaldehyde diamine oxazoline compound represented by formula (6) as a catalyst in catalyzing a deoxygenation reduction reaction of a sulfoxide compound.

[0059] When used as a catalyst, the metal complex is preferably used in an amount of 0.001-10 mol %, more preferably 0.1-5 mol %.

[0060] More specifically, the application is to carry out a deoxygenation reduction reaction on the oxygen-sulfur double bond of the sulfoxide compound in the presence of a catalyst to generate a sulfide compound, and the reaction is carried out in the presence of a catalytic amount of at least one metal complex of formula (6).

[0061] Furthermore, the metal complex containing salicylaldehyde diamine oxazoline compounds can be used to catalyze the deoxygenation reduction reaction of sulfoxide compounds to generate sulfide compounds. The sulfoxide compounds can be dialkyl sulfoxide compounds, alkyl aryl sulfoxide compounds, or diaryl sulfoxide compounds to generate corresponding dialkyl sulfide compounds, alkyl aryl sulfide compounds, or diaryl sulfide compounds. The chemical selectivity and yield of the sulfide product catalyzed by the metal complex of the present application are very high, and the application value is relatively large.

[0062] Furthermore, the metal complex containing salicylaldehyde diamine oxazoline compound can be used as a catalyst to catalyze the deoxygenation reduction reaction of sulfoxide compound in the following reaction formula (i).

[0063]

[0064] Specifically, the deoxygenation reduction reaction of formula (i) is carried out as follows: under nitrogen protection, the metal complex of the salicylaldehyde diamine oxazoline compound shown in formula (6) and phenylsilane, the sulfoxide compound shown in formula (A) and an organic solvent are stirred and reacted at a temperature of 50 to 60° C., and the reaction liquid is subjected to column chromatography to obtain the sulfide compound shown in formula (B). The molar ratio of the sulfoxide compound shown in formula (A), phenylsilane and the metal complex of the salicylaldehyde diamine oxazoline compound shown in formula (6) is 1:1 to 2:0.01 to 0.1. The organic solvent can be toluene.

[0065] The reaction time is generally 10 to 15 hours.

[0066] In the reaction formula (i), in the sulfoxide compound represented by the reaction raw material formula (A), R a , R b Each is independently an alkyl, cycloalkyl, aryl, heteroaryl, etc.; preferably R a , R b Each is independently a C1-C20 alkyl group, a C6-C12 aryl group, or a C3-C12 heterocyclic aryl group;

[0067] The H on the C1-C20 alkyl, C6-C12 aryl, C3-C12 heterocyclic aromatic group is not substituted or is substituted by a substituent D, and the substituent D can be various groups, including but not limited to one or more of C1-C10 alkyl, C3-C10 cycloalkyl, C1-C10 alkoxy, C6-C12 aryl, C3-C12 heterocyclic aromatic group, hydroxyl, F, Cl, Br, I, nitro, amino, trifluoromethyl, aldehyde, carboxyl, C2-C5 ester, thiol, sulfonic acid, silane, siloxy, etc.;

[0068] More preferably, R a , R bEach is independently a C1-C5 alkyl group, a C2-C5 ester group, a phenyl group, a benzyl group, a pyridyl group, a thienyl group or a substituted phenyl group, wherein the substituent on the substituted phenyl group is one or more of a methyl group, a methoxy group, a trifluoromethyl group, a hydroxymethyl group and Cl.

[0069] Preferred R a , R b Each is independently phenyl, benzyl, pyridyl, thienyl or substituted phenyl. a , R b The diaryl sulfoxide compounds are all large sterically hindered aromatic or heterocyclic aromatic groups, have good reduction effects, and the yield and selectivity of the obtained diaryl sulfide products are better than those of the prior art.

[0070] Furthermore, the metal complex containing salicylaldehyde diamine oxazoline compound is used as a catalyst to catalyze the epoxidation reaction of olefin compounds of the following reaction formula (ii). Compared with the known literature report [Inorg.Chem.2013,52,3620-3626] which requires 10 mol% of catalyst, only 5 mol% of catalyst is required in the present invention, and the catalytic activity of the catalyst of the present invention is higher.

[0071]

[0072] Specifically, the epoxidation reaction of formula (ii) is carried out as follows: under nitrogen protection, the metal complex of the salicylaldehyde diamine oxazoline compound shown in formula (6) and iodosobenzene, the olefin compound shown in formula (C) and an organic solvent are stirred and reacted at room temperature, and the reaction liquid is subjected to column chromatography to obtain the epoxide compound shown in formula (D). The molar ratio of the olefin compound shown in formula (C), iodosobenzene and the metal complex of the salicylaldehyde diamine oxazoline compound shown in formula (6) is 1:2-4:0.01-0.1. The organic solvent can be tetrahydrofuran.

[0073] The reaction time is generally 10 to 15 hours.

[0074] In the formula (C), R c It is an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic aromatic group, etc.; preferably, it is a C1-C20 alkyl group, a C6-C12 aryl group; H on the C1-C20 alkyl group, the C6-C12 aryl group is not substituted or is substituted by a substituent E, and the substituent E can be various groups, including but not limited to alkyl, cycloalkyl, alkoxy, aryl, heterocyclic aromatic group, hydroxyl, F, Cl, Br, I, nitro, amino, alkoxy, aldehyde, carboxyl, ester, thiol, sulfonic acid, silane, siloxy, etc.

[0075] The beneficial effects of the present invention are as follows:

[0076] The invention provides a novel salicylaldehyde-containing diamine oxazoline compound.

[0077] The invention also provides an efficient route for synthesizing salicylaldehyde diamine oxazoline compounds, and the total yield of two steps can reach 86%.

[0078] The invention provides a novel stable metal complex formed by a salicylaldehyde diamine-containing oxazoline compound and transition metals Fe, Co, Ni, Cu, Ag, Au, Ru, Rh, Pd, Os and Ir.

[0079] The present invention also provides the use of the metal complex containing salicylaldehyde diamine oxazoline compounds as a homogeneous catalyst, and the catalyst can be used to prepare sulfide compounds through a deoxygenation reduction reaction of the sulfoxide group of the organic compound, and can be particularly used to prepare thioether products with large steric hindrance, and the product yield can reach more than 90%. The prior art reports that the yield of diphenyl sulfide generated by deoxygenation reduction of diphenyl sulfoxide is 48% [Synthetic Communications, 2011, 41, 2251-2255.], by comparison, the yield of diphenyl sulfide prepared by the catalyst of the present invention is 93%.

[0080] The organic compound prepared by the metal complex catalyst of the present invention is an active substance or an intermediate for preparing the substance, and can be used in the production of spices and flavor enhancers, pharmaceutical preparations and agricultural chemicals. DETAILED DESCRIPTION

[0081] The technical solution of the present invention is further described in detail below through specific embodiments:

[0082] The following examples illustrate the present invention. All reactions were carried out in airless nitrogen and degassed solvents. However, the present invention is not limited thereto.

[0083] In the examples, the diamine compound represented by formula (3) is commercially available, and the 2-oxazolinyl bromobenzene compound represented by formula (2) is prepared according to the literature (Org Biomol Chem, 2009, 7, 1723-1734).

[0084] Preparation of compound (4):

[0085] Example A1: Preparation of Compound A1:

[0086]

[0087] Under nitrogen protection, 2-(4,4-dimethyl-4,5-dihydrooxazol-2-yl)bromobenzene (2.5413 g, 10 mmol, 1.0 equiv) and phenylenediamine (2.1628 g, 20 mmol, 2.0 equiv) were reacted with PdCl2(PPh3)2 (0.1754 g, 0.25 mmol, 2.5 mol%), 1,1'-bis(diphenylphosphino)ferrocene (0.1663 g, 0.30 mmol, 3.0 mol%), and sodium tert-butoxide (1.9220 g, 20 mmol, 2.0 equiv) in 20 ml of toluene at 110°C for 12 hours, cooled to room temperature, filtered, washed with dichloromethane, and the filtrate was concentrated and then column chromatographed with petroleum ether: ethyl acetate volume ratio = 5:1 to obtain 2.0820 g (7.4 mmol, 74%) of compound A1 containing oxazoline diamines.

[0088] 1 H NMR: (400MHz, CDCl3) δ9.90 (s, 1H), 7.76 (t, J = 8.0Hz, 1H), 7.20 (t, J = 5.2Hz, 2H), 7.06 (t, J =7.8Hz,1H),6.86-6.72(m,2H),6.70-6.63(m,2H),4.02(s,2H),3.85(s,2H),1.36(s,6H); 13 C NMR: (100MHz, CDCl3) δ162.2,147.3,143.1,132.0,129.5,127.5,126.7,126.5,118.6,116.0,115.7,112.5,109.5,67.8,28.7.

[0089] HRMS(ESI)calculated for[C 19 H 21 N3O]+requires m / z 282.1601, found m / z282.1600.

[0090] Example A2: Preparation of Compound A2:

[0091] A2 Under nitrogen protection, 2-(4-phenyl-4,5-dihydrooxazol-2-yl)bromobenzene (3.0217 g, 10 mmol, 1.0 equiv) and phenylenediamine (2.1628 g, 20 mmol, 2.0 equiv) were reacted with PdCl2(PPh3)2 (0.1754 g, 0.25 mmol, 2.5 mol%), 1,1'-bis(diphenylphosphino)ferrocene (0.1663 g, 0.30 mmol, 3.0 mol%), sodium tert-butoxide (1.9220 g, 20 mmol, 2.0 equiv) in 20 ml of toluene, reacted at 110°C for 12 hours, cooled and filtered, washed with dichloromethane, the filtrate was concentrated and then passed through a column, eluted with petroleum ether: ethyl acetate volume ratio = 5:1, to obtain 2.2399 g (6.8 mmol, 68%) of compound A2 containing oxazoline diamines.

[0092] 1 H NMR: (400MHz, CDCl3) δ9.38 (s, 1H), 8.25 (d, J = 7.2Hz, 1H), 8.09 (d, J = 7.6H) z,2H),7.86-7.75(m,1H),7.66-7.54(m,3H),7.48(t,J=7.2Hz,2H),7.40-7 .32(m,4H),6.77(t,J=8.0Hz,1H);5.43(dd,J=10.0Hz,J=8.4Hz,1H),5.33(s,2H),4.84(dd,J=10.0Hz,J=8.8Hz,1H),4.32(dd,J=8.8Hz,J=8.4Hz,1H) 13 C NMR: (100MHz, CDCl3) δ.165.4,142.4,142.2,142.1,139.3,138.8,132.4,131. 9,129.5,128.6,127.7,126.0,125.9,119.2,119.0,118.3,115.2,70.7,73.2.

[0093] HRMS(ESI)calculated for[C 21 H 21 N3O]+requires m / z 330.1601, found m / z330.1598.

[0094]

[0095] Under nitrogen protection, 2-(4-benzyl-4,5-dihydrooxazol-2-yl)bromobenzene (3.1620 g, 10 mmol, 1.0 equiv) and phenylenediamine (2.1628 g, 20 mmol, 2.0 equiv) were reacted in 20 ml of toluene, PdCl2(PPh3)2 (0.1754 g, 0.25 mmol, 2.5 mol%), 1,1'-bis(diphenylphosphino)ferrocene (0.1663 g, 0.30 mmol, 3.0 mol%), sodium tert-butoxide (1.9220 g, 20 mmol, 2.0 equiv), reacted at 110°C for 12 hours, cooled and filtered, washed with dichloromethane, and the filtrate was concentrated and then passed through a column, eluted with petroleum ether: ethyl acetate volume ratio = 5:1 to obtain 2.6444 g (7.7 mmol, 77%) of compound A3 containing oxazoline diamines.

[0096] 1H NMR: (400MHz, CDCl3) delta 9.93(s,1H),7.82(d,J=8.0Hz,1H),7.41-7.20(m,7H),7.12(t,J=7.6Hz,1H),6.85-6.80(m,2H),6.80-6.70(m,2H),4.75-4.60( 13C NMR:(100MHz,)delta 164.3,147.3,142.9,138.1,132.3,129.7,129.2,128.5,127.1,126.7,126.4,118.6,116.1,115.8,112.8,109.3,70.2,67.9,42.1;

[0097] HRMS(ESI)calculated for[C 22 H 22 N3O]+requires m / z 344.1757, found m / z344.1757.

[0098]

[0099] Under nitrogen protection, 2-(4-isopropyl-4,5-dihydrooxazol-2-yl)bromobenzene (2.6815 g, 10 mmol, 1.0 equiv) and phenylenediamine (2.1628 g, 20 mmol, 2.0 equiv) were reacted in 20 ml of toluene, PdCl2(PPh3)2 (0.1754 g, 0.25 mmol, 2.5 mol%), 1,1'-bis(diphenylphosphino)ferrocene (0.1663 g, 0.30 mmol, 3.0 mol%), sodium tert-butoxide (1.9220 g, 20 mmol, 2.0 equiv), reacted at 110°C for 12 hours, cooled and filtered, washed with dichloromethane, and the filtrate was concentrated and then passed through a column, eluted with petroleum ether: ethyl acetate volume ratio = 5:1 to obtain 2.1856 g (7.4 mmol, 74%) of compound A4 containing oxazoline diamines.

[0100] 1H NMR: (400MHz, CDCl3) delta 9.99(s,1H),7.77(d,J=8.0Hz,1H),7.20(m,2H),7.05(t,J=7.4Hz,1H),6.82(d,J=8.0Hz,1H),6.80-6.73(m,2H),6.69(t,J=7.6Hz,1H),4.3 13C NMR: (100MHz, CDCl3) delta163.8,147.3,142.9,132.1,129.6,126.9,126.9,126.3,118.6,116.1,115.8,112.7,109.5,72.8,68.9,33.2,19.0,18.7;

[0101] HRMS(ESI)calculated for[C 18 H 22 N3O]+requires m / z 296.1757, found m / z296.1756.

[0102]

[0103] Under nitrogen protection, 2-(4-tert-butyl-4,5-dihydrooxazol-2-yl)bromobenzene (2.8218 g, 10 mmol, 1.0 equiv) and phenylenediamine (2.1628 g, 20 mmol, 2.0 equiv) were reacted with PdCl2(PPh3)2 (0.1754 g, 0.25 mmol, 2.5 mol%), 1,1'-bis(diphenylphosphino)ferrocene (0.1663 g, 0.30 mmol, 3.0 mol%), and sodium tert-butoxide (1.9220 g, 20 mmol, 2.0 equiv) in 20 ml of toluene at 110°C for 12 hours, cooled and filtered, washed with dichloromethane, and the filtrate was concentrated and then passed through a column, eluted with petroleum ether: ethyl acetate in a volume ratio of 5:1 to obtain 2.4442 g (7.9 mmol, 79%) of compound A5 containing oxazoline diamines.

[0104] 1H NMR: (400MHz, CDCl3) delta 10.04(s,1H),7.77(dd,J=8.0,1.2Hz,1H),7.24-7.18(m,2H),7.04(t,J=7.2Hz,1H),6.80(d,J=8.4Hz,1H),6.76(t,J=7.2Hz ,2H),6.69(t,J=7.6Hz,1H),4.32-4.22(m,1H),4.16-4.06(m,2H),3.82(s,2H),0.93(s,9H); 13CNMR: (100MHz, CDCl3)delta 163.7,147.3,142.7,132.1,129.6,126.8,126.7,126.2,118.5,116.1,115.7,112.7,109.4,76.2,66.9,33.8,25.9;

[0105] HRMS(ESI)calculated for[C 19 H 24 N3O]+requires m / z 310.1914, found m / z310.1911.

[0106]

[0107] Under nitrogen protection, 2-(4-isopropyl-4,5-dihydrooxazol-2-yl)bromobenzene (2.6816 g, 10 mmol, 1.0 equiv) and 1,2-diphenylethylenediamine (4.2458 g, 20 mmol, 2.0 equiv) were reacted in 20 ml of toluene, PdCl2(PPh3)2 (0.1754 g, 0.25 mmol, 2.5 mol%), 1,1'-bis(diphenylphosphino)ferrocene (0.1663 g, 0.30 mmol, 3.0 mol%), sodium tert-butoxide (1.9220 g, 20 mmol, 2.0 equiv), reacted at 110°C for 12 hours, cooled and filtered, washed with dichloromethane, and the filtrate was concentrated and then passed through a column, eluted with petroleum ether: ethyl acetate volume ratio = 5:1 to obtain 2.4353 g (7.9 mmol, 61%) of compound A6 containing oxazoline diamines.

[0108] 1H NMR: (400MHz, CDCl3) delta 9.65(d,J=7.2Hz,1H),7.72(d,J=8.0Hz,1H),7.42(d,J=6.8Hz,2H),7.34-7.18(m,8H),7 .09(t,J=7.8Hz,1H),6.54(t,J=8.0Hz,1H),6.43(d,J=8.0Hz,1H),4.71(dd,J=6.8,4.4Hz ,1H),4.41(t,J=8.4Hz,1H),4.37(d,J=4.8Hz,1H),4.25(q,J=8.4Hz,1H),4.07(t,J=7.2 Hz,1H),2.00-1.84(m,1H),1.65(s,2H),1.19(d,J=6.8Hz,3H),1.08(d,J=6.8Hz,3H); 13C NMR: (100MHz, CDCl3) delta 165.4,149.0,143.5,136.8,131.8,128.5,126.9,126.7,125.9,117.2,113.6,73.5,72.3,71.3,60.4,32.5,19.6;

[0109] HRMS(ESI)calculated for[C 26 H 30 N3O]+requires m / z 400.5381,found m / z400.5382.

[0110] B) Preparation of salicylaldehyde diamine oxazoline compound B

[0111] Example B1: Preparation of salicylaldehyde diamine oxazoline compound B1

[0112]

[0113] Under nitrogen protection, A1 (1.4068 g, 5.0 mmol, 1 equiv) and 3,5-di-tert-butyl salicylaldehyde (1.1172 g, 5.0 mmol, 1.0 equiv) were heated to boiling in 10 mL of ethanol and reacted for 12 h. After the reaction, the mixture was cooled to room temperature, filtered, washed with dichloromethane, and the filtrate was concentrated and separated by column chromatography (eluted with petroleum ether and ethyl acetate in a volume ratio of 20:1) to obtain 2.2875 g (4.6 mmol, 92%) of a yellow solid containing salicylaldehyde diamine oxazoline compound B1.

[0114] 1H NMR: (400MHz, CDCl3) delta 13.17(s,1H),10.48(s,1H),8.58(s,1H),7.79(d,J=8.0Hz,1H),7.59(d,J=8.0Hz,1H),7.41(t,J=8.4Hz,2H),7.26(t,J=8.4Hz,1H),7.22 13C NMR:(100MHz,)delta 165.3,161.5,158.0,144.7,142.0,140.3,136.7,135.3,131.5,129.8,127.9,126.8,126.6,122.6,120.1,119.6,118.6,117.5,114.4,112.0,67.7,35.0,34.1,31.4,29.4,28.4;

[0115] HRMS(ESI)calculated for[C 32 H 40 N3O2]+requires m / z 498.3115, found m / z498.3114.

[0116]

[0117] Under nitrogen protection, A2 (1.6471 g, 5.0 mmol, 1 equiv) and 3,5-di-tert-butyl salicylaldehyde (1.1172 g, 5.0 mmol, 1.0 equiv) were heated to boiling in 10 mL of ethanol and reacted for 12 h. After the reaction, the temperature was cooled to room temperature, filtered, washed with dichloromethane, and the filtrate was concentrated and separated by column chromatography (eluted with petroleum ether and ethyl acetate in a volume ratio of 20:1) to obtain 2.5629 g (4.7 mmol, 94%) of a chiral salicylaldehyde-containing diamine oxazoline compound B2 as a yellow solid.

[0118] 1H NMR:(400MHz,)delta 13.18(s,1H),10.77(s,1H),8.50(s,1H),7.88(d,J=8.0Hz,1H),7.59(d,J=8.0Hz,1 H),7.43(d,J=2.4Hz,1H),7.38(d,J=8.4Hz,1H),7.32(d,J=7.2Hz,1H),7.22(d,J=7. 6Hz,1H),7.15-7.08(m,4H),7.00-7.08(m,4H),6.80(t,J=7.6Hz,1H),5.40(t,J=9. 2Hz,1H),4.66(t,J=9.2Hz,1H),4.10(t,J=8.4Hz,1H),1.42(s,9H),1.33(s,9H); 13C NMR:(100MHz,CDCl3)delta 164.6,164.4,158.1,145.4,142.2,140.3,136.7,135.4,132.1,130.2,128.4,128.2,127.9,127.1,12 6.8,125.3,123.2,121.1,119.5,118.6,117.2,113.4,110.8,72.9,69.9,35.1,34.1,31.5,29.4,29.0;

[0119] HRMS(ESI)calculated for[C 36 H 40 N3O2]+requires m / z 546.3115, found m / z546.3117.

[0120]

[0121] Under nitrogen protection, A3 (1.7172 g, 5.0 mmol, 1 equiv) and 5-bromosalicylaldehyde (1.0051 g, 5.0 mmol, 1.0 equiv) were heated to boiling in 10 mL of ethanol and reacted for 12 h. After the reaction, the temperature was cooled to room temperature, filtered, washed with dichloromethane, and the filtrate was concentrated and separated by column chromatography (eluted with petroleum ether and ethyl acetate in a volume ratio of 20:1) to obtain 2.2373 g (4.2 mmol, 85%) of a chiral salicylaldehyde-containing diamine oxazoline compound B3 as a yellow solid.

[0122] 1H NMR:(400MHz,)delta 12.81(s,1H),10.83(s,1H),8.48(s,1H),7.79(d,J=8.4Hz,1H),7.63(d,J=8.4Hz,1H),7.48-7.4 4(m,2H),7.39(dd,J=8.8,2.4Hz,1H),7.34-7.26(m,2H),7.20-7.12(m,4H),7.10-7.00(m,3H),6 .86(d,J=8.8Hz,1H),6.80(t,J=7.6Hz,1H),4.56-4.48(m,1H),4.24(t,J=8.4Hz,1H),4.04(t,J= 8.0Hz, 1H), 2.97 (dd, J=13.6, 5.6Hz, 1H), 2.60 (dd, J=13.6, 5.6Hz, 1H); 13CNMR: (100MHz,) delta 163.8,161.5,159.9,144.4,140.4,138.2,135.9,135.6,134.4,131.9,130.1,129.2,128.4,127.8,126.3,122.6,121.0,119.5,119.2,119.2,117.9,114.0,111.7,110.4,70.4,68.0,42.0;

[0123] HRMS(ESI)calculated for[C29H25BrN3O2]+requires m / z 526.1125,found m / z526.1124.

[0124]

[0125] Under nitrogen protection, A4 (1.4769 g, 5.0 mmol, 1 equiv) and 3,5-di-tert-butyl salicylaldehyde (1.1172 g, 5.0 mmol, 1.0 equiv) were heated to boiling in 10 mL of ethanol and reacted for 12 h. After the reaction, the temperature was cooled to room temperature, filtered, washed with dichloromethane, and the filtrate was concentrated and separated by column chromatography (eluted with petroleum ether and ethyl acetate in a volume ratio of 20:1) to obtain 2.3536 g (4.6 mmol, 93%) of a chiral salicylaldehyde-containing diamine oxazoline compound B4 as a yellow solid.

[0126] 1H NMR: (400MHz, CDCl3) delta 13.12(s,1H),10.77(s,1H),8.60(s,1H),7.80(d,J=7.2Hz,1H),7.61(d,J=8.0Hz,1H),7.46-7.40(m ,2H),7.28(dt,J=8.0,2.0Hz,1H),7.22(dt,J=7.2,1.6Hz,1H),7.19(d,J=2.4Hz,1H),7.15(d,J=8.0 Hz,1H),7.05(t,J=7.2Hz,1H),6.77(t,J=7.2Hz,1H),4.27(t,J=8.0Hz,1H),4.05(q,J=7.6Hz,1H),3 .95(t,J=8.0Hz,1H),1.68-1.56(m,1H),1.43(s,9H),1.32(s,9H),0.73(dd,J=12.8,6.4Hz,6H); 13C NMR:(100MHz,CDCl3)delta 164.7,163.1,158.0,144.9,141.7,140.4,136.7,135.6,131.7,130.0,127.9,127.0,126.8,122.7,1 20.3,119.7,118.8,117.4,113.7,111.5,72.8,68.9,35.1,34.2,33.0,31.5,29.5,27.0,18.9,18.4;

[0127] HRMS(ESI)calculated for[C 33 H 42 N3O2]+requires m / z 512.3272,found m / z512.3271.

[0128]

[0129] Under nitrogen protection, A5 (1.5470 g, 5.0 mmol, 1 equiv) and 3,5-di-tert-butyl salicylaldehyde (1.1172 g, 5.0 mmol, 1.0 equiv) were heated to boiling in 10 mL of ethanol and reacted for 12 h. After the reaction, the temperature was cooled to room temperature, filtered, washed with dichloromethane, and the filtrate was concentrated and separated by column chromatography (eluted with petroleum ether and ethyl acetate in a volume ratio of 20:1) to obtain 2.3903 g (4.5 mmol, 91%) of a chiral salicylaldehyde-containing diamine oxazoline compound B5 as a yellow solid.

[0130] 1H NMR: (400MHz, CDCl3) delta 13.19(s,1H),10.80(s,1H),8.64(s,1H),7.84(d,J=7.6Hz,1H),7.66(d,J=8.4H z,1H),7.50(d,J=9.2Hz,1H),7.46(d,J=2.4Hz,1H),7.33(d,J=8.4Hz,1H),7.26( d,J=8.0Hz,1H),7.24-7.16(m,2H),7.11(t,J=7.2Hz,1H),6.82(t,J=7.2Hz,1H), 4.26-4.16(m,1H),4.14-4.04(m,2H),1.47(s,9H),1.36(s,9H),0.74(s,9H); 13C NMR:(100MHz,CDCl3)delta 164.7,158.0,145.0,140.3,136.6,135.5,131.6,130.0,127.8,126.9,126.7,122.8,12 0.5,119.8,118.8,117.3,113.5,111.2,76.0,66.9,35.0,34.1,33.5,31.5,29.4,25.6;

[0131] HRMS(ESI)calculated for[C 34 H 44 N3O2]+requires m / z 526.3428, found m / z526.3428.

[0132]

[0133] Under nitrogen protection, A6 (1.9976 g, 5.0 mmol, 1 equiv) and 3,5-di-tert-butyl salicylaldehyde (1.1173 g, 5.0 mmol, 1.0 equiv) were heated to boiling in 10 mL of ethanol and reacted for 12 h. After the reaction, the temperature was cooled to room temperature, filtered, washed with dichloromethane, and the filtrate was concentrated and separated by column chromatography (eluted with petroleum ether and ethyl acetate in a volume ratio of 20:1) to obtain 2.8274 g (4.6 mmol, 92%) of a chiral salicylaldehyde-containing diamine oxazoline compound B6 as a yellow solid.

[0134] 1H NMR: (400MHz, CDCl3) delta 13.39(s,1H),9.56(d,J=5.6Hz,1H),8.45(s,1H),7.73(d,J=7.6Hz,1H),7.44(d,J=2.0Hz,1H),7 .32-7.19(m,10H),7.13(t,J=7.2Hz,1H),7.08(d,J=2.0Hz,1H),6.59(t,J=7.2Hz,1H),6.52(d,J =8.4Hz,1H),5.03(t,J=6.4Hz,1H),4.65(d,J=6.8Hz,1H),4.25(t,J=7.2Hz,1H),4.10-3.98(m,2 13C NMR:(100MHz,CDCl3)delta 167.3,163.6,158.0,148.3,140.7,140.2,140.0,136.6,132.1,129.7,128.2,128.2,128.1,127.7,127.5,127 .2,127.1,126.3,118.1,114.7,111.8,109.3,80.4,72.7,68.1,64.7,35.1,34.2,32.9,31.6,29.5,19.4,18.2;

[0135] HRMS(ESI)calculated for[C 41 H 50 N3O2]+requires m / z 615.3826, found m / z615.3825.

[0136] c) Preparation of Metal Complex C

[0137] Embodiment C1:

[0138]

[0139] Under nitrogen protection, B1 (0.4974 g, 1.0 mmol, 1.0 equiv) and cobalt acetate (0.1681 g, 0.95 mmol, 0.95 equiv) were added to 1.0 mL of anhydrous ethanol, heated to boiling, reacted for 12 h, spin-dried, washed with a small amount of ethanol, filtered, and dried to obtain 0.4425 g (0.79 mmol, 84%) of the metal complex C1.

[0140] Anal.Calcd for C 32 H 37 CoN3O2:Found:C,69.30;H,6.72;Co,10.63;N,7.58;O,5.77

[0141] The same method can be used to obtain the following metal complexes (C2-C7):

[0142]

[0143]

[0144] d) Deoxygenation reduction reaction of sulfoxide compounds catalyzed by metal complex C1

[0145] Under nitrogen protection, metal complex C1 (0.025 mmol), toluene (1.0 mL), and phenylsilane (1.0 mmol) were added to a dry reaction tube. After stirring for 10 min, sulfoxide substrate (0.5 mmol) was added and then stirred at 50 ° C for 12 h. After the reaction was completed, it was cooled to room temperature, 5 mL of petroleum ether was added to dilute, and filtered (eluted with petroleum ether and ethyl acetate in a volume ratio of 10:1). After the filtrate was concentrated, column chromatography was separated (eluted with petroleum ether) to obtain the product.

[0146] Example D1: Phenyl Methyl Sulfide

[0147]

[0148] Oily liquid, 96% yield, 1 H NMR: (400MHz, CDCl3) delta 7.32-7.20 (m, 4H), 7.13 (t, J = 6.8Hz, 1H), 2.47 (s, 3H);

[0149] Example D2: 4-Methylphenyl methyl sulfide

[0150]

[0151] Oily liquid, 94% yield, 1H NMR: (400MHz, CDCl3) delta 7.18 (d, J = 8.0 Hz, 2H), 7.10 (d, J = 8.0 Hz, 2H), 2.46 (s, 3H), 2.31 (s, 3H);

[0152] Example D3: Dibenzyl sulfide

[0153]

[0154] White solid, 94% yield, 1H NMR: (400MHz, CDCl3) delta 7.34-7.20 (m, 10H), 3.59 (s, 4H);

[0155] Example D4: Diphenyl sulfide

[0156]

[0157] Colorless liquid, 93% yield, 1H NMR: (400MHz, CDCl3) delta 7.38-7.30 (m, 5H), 7.30-7.27 (m, 3H), 7.26-7.20 (m, 2H);

[0158] By changing different sulfoxide compound substrates, the corresponding sulfide compounds were prepared. The yields and NMR data of the sulfide compounds prepared from different substrates are shown in Table 1 below:

[0159] Table 1

[0160]

[0161]

[0162]

[0163] e) Epoxidation of olefins catalyzed by metal complex C1

[0164] At room temperature, under nitrogen protection, metal complex C1 (0.025 mmol), tetrahydrofuran (1.0 mL), iodophenyl (1.0 mmol), and styrene compound (0.5 mmol) were added to a dry reaction tube, and then stirred at room temperature for 12 h, and then the product was separated by column chromatography.

[0165] Example E1: (±)-4-Chlorostyrene epoxide

[0166]

[0167] Yellow liquid, 82% yield, 1H NMR: (400MHz, CDCl3) delta 7.30 (d, J = 8.4Hz, 2H), 7.20 (d, J = 8.4Hz, 2H), 3.85-3.79 (m, 1H), 3.13 (t, J = 4.8Hz, 1H), 2.74 (dd, J = 4.8, 2.0Hz, 1H).

[0168] Example E2: (±)-4-Methoxystyrene epoxide

[0169]

[0170] Colorless liquid, 91% yield, 1 H NMR: (400MHz, CDCl3) delta 7.20 (d, J = 8.4Hz, 2H), 6.88 (d, J = 8.4Hz, 2H), 3.89-3.76 (m, 4H), 3.15-3.10 (m, 1H), 2.81 (dd, J = 5.2, 2.4Hz, 1H).

[0171] Example E3: (±)-Naphthalene Ethylene Epoxide

[0172]

[0173] White solid, 86% yield, 1 H NMR: (400MHz, CDCl3) delta 7.92-7.76(m,3H),7.55-7.46(m,3H),7.36(dd,J=8.4,2.0Hz,1H),4.06(dd, J=4.0, 2.4Hz, 1H), 3.26 (dd, J=5.2, 4.0Hz, 1H), 2.94 (dd, J=5.6, 2.4Hz, 1H).

[0174] F): Comparative experiment on catalytic performance and reaction conditions of various catalysts

[0175]

[0176] The metal complex C1 in Example D12 was replaced by C2-C7, and the reaction conditions remained unchanged. The yield of 4,4'-dimethyl diphenyl sulfide and the recovery rate of unreacted raw materials are shown in Table 2 below.

[0177] Table 2

[0178]

[0179] a represents the NMR yield.

[0180] The results in Table 2 show that the metal complex catalysts C1 to C7 of the present invention have good catalytic activity for the reduction reaction of large sterically hindered sulfoxide compounds, and the yield of anisole is higher than that of the prior art.

[0181] The above examples are only some specific embodiments of the present invention. Obviously, the present invention is not limited to the above embodiments, and there may be many variations. All variations that can be directly derived or associated with the contents disclosed by ordinary technicians in this field should be considered to be within the scope of protection of the present invention.

Claims

1. A salicylaldehyde diamine oxazoline compound, the structural formula of which is shown in the following formula (1): R 1 , R 2 Each independently represents H, one of the following groups which are unsubstituted or substituted by one or more substituents A: C1-C12 alkyl, C5-C12 cycloalkyl, C6-C12 aryl; the substituent A is one or more of C1-C5 alkyl, C1-C5 alkoxy, phenyl, C1-C5 fluoroalkyl, C1-C5 fluoroalkoxy, hydroxyl, and halogen; R 3 , R 4 Each of the following groups is independently H, unsubstituted or substituted by one or more substituents A: C1-C12 alkyl, C5-C12 cycloalkyl, C6-C12 aryl; the substituent A is one or more of C1-C5 alkyl, C1-C5 alkoxy, phenyl, C1-C5 fluoroalkyl, C1-C5 fluoroalkoxy, hydroxyl, halogen; R 5 , R 6 , R 7 , R 8 Each is independently H, C1-C4 fluoroalkoxy, F, Cl, nitro, or C1-C12 alkyl which is unsubstituted or substituted with 1-2 C1-C4 alkoxy groups; R 9 , R 10 Each is independently H, C1-C12 alkyl, C1-C4 fluoroalkoxy, F, Cl, nitro, C5-C12 cycloalkyl, C6-C12 aryl; or R 9 , R 10 and the two carbon atoms connected thereto are connected to form a ring to form a C5-C12 cycloalkyl, a C6-C12 aryl or a C5-C12 heterocyclic aromatic group; the H on the C5-C12 cycloalkyl, the C6-C12 aryl or the C5-C12 heterocyclic aromatic group is not substituted or is substituted by a substituent B, and the substituent B is a C1-C5 alkyl, a C1-C5 alkoxy, a phenyl, a hydroxyl, a nitro or a halogen; R 11 is H, one of the following groups which is unsubstituted or substituted by one or more substituents A: C1-C12 alkyl, C5-C12 cycloalkyl, C6-C12 aryl; the substituent A is C1-C5 alkyl, C1-C5 alkoxy, phenyl, C1-C5 fluoroalkyl, C1-C5 fluoroalkoxy, hydroxyl or halogen; R 12 , R 13 , R 14 , R 15 Each is independently H, C1-C12 alkyl which is unsubstituted or substituted by 1-2 C1-C4 alkoxy groups, C1-C4 fluoroalkoxy group, F, Cl, Br, nitro, or C5-C12 cycloalkyl which is unsubstituted or substituted by 1-3 substituents C, wherein the substituent C is C1-C4 alkyl or C1-C4 alkoxy group.

2. The salicylaldehyde diamine oxazoline compound according to claim 1, characterized in that R 1 is C1-C12 alkyl, phenyl or benzyl; R 2 is H or C1-C12 alkyl R 3 , R 4 Each is independently H, C1-C12 alkyl; R 5 , R 6 , R 7 , R 8 Each is independently H or C1-C12 alkyl; R 9 , R 10 Each is independently H, C1-C12 alkyl, C6-C12 aryl or R 9 , R 10 and the two carbon atoms connected thereto are linked to form a ring to form a phenyl group or a naphthyl group; R 11 is H or C1-C12 alkyl; R 12 , R 13 , R 14 , R 15 Each is independently H, C1-C12 alkyl, F, Cl or Br.

3. The salicylaldehyde diamine oxazoline compound according to claim 1, characterized in that R 1 , R 2 When they are different substituents, the compound represented by formula (1) is a chiral salicylaldehyde diamine-containing oxazoline compound, and the chiral salicylaldehyde diamine-containing oxazoline compound is highly optically pure, and the highly optically pure compound means having an enantiomeric selectivity of more than 90%.

4. The method for preparing the salicylaldehyde diamine oxazoline compound of formula (1) as claimed in claim 1, characterized in that The method comprises the following steps: (a) Under nitrogen protection, the 2-oxazolinyl bromobenzene compound represented by formula (2) and the diamine compound represented by formula (3) are subjected to a coupling reaction in the presence of a catalyst to obtain a compound represented by formula (4); (b) Under nitrogen protection, the compound represented by formula (4) and the salicylaldehyde compound represented by formula (5) are subjected to condensation reaction to obtain the salicylaldehyde diamine-containing oxazoline compound represented by formula (1); R 1 ~R 15 The definition as in claim 1.

5. A metal complex containing a salicylaldehyde diamine oxazoline compound, the metal complex being a compound containing a salicylaldehyde diamine oxazoline compound as claimed in claim 1 and a transition metal salt ME n The general formula of the metal complex containing salicylaldehyde diamine oxazoline compound obtained by complexation reaction is as shown in the following formula (6): In formula (6), R 1 -R 15 The definition of is as in claim 1; In formula (6), M is a transition metal such as Fe, Co, Ni, Cu, Ag, Au, Ru, Rh, Pd, Os or Ir; E is any one of F, Cl, Br, I, CN, cyanate, tetrafluoroborate, isocyanate, carbonate, formate, acetate, propionate, methanesulfonate, trichloromethylsulfonate, phenylsulfonate, toluenesulfonate, phosphate, and hexafluorophosphate; n is the number of E, which can be 0, 1, 2 or 3.

6. The method for preparing the metal complex containing salicylaldehyde diamine oxazoline compound as claimed in claim 5, characterized in that The method is: Under nitrogen protection, the salicylaldehyde diamine oxazoline compound represented by formula (1) and the transition metal salt ME n The reaction is carried out in an organic solvent for 1 to 20 hours to obtain a metal complex containing a salicylaldehyde diamine oxazoline compound represented by formula (6); the organic solvent is ethanol.

7. Use of the metal complex containing salicylaldehyde diamine oxazoline compound as claimed in claim 5 as a catalyst in catalyzing the deoxygenation reduction reaction of sulfoxide compounds.

8. The use according to claim 7, characterized in that The metal complex containing salicylaldehyde diamine oxazoline compound is used as a catalyst in catalyzing the deoxygenation reduction reaction of sulfoxide compounds in the following reaction formula (i); R a , R b Each is independently an alkyl group, a cycloalkyl group, an aryl group or a heteroaryl group.

9. The use according to claim 8, characterized in that The deoxygenation reduction reaction of formula (i) is carried out as follows: under nitrogen protection, the metal complex of the salicylaldehyde diamine oxazoline compound represented by formula (6) and phenylsilane, the sulfoxide compound represented by formula (A) and an organic solvent are stirred and reacted at a temperature of 50 to 60° C., and the reaction liquid is subjected to column chromatography to obtain the sulfide compound represented by formula (B); R a , R b Each is independently a C1-C20 alkyl group, a C6-C12 aryl group, or a C3-C12 heterocyclic aryl group; The H on the C1-C20 alkyl, C6-C12 aryl, and C3-C12 heterocyclic aromatic group is not substituted or is substituted by a substituent D, and the substituent D is one or more of a C1-C10 alkyl, a C3-C10 cycloalkyl, a C1-C10 alkoxy, a C6-C12 aryl, a C3-C12 heterocyclic aromatic group, a hydroxyl, F, Cl, Br, I, a nitro, an amino, a trifluoromethyl, an aldehyde, a carboxyl, a C2-C5 ester, a thiol, a sulfonic acid, a silyl, a siloxy, and the like.

10. Use of the metal complex containing salicylaldehyde diamine oxazoline compound as claimed in claim 5 as a catalyst in catalyzing the epoxidation reaction of olefin compounds of the following reaction formula (ii): In the formula (C), R c is an alkyl group, a cycloalkyl group, an aryl group or a heteroaryl group.

Images