5-aryl benzophenanthridine-6 (5H)-ketone C-N axial chiral compound as well as preparation method and application thereof

Abstract

The invention discloses a 5-aryl benzophenanthridine-6 (5H)-ketone C-N axial chiral compound. The structure of the 5-aryl benzophenanthridine-6 (5H)-ketone C-N axial chiral compound is shown as a formula I in the specification. The invention further discloses a preparation method of the 5-aryl benzophenanthridine-6 (5H)-ketone C-N axial chiral compound, compounds shown in a general formula II and a general formula III are used as raw materials and react in a solvent under the action of a palladium catalyst, norbornene, a chiral ligand, alkali and an additive, and after the reaction is finished, a reaction product is separated to obtain the 5-aryl benzophenanthridine-6 (5H)-ketone C-N axial chiral compound. The method has the advantages of cheap and easily available raw materials, simple preparation process, wide substrate application range, high product yield and high enantioselectivity, and the prepared 5-aryl benzophenanthridine-6 (5H)-ketone C-N axial chiral compound has wide application prospects in the fields of asymmetric catalysis and photoelectric materials. # imgabs0 #

Description

Technical Field

[0001] The present invention belongs to the field of compound preparation, and specifically relates to a 5-arylbenzophenanthridine-6(5H)-one C–N axial chiral compound and a preparation method and application thereof. Background Art

[0002] C–N chiral skeletons are widely found in natural products, drug molecules, chiral ligands and catalysts, and their synthesis has received extensive attention in the synthetic chemistry community. Compared with the widely studied C–C chiral biaryl compounds, the C–N chiral axis has a greater rotational freedom and a lower flipping energy barrier due to the different hybridization mode of the nitrogen atom, and its asymmetric construction is more challenging.

[0003] Journal Tetrahedron: Asymmetry, Volume 14, Issue 5, Pages 587-592, "N-allylation ofanilides with chiral palladium catalysts: the first catalytic asymmetricsynthesis of axially chiral anilides" Under palladium-catalyzed allylation conditions, the catalytic asymmetric synthesis of axially chiral anilines was carried out for the first time using chiral phosphine ligands, triggering the development of a series of methods for synthesizing C–N chiral axial skeletons.

[0004] The current methods for synthesizing C–N chiral axis skeletons can be divided into the following four categories: (1) desymmetrization reaction (path a); (2) direct asymmetric coupling of C–N axis (path b), including transition metal catalysis and organic catalysis C–N bond construction reactions; (3) asymmetric cyclization reaction to construct aromatic rings (path c); (4) dynamic kinetic resolution method (path d), including asymmetric N–H and C–N functionalization reactions. The establishment of these catalytic systems has made a remarkable contribution to the asymmetric synthesis of C–N axis chiral skeletons.

[0005] The invention patent with the authorization announcement number CN 111662158 B discloses a method for preparing an axial chiral biaryl compound and a chiral fluorenol compound. The method uses aryl iodide, aryl bromide and olefin as starting materials, and reacts in an organic solvent at 50°C to 150°C under the action of a palladium catalyst, a phosphine ligand, a chiral norbornene derivative and a base, to obtain a biaryl axial chiral compound and a chiral fluorenol compound.

[0006] The invention patent application with publication number CN 113372184 A discloses a method for synthesizing C-N axial chiral phenanthridinone compounds based on a chiral transfer strategy. The method uses easily available aryl iodides and aryl bromides with amide group side chains as starting materials, and reacts in an organic solvent at 40-100°C under the action of a palladium catalyst, a phosphine ligand, a chiral norbornene derivative, and a base, to obtain C-N axial chiral phenanthridinone compounds by stirring.

[0007] Although the research on the synthesis of C-N chiral axis compounds has a certain foundation, there are still many areas that need to be improved in terms of reaction efficiency, substrate applicability and product diversification. Therefore, it is of great research value to develop a method to construct C-N chiral axis more quickly and directly from simple and readily available raw materials, improve the economic efficiency of the reaction, and obtain diversified products. Summary of the invention

[0008] To solve the above problems, the present invention provides a 5-arylbenzophenanthridine-6(5H)-one C–N axial chiral compound. The substituents in the compound can be a variety of different functional groups, so that the compound has good catalytic activity and photoluminescence performance, and has broad application prospects in the field of asymmetric catalysis and optoelectronic materials.

[0009] A 5-arylbenzophenanthridine-6(5H)-one C–N axial chiral compound, the structure of which is shown in Formula I:

[0010] Among them, R x Methyl, OTBS, The wavy line is the connection location;

[0011] R y For H, Br, The wavy line is the connection location;

[0012] R z is H, methyl, methoxy, nitro or fluorine;

[0013] The dotted line indicates that the benzene ring structure is an ortho-monosubstituted or para-substituted structure.

[0014] The present invention also provides a method for preparing a 5-arylbenzophenanthridine-6(5H)-one C–N axial chiral compound. The method has cheap and readily available raw materials, good substrate universality, and a simple preparation process. The 5-arylbenzophenanthridine-6(5H)-one C–N axial chiral compound can be synthesized in one step, and the yield and enantioselectivity of the target product are high.

[0015] A method for preparing a 5-arylbenzophenanthridine-6(5H)-one C–N axial chiral compound comprises the following steps:

[0016] The compounds represented by general formula II and general formula III are used as raw materials, reacted in a solvent under the action of a palladium catalyst, norbornene, a chiral ligand, a base and an additive, and the reaction product is separated after the reaction is completed to obtain a compound represented by formula I;

[0017] The reaction formula is as follows:

[0018]

[0019] Among them, in the compound represented by general formula II, R x Selected from methyl, OTBS, The wavy line is the connection location;

[0020] R y Selected from H, Br, The wavy line is the connection location;

[0021] R z is selected from H, methyl, methoxy, nitro or fluorine;

[0022] The compound shown in the general formula III is selected from wherein R is H, methyl, methoxy, fluoro, bromo, cyclopropyl or phenyl.

[0023] Preferably, the palladium catalyst is one of palladium acetate, palladium trifluoroacetate, Pd2(dba)3, palladium chloride, palladium bromide or Pd(MeCN)Cl2.

[0024] Preferably, the chiral ligand is one of the following compounds L1-L27:

[0025]

[0026] Preferably, the base is one of potassium carbonate, cesium carbonate, sodium carbonate, silver carbonate, silver sulfate, silver phosphate, silver nitrate or silver acetate.

[0027] Preferably, the additive is or One of them.

[0028] Preferably, the solvent is one or more of tetrahydrofuran, 1,4-dioxane, 1,2-dichloroethane, dichloromethane, chloroform, toluene, N,N-dimethylformamide, dimethyl sulfoxide, and water.

[0029] Preferably, the palladium catalyst is Pd2(dba)3, the chiral ligand is the chiral bisimidazoline ligand L25, the base is silver sulfate, and the additive is

[0030] Preferably, the amount of the compound represented by the general formula III is 1.2 to 1.5 times the amount of the compound represented by the general formula II.

[0031] Preferably, the amount of the palladium catalyst is 0.05 to 0.2 times the amount of the compound represented by formula II.

[0032] Preferably, the amount of the norbornene is 1.0 to 2.0 times the amount of the compound represented by formula II.

[0033] Preferably, the amount of the chiral ligand is 0.1 to 0.2 times the amount of the compound represented by formula II.

[0034] Preferably, the amount of the base is 1.0 to 3.0 times the amount of the compound represented by formula II.

[0035] Preferably, the ratio of the mass of the additive to the amount of the compound represented by formula II is 50 mg to 100 mg / 0.1 mmol.

[0036] The amount of solvent used in the present invention can meet the reaction requirements. Preferably, the ratio of the amount of the compound represented by the general formula II to the volume of the solvent is 1.0 mmol: 10-20 mL.

[0037] Preferably, the reaction temperature is 65°C to 100°C, and the reaction time is 6h to 48h.

[0038] More preferably, the reaction temperature is 80° C. and the reaction time is 12 h to 48 h.

[0039] The present invention also provides the application of the 5-arylbenzophenanthridine-6(5H)-one C–N axial chiral compound in the field of asymmetric catalysis and optoelectronic materials. The 5-arylbenzophenanthridine-6(5H)-one C–N axial chiral compound of the present invention has good catalytic activity and photoluminescence performance, and has broad application prospects in the field of asymmetric catalysis and optoelectronic materials.

[0040] Compared with the prior art, the present invention has at least the following beneficial effects:

[0041] (1) The 5-arylbenzophenanthridine-6(5H)-one C–N axial chiral compound of the present invention has good catalytic activity and photoluminescence performance, and has broad application prospects in the field of asymmetric catalysis and optoelectronic materials.

[0042] (2) The method of the present invention can synthesize 5-arylbenzophenanthridine-6(5H)-one C–N axial chiral compounds in one step in an efficient, simple and economical manner, providing a novel and efficient strategy for the rapid construction of C–N axial chiral compounds.

[0043] (3) The method of the present invention has the advantages of cheap and readily available raw materials, mild reaction conditions, simple preparation process, wide substrate application range, high product yield and enantioselectivity, and easy scale-up. It has great application potential and lays a good foundation for industrial production. DETAILED DESCRIPTION

[0044] The following non-limiting embodiments may enable a person skilled in the art to more fully understand the present invention, but are not intended to limit the present invention in any way.

[0045] The test methods described in the following examples are conventional methods unless otherwise specified; the reagents and materials described are commercially available unless otherwise specified.

[0046] Example 1

[0047] Preparation of (S)-5-(2-tert-butyl)phenylbenzophenanthridine-6(5H)-one (Compound 1)

[0048] At room temperature, 1-iodonaphthalene (0.15 mmol), 2-bromobenzoyl-N-(2-tert-butyl)aniline (0.1 mmol), Pd2(dba)3 (4.9 mg, 0.005 mmol), L25 (S, S; 10.2 mg, 0.02 mmol), silver sulfate (62.3 mg, 0.2 mmol), toluene (2.0 mL), water (0.2 mL) were added in sequence into a 10 mL Schlenk bottle protected by nitrogen. (100 mg), norbornene (NBE) (15 mg, 0.15 mmol). The resulting mixture was reacted at 80 ° C for 36 hours. After the reaction was complete, the reaction was cooled to room temperature, the resulting product was diluted with ethyl acetate and filtered through a small section of diatomaceous earth to obtain the corresponding filtrate, and then the solvent was removed by rotary evaporation under reduced pressure, and the target compound was obtained by column chromatography. The column chromatography filler was silica gel and the eluent was petroleum ether / ethyl acetate.

[0049] The compound 1 prepared in this example is a yellow liquid with an isolated yield of 95%. The enantiomeric excess of the product determined by chiral HPLC is 91%. 1H NMR (400MHz, CDCl3), δ: 8.58 (d, J = 7.9 Hz, 1H), 8.41 (dd, J = 15.6, 8.6 Hz, 2H), 7.86-7.79 (m, 2H), 7.75 (d, J = 8.7 Hz, 2H), 7.63 (t, J = 7.6 Hz, 1H), 7.50 (t, J = 7.9 Hz, 1H), 7.36 (t, J = 7.5 Hz, 1H), 7.28 (t, J = 7.7 Hz, 1H), 7.23 (d, J = 8.8 Hz, 1H), 7.00 (m, 2H), 1.20 (s, 9H), and its structural formula is shown below:

[0050]

[0051] Example 2

[0052] Preparation of (S)-5-(2-tert-butyl)phenyl-12-cyclopropylbenzophenanthridine-6(5H)-one (Compound 2)

[0053] The process is the same as in Example 1 except that the 1-iodonaphthalene in Example 1 is replaced by the same molar amount of 1-cyclopropyl-4-iodonaphthalene.

[0054] The compound 2 prepared in this example is a colorless liquid with an isolation yield of 80%. The enantiomeric excess of the product determined by chiral HPLC is 90%. 1 H NMR (400MHz, CDCl3), δ: 8.57 (d, J = 7.7Hz, 1H), 8.50 (d, J = 8.3Hz, 1H), 8.44 (d, J = 8.5Hz, 1H), 8.2 4(s,1H),7.84(t,J=7.8Hz,1H),7.75(d,J=7.7Hz,1H),7.61(t,J=7.6Hz,1H),7.48(t,J=7.4Hz, 1H), 7.44 (t, J = 7.6 Hz, 1H), 7.41 (d, J = 9.1 Hz, 1H), 7.25 (t, J = 7.7 Hz, 1H), 7.07–7.00 (m, 1H), 6.95–6.89 (m, 1H), 2.35 (td, J = 8.4, 4.2 Hz, 1H), 1.23 (s, 9H), 1.16 (d, J = 8.6 Hz, 2H), 0.89 (dd, J = 15.7 5.8 Hz 2H), and its structural formula is shown below:

[0055]

[0056] Example 3

[0057] Preparation of (S)-5-(2-tert-butyl)phenyl-12-methylbenzophenanthridine-6(5H)-one (Compound 3)

[0058] The process is the same as in Example 1 except that the 1-iodonaphthalene in Example 1 is replaced by the same molar amount of 1-methyl-4-iodonaphthalene.

[0059] The compound 3 prepared in this example is a yellow liquid with an isolation yield of 82%. The enantiomeric excess of the product determined by chiral HPLC is 85%. 1 H NMR (400MHz, CDCl3), δ: 8.58 (d, J = 7.9 Hz, 1H), 8.43 (d, J = 8.3 Hz, 1H), 8.24 (s, 1H), 7.98 (d, J = 8.4 Hz, 1H), 7.83 (t, J = 7.8 Hz, 1H), 7.74 (d, J = 8.3 Hz, 1H), 7.61 (t, J = 7.6 Hz, 1H), 7.48 (t, J = 7.9 Hz, 1H), 7.42 (d, J = 7.2 Hz, 2H), 7.25 (t, J = 7.4 Hz, 1H), 7.05–6.97 (m, 1H), 6.94 (d, J = 7.9 Hz, 1H), 2.77 (s, 3H), 1.22 (s, 9H), and its structural formula is shown below:

[0060]

[0061] Example 4

[0062] Preparation of (S)-5-(2-tert-butyl)phenyl-12-methoxybenzophenanthridine-6(5H)-one (Compound 4)

[0063] The process is the same as in Example 1 except that the 1-iodonaphthalene in Example 1 is replaced by the same molar amount of 1-methoxy-4-iodonaphthalene and the toluene is replaced by the same volume of 1,2-dichloroethane.

[0064] The compound 4 prepared in this example is a colorless liquid with an isolated yield of 64%. The enantiomeric excess of the product determined by chiral HPLC is 79%. 1H NMR (400MHz, CDCl3), δ: 8.61 (d, J = 8.5 Hz, 1H), 8.37 (dd, J = 15.7, 8.6 Hz, 2H), 7.89-7.82 (m, 1H), 7.76-7.73 (m, 1H), 7.69 (s, 1H), 7.64 (t, J = 7.5 Hz, 1H), 7.52-7.47 (m, 1H), 7.40 (t, J = 7.6 Hz, 1H), 7.28 (dd, J = 9.0, 6.1 Hz, 2H), 7.05 (td, J = 7.2, 6.6, 3.7 Hz, 1H), 6.99 (d, J = 6.6 Hz, 1H), 4.18 (s, 3H), 1.21 (s, 9H), and its structural formula is shown below:

[0065]

[0066] Example 5

[0067] Preparation of (S)-5-(2-tert-butyl)phenyl-12-fluorobenzophenanthridine-6(5H)-one (Compound 5)

[0068] The process is the same as in Example 1 except that the 1-iodonaphthalene in Example 1 is replaced by the same molar amount of 1-fluoro-4-iodonaphthalene.

[0069] The compound 5 prepared in this example is beige foam, and its isolated yield is 55%. The enantiomeric excess of the product determined by chiral HPLC is 87%. 1 H NMR (400MHz, CDCl3), δ: 8.59 (d, J = 7.7Hz, 1H), 8.30 (d, J = 8.3Hz, 1H), 8.14 (d, J = 8.3Hz, 1H ),8.08(d,J=11.6Hz,1H),7.90–7.84(m,1H),7.77–7.75(m,1H),7.66(t,J=7.5Hz,1H),7. 54–7.49 (m, 1H), 7.45 (t, J = 7.5 Hz, 1H), 7.30 (td, J = 7.6, 1.6 Hz, 1H), 7.24 (d, J = 11.5 Hz, 1H), 7.08 (ddd, J = 8.8, 6.9, 1.7 Hz, 1H), 6.99 (dd, J = 7.7, 1.6 Hz, 1H), 1.20 (s, 9H), and its structural formula is shown below:

[0070]

[0071] Example 6

[0072] Preparation of (S)-5-(2-tert-butyl)phenyl-12-bromobenzophenanthridine-6(5H)-one (Compound 6)

[0073] The process is the same as in Example 1 except that the 1-iodonaphthalene in Example 1 is replaced by the same molar amount of 1-bromo-4-iodonaphthalene.

[0074] The compound 6 prepared in this example is a yellow foam, and its isolated yield is 54%. The enantiomeric excess of the product determined by chiral HPLC is 87%. 1 H NMR (400MHz, CDCl3), δ: 8.72 (s, 1H), 8.58 (dd, J = 7.8, 1.5Hz, 1H), 8.36 (d, J = 8.3Hz, 1H), 8.3 2(dd,J=8.4,1.5Hz,1H),7.87(ddd,J=8.4,7.0,1.5Hz,1H),7.76(dd,J=8.3,1.5Hz,1H),7.69 –7.62(m,1H),7.49(dddd,J=15.0,8.2,7.0,1.3Hz,2H),7.43(d,J=9.1Hz,1H),7.30–7.26(m,1H),7.07(ddd,J=8.8,6.8,1.5Hz,1H),6.94(dd,J=7.8,1.6Hz,1H),1.22(s,9H), its structural formula is as follows:

[0075]

[0076] Example 7

[0077] Preparation of (S)-5-(2-tert-butyl)phenyl-12-phenylbenzophenanthridine-6(5H)-one (Compound 7)

[0078] The process is the same as in Example 1 except that the 1-iodonaphthalene in Example 1 is replaced by the same molar amount of 1-phenyl-4-iodonaphthalene.

[0079] The compound 7 prepared in this example is a yellow liquid with an isolated yield of 88%. The enantiomeric excess of the product determined by chiral HPLC is 92%. 1H NMR (400MHz, CDCl3), δ: 8.62 (d, J = 7.9 Hz, 1H), 8.42 (d, J = 8.3 Hz, 1H), 8.34 (s, 1H), 7.89 (d, J = 8.4 Hz, 1H), 7.83 (t, J = 7.7 Hz, 1H), 7.80 (d, J = 8.2 Hz, 1H), 7.64 (t, J = 7.5 Hz, 1H), 7.59–7.47 (m, 7H), 7.30 (q, J = 7.8 Hz, 2H), 7.04 (t, J = 8.0 Hz, 1H), 7.00 (d, J = 7.8 Hz, 1H), 1.31 (s, 9H), and its structural formula is shown below:

[0080]

[0081] Example 8

[0082] Preparation of (S)-5-(2-(tert-butyldimethylsilyloxy)propyl)phenyl-4-methylbenzophenanthridine-6(5H)-one (Compound 8)

[0083] The method is the same as that in Example 1 except that the 1-iodonaphthalene in Example 1 is replaced by an equal molar amount of 2-methyl-1-iodobenzene, and the 2-bromobenzoyl-N-(2-tert-butyl)aniline is replaced by an equal molar amount of 2-bromobenzoyl-N-(2-(tert-butyldimethylsilyloxy)propyl)aniline.

[0084] The compound 8 prepared in this example is a yellow liquid, and its isolation yield is 81%. The enantiomeric excess of the product determined by chiral HPLC is 81%. 1 H NMR (400MHz, CDCl3), δ: 8.50 (dd, J=8.0, 1.4Hz, 1H), 8.33 (d, J=8.3Hz, 1H), 8.26 (dd, J=6.3, 3. 4Hz,1H),7.93(dd,J=8.2,1.6Hz,1H),7.79(ddd,J=8.5,7.1,1.5Hz,1H),7.59(t,J=7.7Hz,1H), 7.49–7.44 (m, 1H), 7.29 (td, J = 7.6, 1.6 Hz, 1H), 7.19 (d, J = 6.3 Hz, 2H), 7.11 (dd, J = 7.8, 1.5 Hz, 1H), 1.70 (s, 3H), 1.45 (s, 3H), 1.32 (s, 3H), 0.86 (s, 9H), 0.09 (s, 3H), -0.01 (s, 3H), and its structural formula is shown below:

[0085]

[0086] Example 9

[0087] Preparation of (S)-5-(2-(tert-butyldimethylsilyloxy)propyl)phenyl-4-phenylbenzophenanthridine-6(5H)-one (Compound 9)

[0088] The same as in Example 1 except that 1-iodonaphthalene in Example 1 was replaced by an equal molar amount of 2-phenyl-1-iodobenzene, and 2-bromobenzoyl-N-(2-tert-butyl)aniline was replaced by an equal molar amount of 2-bromobenzoyl-N-(2-(tert-butyldimethylsilyloxy)propyl)aniline.

[0089] The compound 9 prepared in this example is a yellow liquid with an isolated yield of 65%. The enantiomeric excess of the product determined by chiral HPLC is 83%. 1 H NMR (400MHz, CDCl3), δ: 8.52 (dt, J=8.1, 1.8Hz, 1H), 8.42–8.32 (m, 2H), 7.86–7.79 (m, 1H), 7.6 9(dt,J=8.3,1.9Hz,1H),7.61(td,J=7.6,2.1Hz,1H),7.31–7.20(m,1H),7.10–6.95(m,4H),6. 89–6.77 (m, 2H), 6.65 (dt, J = 7.9, 1.8 Hz, 1H), 6.58 (ddd, J = 9.7, 6.0, 4.2 Hz, 2H), 1.05 (dd, J = 5.9, 2.2 Hz, 6H), 0.88 (d, J = 2.3 Hz, 9H), -0.02 (d, J = 2.3 Hz, 3H), -0.06 (d, J = 2.3 Hz, 3H), its structural formula is shown below:

[0090]

[0091] Example 10

[0092] Preparation of (S)-12-(2-tert-butylphenyl)benzofuranylbenzophenanthridine-13(12H)-one (Compound 10)

[0093] The process is the same as in Example 1 except that the 1-iodonaphthalene in Example 1 is replaced by the same molar amount of 1-iodobenzofuran.

[0094] The compound 10 prepared in this example is a white foam with an isolated yield of 86%. The enantiomeric excess of the product determined by chiral HPLC is 91%. 1H NMR (400MHz, CDCl3), δ: 8.56 (d, J=8.9Hz, 1H), 8.52 (dd, J=7.9, 1.5Hz, 1H), 8.38 (d, J=8.3Hz,1H),7.91–7.75(m,2H),7.68–7.55(m,3H),7.47(dd,J=8.1,1.2Hz,1H),7.3 3 (td, J = 7.6, 1.5 Hz, 1H), 7.26 (td, J = 7.8, 7.1, 1.2 Hz, 1H), 7.20 (dd, J = 7.8, 1.5 Hz, 1H), 6.73 (ddd, J = 8.5, 7.1, 1.3 Hz, 1H), 4.95 (d, J = 8.5 Hz, 1H), 1.21 (s, 9H), its structural formula is as follows:

[0095]

[0096] Embodiment 11

[0097] Preparation of (S)-5-(2-tert-butyl)phenylbenzophenanthrolin-6(5H)-one (Compound 11)

[0098] The process is the same as in Example 1 except that the 1-iodonaphthalene in Example 1 is replaced by the same molar amount of 5-iodoquinoline and the toluene is replaced by the same volume of 1,2-dichloroethane.

[0099] The compound 11 prepared in this example is a yellow solid with an isolated yield of 74%. The enantiomeric excess of the product determined by chiral HPLC is 85%. 1 H NMR (400MHz, CDCl3), δ: 8.76 (d, J = 3.9Hz, 1H), 8.68 (d, J = 9.0Hz, 1H), 8.59 (d, J = 7.9Hz, 1H),8.45(d,J=8.3Hz,1H),8.10(d,J=9.0Hz,1H),7.89(t,J=7.5Hz,1H),7.78(d,J=7.9 Hz, 1H), 7.68 (t, J = 7.5 Hz, 1H), 7.55 (t, J = 7.7 Hz, 1H), 7.41 (d, J = 9.1 Hz, 1H), 7.35 (t, J = 7.6 Hz, 1H), 7.05 (d, J = 8.1 Hz, 1H), 6.94 (dd, J = 9.3, 3.8 Hz, 1H), 1.16 (s, 9H), and its structural formula is shown below:

[0100]

[0101] Example 12

[0102] Preparation of (S)-5-(2-tert-butyl)phenyl-9-fluorobenzophenanthridine-6(5H)-one (Compound 12)

[0103] The process is the same as in Example 1 except that the 2-bromobenzoyl-N-(2-tert-butyl)aniline in Example 1 is replaced with an equal molar amount of 2-bromo-4-fluorobenzoyl-N-(2-tert-butyl)aniline.

[0104] The compound 12 prepared in this example is a yellow liquid with an isolated yield of 76%. The enantiomeric excess of the product determined by chiral HPLC is 91%. 1 H NMR (400MHz, CDCl3), δ: 8.60 (dd, J = 8.8, 6.1 Hz, 1H), 8.24 (d, J = 8.8 Hz, 1H), 8.04 (dd, J = 10.8, 2.3 Hz, 1H), 7.83 (d, J = 8.1 Hz, 1H), 7.77 (dt, J = 8.4, 2.2 Hz, 2H), 7.52 (t, J = 7.7 Hz, 1H), 7.39 (t, J = 7.5 Hz, 1H), 7.36-7.27 (m, 2H), 7.23 (d, J = 9.2 Hz, 1H), 7.06-6.94 (m, 2H), 1.20 (s, 9H), and its structural formula is shown below:

[0105]

[0106] Example 13

[0107] Preparation of (S)-5-(2-tert-butyl)phenyl-9-methylbenzophenanthridine-6(5H)-one (Compound 13)

[0108] The process is the same as in Example 1 except that the 2-bromobenzoyl-N-(2-tert-butyl)aniline in Example 1 is replaced by the same molar amount of 2-bromo-4-methylbenzoyl-N-(2-tert-butyl)aniline, and the toluene is replaced by the same volume of 1,2-dichloroethane.

[0109] The compound 13 prepared in this example is a white foam with an isolated yield of 52%. The enantiomeric excess of the product determined by chiral HPLC is 90%. 1H NMR (400MHz, CDCl3), δ: 8.48 (d, J = 8.1 Hz, 1H), 8.41 (d, J = 8.8 Hz, 1H), 8.22 (s, 1H), 7.82 (dd, J = 8.1, 1.5 Hz, 1H), 7.76 (d, J = 8.5 Hz, 2H), 7.54–7.48 (m, 1H), 7.46 (d, J = 8.1 Hz, 1H), 7.36 (t, J = 7.4 Hz, 1H), 7.29 (td, J = 7.5, 1.5 Hz, 1H), 7.23 (d, J = 9.1 Hz, 1H), 7.01 (ddt, J = 8.9, 6.1, 3.0 Hz, 2H), 2.63 (s, 3H), 1.20 (s, 9H), and its structural formula is shown below:

[0110]

[0111] Embodiment 14

[0112] Preparation of (S)-5-(2-tert-butyl)phenyl-8-nitrobenzophenanthridine-6(5H)-one (Compound 14)

[0113] The same as Example 1 except that the 2-bromobenzoyl-N-(2-tert-butyl)aniline in Example 1 was replaced with 2-bromo-5-nitrobenzoyl-N-(2-tert-butyl)aniline of the same molar amount.

[0114] The compound 14 prepared in this example is a yellow solid with an isolated yield of 72%. The enantiomeric excess of the product determined by chiral HPLC is 90%. 1 H NMR (400MHz, CDCl3), δ: 9.40 (d, J = 2.4Hz, 1H), 8.63 (dd, J = 9.0, 2.5Hz, 1H), 8.57 (d, J = 9.1Hz ,1H),8.37(d,J=8.9Hz,1H),7.86(d,J=8.1Hz,1H),7.82(d,J=8.9Hz,1H),7.79(dd,J=8.2,1. 4Hz,1H),7.58–7.51(m,1H),7.44(t,J=7.4Hz,1H),7.32(td,J=7.5,1.4Hz,1H),7.28–7.23(m,2H),7.06(ddd,J=8.7,6.7,1.5Hz,1H),6.98(dd,J=7.8,1.4Hz,1H),1.21(s,9H), its structural formula is as follows:

[0115]

[0116] Embodiment 15

[0117] Preparation of (S)-5-(2-tert-butyl)phenyl-8-methoxybenzophenanthridine-6(5H)-one (Compound 15)

[0118] Except that the 2-bromobenzoyl-N-(2-tert-butyl)aniline in Example 1 is replaced with 2-bromo-5-methoxybenzoyl-N-(2-tert-butyl)aniline of the same molar amount, the rest are the same as Example 1.

[0119] The compound 15 prepared in this example is a white foam with an isolated yield of 51%. The enantiomeric excess of the product determined by chiral HPLC is 89%. 1 H NMR (400MHz, CDCl3), δ: 8.36 (t, J = 8.3 Hz, 1H), 7.99 (m, 1H), 7.82 (d, J = 8.0 Hz, 1H), 7.76 (d, J = 9.2 Hz, 2H), 7.51 (t, J = 7.8 Hz, 1H), 7.45 (dd, J = 9.0, 2.7 Hz, 1H), 7.35 (t, J = 7.4 Hz, 1H), 7.29 (t, J = 7.6 Hz, 1H), 7.20 (d, J = 9.1 Hz, 1H), 7.00 (m, 2H), 3.98 (s, 3H), 1.20 (s, 9H), and its structural formula is shown below:

[0120]

[0121] Example 16

[0122] Preparation of (S)-5-(2-tert-butyl)phenyl-8,9-difluorobenzophenanthridine-6(5H)-one (Compound 16)

[0123] The process is the same as that of Example 1 except that the 2-bromobenzoyl-N-(2-tert-butyl)aniline in Example 1 is replaced by the same molar amount of 2-bromo-4,5-difluorobenzoyl-N-(2-tert-butyl)aniline.

[0124] The compound 16 prepared in this example is a yellow foam with an isolated yield of 79%. The enantiomeric excess of the product determined by chiral HPLC is 89%. 1H NMR (400MHz, CDCl3), δ: 8.34 (dd, J = 10.4, 8.4 Hz, 1H), 8.20-8.12 (m, 2H), 7.84 (dd, J = 8.1, 1.5 Hz, 1H), 7.80-7.74 (m, 2H), 7.57-7.49 (m, 1H), 7.42-7.37 (m, 1H), 7.30 (td, J = 7.5, 1.5 Hz, 1H), 7.21 (d, J = 9.2 Hz, 1H), 7.06-6.95 (m, 2H), 1.19 (s, 9H), and its structural formula is shown below:

[0125]

[0126] Embodiment 17

[0127] Preparation of (S)-5-(2-tert-butyl)phenyl-8,9-difluorobenzophenanthridine-6(5H)-one (Compound 17)

[0128] The process is the same as in Example 1 except that the 2-bromobenzoyl-N-(2-tert-butyl)aniline in Example 1 is replaced with an equal molar amount of 2-bromo-4-methyl-5-fluorobenzoyl-N-(2-tert-butyl)aniline.

[0129] The compound 17 prepared in this example is a yellow foam, and its isolated yield is 77%. The enantiomeric excess of the product determined by chiral HPLC is 89%. 1 H NMR (400MHz, CDCl3), δ: 8.33 (d, J = 8.8 Hz, 1H), 8.25 (d, J = 6.7 Hz, 1H), 8.16 (d, J = 9.6 Hz, 1H), 7.82 (d, J = 8.1 Hz, 1H), 7.76 (d, J = 8.5 Hz, 2H), 7.52 (t, J = 7.7 Hz, 1H), 7.37 (t, J = 7.4 Hz, 1H), 7.30 (t, J = 7.4 Hz, 1H), 7.21 (d, J = 9.1 Hz, 1H), 7.01 (dd, J = 12.8, 7.9 Hz, 2H), 2.56 (s, 3H), 1.20 (s, 9H), and its structural formula is shown below:

[0130]

[0131] Embodiment 18

[0132] Preparation of (S)-5-(2-tert-butyl)phenyl-8,9-dimethoxybenzophenanthridine-6(5H)-one (Compound 18)

[0133] The process is the same as in Example 1 except that the 2-bromobenzoyl-N-(2-tert-butyl)aniline in Example 1 is replaced by the same molar amount of 2-bromo-4,5-dimethoxybenzoyl-N-(2-tert-butyl)aniline, and the toluene is replaced by the same volume of 1,2-dichloroethane.

[0134] The compound 18 prepared in this example is a white foam with an isolated yield of 37%. The enantiomeric excess of the product determined by chiral HPLC is 88%. 1 H NMR (400MHz, CDCl3), δ: 8.29 (d, J = 8.7 Hz, 1H), 7.97 (s, 1H), 7.82 (d, J = 8.1 Hz, 1H), 7.75 (d, J = 8.0 Hz, 3H), 7.51 (t, J = 7.8 Hz, 1H), 7.36 (t, J = 7.4 Hz, 1H), 7.29 (t, J = 7.6 Hz, 1H), 7.22 (d, J = 9.2 Hz, 1H), 7.00 (d, J = 7.9 Hz, 2H), 4.16 (s, 3H), 4.05 (s, 3H), 1.20 (s, 9H), and its structural formula is shown below:

[0135]

[0136] Embodiment 19

[0137] Preparation of (S)-5-(2-tert-butyl-4-bromo)phenylbenzophenanthridine-6(5H)-one (Compound 19)

[0138] The process is the same as in Example 1 except that the 2-bromobenzoyl-N-(2-tert-butyl)aniline in Example 1 is replaced with an equal molar amount of 2-bromobenzoyl-N-(2-tert-butyl-4-bromo)aniline.

[0139] The compound 19 prepared in this example is a yellow solid with an isolated yield of 70%. The enantiomeric excess of the product determined by chiral HPLC is 79%. 1 H NMR (400MHz, CDCl3), δ: 8.57 (dd, J = 7.9, 1.5 Hz, 1H), 8.41 (dd, J = 15.4, 8.6 Hz, 2H), 7.88 (d, J = 2.3 Hz, 1H), 7.87-7.83 (m, 2H), 7.78 (d, J = 8.8 Hz, 1H), 7.64 (t, J = 7.4 Hz, 1H), 7.44-7.38 (m, 2H), 7.35 (d, J = 9.1 Hz, 1H), 7.11 (ddd, J = 8.8, 6.8, 1.6 Hz, 1H), 6.87 (d, J = 8.4 Hz, 1H), 1.21 (s, 9H), the structural formula is shown below:

[0140]

[0141] Embodiment 20

[0142] Preparation of (S)-5-(2-tert-butyl-4-phenylethynyl)phenylbenzophenanthridine-6(5H)-one (Compound 20)

[0143] The process is the same as in Example 1 except that the 2-bromobenzoyl-N-(2-tert-butyl)aniline in Example 1 is replaced with an equal molar amount of 2-bromobenzoyl-N-(2-tert-butyl-4-phenylethynyl)aniline.

[0144] The compound 20 prepared in this example is a yellow foam with an isolated yield of 65%. The enantiomeric excess of the product determined by chiral HPLC is 88%. 1 H NMR (400MHz, CDCl3), δ: 8.59 (dd, J = 8.0, 1.5Hz, 1H), 8.42 (dd, J = 15.4, 8.6Hz, 2H), 7.94 (d, J = 2.0Hz, 1H), 7.89-7.83 (m, 2H), 7.79 (d, J = 8.9Hz, 1H), 7.65 (t, J = 7.5Hz, 1H), 7.61 (dd, J = 7.7, 1.8Hz, 2H), 7.46 (dd, J = 8.0, 1.9Hz, 1H), 7.39 (dq, J = 7.9, 5.9Hz, 5H), 7.13-7.06 (m, 1H), 7.00 (d, J = 7.9Hz, 1H), 1.25 (s, 9H), and its structural formula is shown below:

[0145]

[0146] Embodiment 21

[0147] Preparation of (S)-5-(2,5-di-tert-butyl)phenylbenzophenanthridine-6(5H)-one (Compound 21)

[0148] The process is the same as in Example 1 except that the 2-bromobenzoyl-N-(2-tert-butyl)aniline in Example 1 is replaced by the same molar amount of 2-bromobenzoyl-N-(2,5-di-tert-butyl)aniline and the toluene is replaced by the same volume of 1,2-dichloroethane.

[0149] The compound 21 prepared in this example is a yellow foam with an isolated yield of 55%. The enantiomeric excess of the product determined by chiral HPLC is 90%. 1H NMR (400MHz, CDCl3), δ: 8.60 (d, J = 7.8 Hz, 1H), 8.43 (dd, J = 15.8, 8.5 Hz, 2H), 7.86 (t, J = 7.8 Hz, 1H), 7.82 (d, J = 8.0 Hz, 1H), 7.77 (d, J = 8.6 Hz, 1H), 7.70–7.61 (m, 2H), 7.56–7.52 (m, 1H), 7.35 (t, J = 7.4 Hz, 1H), 7.06–7.00 (m, 2H), 6.96 (t, J = 8.1 Hz, 1H), 1.22 (s, 9H), 1.15 (s, 9H), and its structural formula is shown below:

[0150]

[0151] Embodiment 22

[0152] Preparation of (S)-5-(2-tert-butyl-4-(3-acetyl)phenyl)phenylbenzophenanthridine-6(5H)-one (Compound 22)

[0153] The process is the same as in Example 1 except that the 2-bromobenzoyl-N-(2-tert-butyl)aniline in Example 1 is replaced with an equal molar amount of 2-bromobenzoyl-N-(2-tert-butyl-4-(3-acetyl)phenyl)aniline.

[0154] The compound 22 prepared in this example is a white foam with an isolated yield of 73%. The enantiomeric excess of the product determined by chiral HPLC is 86%. 1 H NMR (400MHz, CDCl3), δ: 8.60 (d, J=6.7Hz, 1H), 8.44 (dd, J=13.9, 8.6Hz, 2H), 8.29 (s, 1H), 8.02–7.97(m,2H),7.92–7.84(m,3H),7.80(d,J=8.8Hz,1H),7.65(t,J=7.5Hz,1H),7.60( t, J = 7.7 Hz, 1H), 7.54 (dd, J = 8.1, 2.2 Hz, 1H), 7.44 (d, J = 9.1 Hz, 1H), 7.39 (t, J = 7.4 Hz, 1H), 7.10 (d, J = 8.0 Hz, 1H), 7.06 (td, J = 6.9, 3.3 Hz, 1H), 2.70 (s, 3H), 1.28 (s, 9H), its structural formula is shown below:

[0155]

[0156] Embodiment 23

[0157] Preparation of (S)-5-(2-tert-butyl)phenyl-8,9-difluorobenzophenanthridine-6(5H)-one (Compound 23)

[0158] The method is the same as that of Example 1 except that the 1-iodonaphthalene in Example 1 is replaced by the same molar amount of 1-iodobenzofuran, and the 2-bromobenzoyl-N-(2-tert-butyl)aniline is replaced by the same molar amount of 2-bromo-4,5-difluorobenzoyl-N-(2-tert-butyl)aniline.

[0159] The compound 23 prepared in this example is a yellow foam, and its isolated yield is 64%. The enantiomeric excess of the product determined by chiral HPLC is 90%. 1 H NMR (400MHz, CDCl3), δ: 8.42–8.22 (m, 2H), 8.11 (dd, J = 12.0, 7.0 Hz, 1H), 7.87 (dd, J = 8.3, 1.5 Hz, 1H), 7.72–7.58 (m, 2H), 7.47 (dd, J = 8.1, 1.2 Hz, 1H), 7.34 (td, J = 7.5, 1.5 Hz, 1H), 7.30–7.25 (m, 1H), 7.17 (dd, J = 7.8, 1.5 Hz, 1H), 6.74 (ddd, J = 8.5, 7.1, 1.3 Hz, 1H), 4.93 (dd, J = 8.6, 1.1 Hz, 1H), 1.20 (s, 9H), and its structural formula is shown below:

[0160]

[0161] Embodiment 24

[0162] Preparation of (S)-5-(2-tert-butyl)phenyl-8,9-dimethoxybenzophenanthridine-6(5H)-one (Compound 24)

[0163] The method is the same as that of Example 1 except that the 1-iodonaphthalene in Example 1 is replaced by the same molar amount of 1-iodobenzofuran, and the 2-bromobenzoyl-N-(2-tert-butyl)aniline is replaced by the same molar amount of 2-bromo-4,5-dimethoxybenzoyl-N-(2-tert-butyl)aniline.

[0164] The compound 24 prepared in this example is a white foam with an isolated yield of 89%. The enantiomeric excess of the product determined by chiral HPLC is 90%. 1H NMR (400MHz, CDCl3), δ: 8.43 (d, J=8.9Hz, 1H), 7.89 (s, 1H), 7.85 (dd, J=8.3, 1.4Hz, 1H ),7.70(s,1H),7.66–7.56(m,2H),7.46(dd,J=8.2,1.2Hz,1H),7.33(td,J=7.5,1.4Hz, 1H), 7.25 (td, J = 7.6, 7.1, 1.1 Hz, 1H), 7.19 (dd, J = 7.8, 1.5 Hz, 1H), 6.72 (ddd, J = 8.5, 7.2, 1.2 Hz, 1H), 4.92 (d, J = 8.5 Hz, 1H), 4.15 (s, 3H), 4.03 (s, 3H), 1.19 (s, 9H), its structural formula is as follows:

[0165]

[0166] Embodiment 25

[0167] Preparation of (S)-5-(2-(1-(tert-butyldimethylsilyloxy))-2-methylpropyl)phenylbenzophenanthridine-6(5H)-one (Compound 25)

[0168] The process is the same as in Example 1 except that the 2-bromobenzoyl-N-(2-tert-butyl)aniline in Example 1 is replaced by an equal molar amount of 2-bromobenzoyl-N-(2-(1-(tert-butyldimethylsilyloxy))-2-methylpropyl)aniline.

[0169] The compound 25 prepared in this example is a yellow solid with an isolated yield of 83%. The enantiomeric excess of the product determined by chiral HPLC is 92%. 1 H NMR (400MHz, CDCl3), δ: 8.58 (dd, J=7.9, 1.4Hz, 1H), 8.42 (dd, J=16.8, 8.5Hz, 2H), 7.86 (t, J=7 .7Hz,1H),7.83–7.75(m,3H),7.64(t,J=7.5Hz,1H),7.52(t,J=7.8Hz,1H),7.39–7.31(m,2H), 7.17 (d, J = 9.1 Hz, 1H), 7.07 (d, J = 7.8 Hz, 1H), 7.00 (ddd, J = 8.8, 6.7, 1.5 Hz, 1H), 3.60–3.30 (dd, J = 24.0, 12.0 Hz, 2H), 1.14 (d, J = 11.7 Hz, 6H), 0.77 (s, 9H), -0.21 (d, J = 20.7 Hz, 6H), its structural formula is shown below:

[0170]

[0171] Embodiment 26

[0172] Preparation of (S)-5-(2-(tert-butyldimethylsilyloxy)propyl)phenylbenzophenanthridine-6(5H)-one (Compound 26)

[0173] The process is the same as in Example 1 except that the 2-bromobenzoyl-N-(2-tert-butyl)aniline in Example 1 is replaced by an equal molar amount of 2-bromobenzoyl-N-(2-(tert-butyldimethylsilyloxy)propyl)aniline.

[0174] The compound 26 prepared in this example is a yellow liquid with an isolated yield of 87%. The enantiomeric excess of the product determined by chiral HPLC is 95%. 1 H NMR (400MHz, CDCl3), δ: 8.58 (dd, J = 7.9, 1.4Hz, 1H), 8.43 (d, J = 8.3Hz, 1H), 8.39 (d, J = 8.8Hz, 1H), 8.06 (dd,J=8.2,1.5Hz,1H),7.86(ddd,J=8.3,7.1,1.5Hz,1H),7.81(dd,J=8.0,1.4Hz,1H),7.77(d,J=8.8Hz ,1H),7.64(t,J=7.5Hz,1H),7.53(t,J=8.0Hz,1H),7.36(t,J=7.4Hz,1H),7.33–7.27(m,2H),6.99(ddd,J=16.3,8.3,1.5Hz,2H),1.53(s,3H),1.24(s,3H),0.87(s,9H),0.05(s,3H),-0.06(s,3H), its structural formula is shown below:

[0175]

[0176] Embodiment 27

[0177] Preparation of (S)-5-(2-(1-hydroxy-2-methylpropyl))phenylbenzophenanthridine-6(5H)-one (Compound 27)

[0178] The process is the same as in Example 1 except that the 2-bromobenzoyl-N-(2-tert-butyl)aniline in Example 1 is replaced by an equal molar amount of 2-bromobenzoyl-N-(2-(1-hydroxy-2-methylpropyl))aniline.

[0179] The compound 27 prepared in this example is a white foam with an isolated yield of 82%. The enantiomeric excess of the product determined by chiral HPLC is 79%. 1H NMR (400MHz, CDCl3), δ: 8.61 (d, J=8.0Hz, 1H), 8.46 (dd, J=15.1, 8.4Hz, 2H), 7.90 (t, J=7.8Hz ,1H),7.86(d,J=8.1Hz,1H),7.82(dd,J=8.9,2.8Hz,2H),7.66(t,J=7.6Hz,1H),7.57(t,J=8.1 Hz, 1H), 7.40(t, J=7.5Hz, 1H), 7.35(t, J=7.7Hz, 1H), 7.25(d, J=9.6Hz, 1H), 7.10–7.02(m, 1H), 6.94(d, J=7.8Hz, 1H), 3.67–3.57(m, 2H), 2.56(br, 1H), 1.39(s, 3H), 1.08(s, 3H), and its structural formula is shown below:

[0180]

Claims

1. A 5-arylbenzophenanthridine-6(5H)-one C–N axial chiral compound, characterized in that: The structure of the 5-arylbenzophenanthridine-6(5H)-one C–N axial chiral compound is shown in Formula I: Among them, R x Methyl, OTBS, The wavy line is the connection location; R y For H, Br, The wavy line is the connection location; R z is H, methyl, methoxy, nitro or fluorine; The dotted line indicates that the benzene ring structure is an ortho-monosubstituted or para-substituted structure.

2. The method for preparing a 5-arylbenzophenanthridine-6(5H)-one C-N axial chiral compound according to claim 1, characterized in that: The following steps are involved: The compounds represented by general formula II and general formula III are used as raw materials, reacted in a solvent under the action of a palladium catalyst, norbornene, a chiral ligand, a base and an additive, and the reaction product is separated after the reaction is completed to obtain a compound represented by formula I; The reaction formula is as follows: Among them, in the compound represented by general formula II, R x Selected from methyl, OTBS, The wavy line is the connection location; R y Selected from H, Br, The wavy line is the connection location; R z is selected from H, methyl, methoxy, nitro or fluorine; The compound shown in the general formula III is selected from wherein R is H, methyl, methoxy, fluoro, bromo, cyclopropyl or phenyl.

3. The method for preparing a 5-arylbenzophenanthridine-6(5H)-one C-N axial chiral compound according to claim 2, characterized in that: The palladium catalyst is one of palladium acetate, palladium trifluoroacetate, Pd2(dba)3, palladium chloride, palladium bromide or Pd(MeCN)Cl2.

4. The method for preparing a 5-arylbenzophenanthridine-6(5H)-one C-N axial chiral compound according to claim 2, characterized in that: The chiral ligand is one of the following compounds L1-L27:

5. The method for preparing a 5-arylbenzophenanthridine-6(5H)-one C-N axial chiral compound according to claim 2, characterized in that: The base is one of potassium carbonate, cesium carbonate, sodium carbonate, silver carbonate, silver sulfate, silver phosphate, silver nitrate or silver acetate; the additive is MS, MS or One of the MS.

6. The method for preparing a 5-arylbenzophenanthridine-6(5H)-one C-N axial chiral compound according to claim 2, characterized in that: The solvent is one or more of tetrahydrofuran, 1,4-dioxane, 1,2-dichloroethane, dichloromethane, chloroform, toluene, N,N-dimethylformamide, dimethyl sulfoxide and water.

7. The method for preparing a 5-arylbenzophenanthridine-6(5H)-one C-N axial chiral compound according to claim 2, characterized in that: The palladium catalyst is Pd2(dba)3, the chiral ligand is the chiral bisimidazoline ligand L25, the base is silver sulfate, and the additive is MS.

8. The method for preparing a 5-arylbenzophenanthridine-6(5H)-one C-N axial chiral compound according to claim 2, characterized in that: The amounts of the compound represented by the general formula III, the palladium catalyst, norbornene, the chiral ligand and the base are 1.2 to 1.5 times, 0.05 to 0.2 times, 1.0 to 2.0 times, 0.1 to 0.2 times and 1.0 to 3.0 times the amount of the compound represented by the general formula II, respectively; the ratio of the mass of the additive to the amount of the compound represented by the general formula II is 50 mg to 100 mg / 0.1 mmol; the ratio of the amount of the compound represented by the general formula II to the volume of the solvent is 1.0 mmol: 10 to 20 mL.

9. The method for preparing a 5-arylbenzophenanthridine-6(5H)-one C-N axial chiral compound according to claim 2, characterized in that: The reaction temperature is 65°C to 100°C, and the reaction time is 6h to 48h.

10. Use of the 5-arylbenzophenanthridine-6(5H)-one C–N axial chiral compound according to claim 1 in the field of asymmetric catalysis and optoelectronic materials.

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