CN100584459C - Application of Dehydroabietine Aminothiourea Catalyst in High Enantiomeric Two-handed Synthesis of Chiral Compounds - Google Patents

Abstract

The invention discloses the application of a dehydroabietic amine-chiral thiourea catalyst in the dual-handed synthesis of gamma-nitro-aromatic ketones and gamma-nitro-aromatic heteroketone chiral compounds with high enantiomers. The invention successfully utilizes natural chiral sources to synthesize a new class of dehydroabietic amine-chiral thiourea catalysts with high catalytic activity. This type of catalyst is cheap, easy to modify and prepare, simple to handle, easy to separate and recover from the product, recyclable, and expands the range of limited known thiourea catalysts. The invention realizes the high-efficiency and high-activity asymmetric catalysis of the same catalyst in the same reaction system to generate high optically pure target products with different configurations. The method is simple to operate, does not use metal reagents, and has less environmental pollution; the reaction condition is mild, and it does not need to be carried out under harsh anhydrous and oxygen-free conditions, and the reaction can be carried out in the air.

Description

Application of Dehydroabietine Aminothiourea Catalyst in High Enantiomeric Two-handed Synthesis of Chiral Compounds

technical field

The invention relates to the application of a class of dehydroabietic amine-chiral thiourea catalysts in the dual-handed synthesis of gamma-nitro-aromatic ketones and gamma-nitro-aromatic heteroketone chiral compounds with high enantiomers.

Background technique

As a new concept in the 21st century, asymmetric organocatalysis has become an important tool for building molecular skeletons due to its high efficiency and high selectivity. It plays a huge role in organic synthesis and the pharmaceutical industry. The development of biology provides broad application prospects. Asymmetric Michael addition products: γ-nitrocarbonyl compounds are a class of very useful synthetic intermediates in organic synthesis. For example: gamma-nitro-aromatic ketones and gamma-nitro-aromatic heteroketone chiral compounds can be further converted into very useful chiral pyrrolidine derivatives etc. (R.Galeazzi, G.Martelli, G.Mobbili, M.Orena, S.Rinaldi, Tetrahedron: Asymmetry 2003, 14, 3353.), and the chiral compounds of different configurations have different pharmaceutical activities. Therefore, if the synthesis of chiral compounds of γ-nitro-aromatic ketones and γ-nitro-aromatic heteroketones with different configurations can be realized, it will greatly promote the development of pharmaceutical synthesis.

Takemoto et al. (T.Okino, Y.Hoashi, Y.Takemoto, J.Am.Chem.Soc.2003, 125, 12672..) reported for the first time the Michael addition reaction catalyzed by a chiral bifunctional thiourea catalyst, they The addition of diethyl malonate to a series of aryl-substituted nitroethenes was efficiently catalyzed by thiourea catalysts in good yields but only in the (S) configuration. into a product.

So far, several research groups have synthesized and reported their own bifunctional thiourea catalysts and applied them in the Michael addition reaction of nitroalkenes. For example: Wang et al. (J.Wang, H.Li, W.H.Duan, L.S.Zu, W.Wang, Org.Lett.2005, 7, 4713.) reported a chiral binaphthylthiourea catalyst 1a; Soós group ( B.Vakulya, S.Varga, A.Csampai, T.Soos, Org.Lett.2005, 7, 1967.), Connon group (S.H.McCooey, S.J.Connon, Angew.Chem.Int.Ed.2005, 44, 6367 .) and Dixon group (P.S.Hynes, D.Stranges, P.A.Stupple, A.Guarna, D.J.Dixon, Org.Lett.2007,9,2107.) modify the structure of natural cinchona alkaloids, replace C- with thiourea The hydroxyl group on 9 has designed a novel bifunctional thiourea catalyst 2a-2b derived from cinchona base; 6366.) reported the bifunctional catalyst 3a of a primary aminothiourea; Urea Catalysts 4a-4b; Tang et al. (C-L.Cao, M-C.Ye, X-L.Sun, Y.Tang, Org.Lett.2006, 8, 2901.) reported proline-derived thiourea bifunctional chiral catalysts 5a; In addition, recently, Ma et al. (K.Liu, H-F.Cui, J.Nie, K-Y.Dong, X-J.Li, J-A.Ma, Org.Lett.2007, 9, 923.), reported the Sugar ring-derived thiourea bifunctional organocatalysts 6a–6b. The chemical structural formulas of thiourea catalysts 1a, 2a-2b, 3a, 4a-4b, 5a and 6a-6b are shown in FIG. 1 . Although the above research groups have synthesized a variety of thiourea catalysts and successfully applied them in asymmetric chiral synthesis, compared with other types of catalysts, there are very few thiourea catalysts reported so far, and their design and synthesis is still a challenge. Quite a challenge. At present, the design and synthesis of new high-efficiency thiourea catalysts is still the goal of organic chemists. And it is worth noting that the chiral amine-thiourea catalyst reported above can only show high catalytic activity in effectively controlling one of the configurations of the reaction products, and when this type of chiral amine-thiourea catalyst is in The reactions that control the other configuration of the reaction product show poor reactivity. For example: the thiourea bifunctional organic catalysts 6a-6b derived from sugar rings reported by Ma et al., when the configuration of the cyclohexanediamine moiety in the thiourea catalyst is (1R, 2R), it effectively catalyzes the reaction of acetophenone on Asymmetric Michael addition of nitroalkenes, and the addition product is (S)-γ-nitroketone. However, when the configuration of cyclohexanediamine in the catalyst is (1S, 2S), poor reactivity is shown, and the adduct (R)-γ-nitroacetophenone generated has only 46% Yield, and enantioselectivity also has obvious decline (see Figure 2), that is to say that the sugar ring part in this catalyst has very high selectivity to the cyclohexanediamine part in exerting its catalytic activity. This study shows that only when the configuration of the cyclohexanediamine moiety is (1R, 2R), the thiourea catalyst can show high catalytic efficiency, obtain good yield and well-controlled configuration in the stereo space (Si- surface manual control) to obtain (S)-γ-nitroketone with high optical purity. However, the sugar ring moiety in the thiourea catalyst showed poor compatibility to (1S,2S)-cyclohexanediamine, resulting in the addition product (R) -γ-Nitroacetophenone not only showed poor yield, but also relatively low enantioselectivity. More importantly, no related synthetic methods for the synthesis of γ-nitro-aromatic heteroketone chiral compounds with high enantiomers have been reported so far.

Contents of the invention

In view of the current thiourea catalysts can only effectively catalyze the synthesis of a reaction product of a configuration in the same reaction catalysis system, the purpose of the present invention is to provide a class that can effectively catalyze the synthesis of two configurations in the same reaction catalysis system Configuration ((S) configuration or (R) configuration) reaction product of dehydroabietamine-chiral thiourea catalyst.

Another object of the present invention is to provide a hand-controlled synthesis of γ-nitro-aromatic ketones and γ-nitro-aromatic heteroketone chiral compounds with high enantiomers and a preparation method thereof.

Another object of the present invention is the application of dehydroabietic amine-chiral thiourea catalyst in the hand-controlled synthesis of gamma-nitro-aromatic ketones and gamma-nitro-aromatic heteroketone chiral compounds with high enantiomers .

(1). A class of dehydroabietic amine-chiral thiourea catalyst, its structural formula is as shown in (I):

(I) n is 1 in the formula, or is 0; R group is (1S, 2S)-cyclohexanediamine, or is (1S, 2R)-cyclohexanediamine, or is 3,5-ditrifluoro methylaniline.

A kind of preparation method of dehydroabietamine-chiral thiourea catalyst:

Dissolve dehydroabietamine or degraded dehydroabietamine in anhydrous ether solution, add dehydroabietamine or dehydroabietamine 1 times the amount of dicyclohexylcarbodiimide (DCC), after stirring for 15 minutes, Add dehydroabietamine or dehydroabietamine 5 times the amount of carbon disulfide dropwise at 0°C, react for 8 hours, filter, and column chromatography (H60 silica gel, n-hexane:ethyl acetate=5:1) to obtain the iso Thiocyanate; then (1S, 2S)-cyclohexanediamine, or (1R, 2R)-cyclohexanediamine, or 3,5-bistrifluoromethylaniline were dissolved in anhydrous dichloromethane, Isothiocyanate was added dropwise at 0°C, reacted at room temperature for 12 hours, and the final product was obtained after column chromatography (H60 silica gel, ethyl acetate:methanol=6:1).

Above-mentioned reaction is expressed as follows with chemical formula:

(2). Gamma-nitro-aromatic ketone chiral compounds, the structural formula of which is shown in (II):

(S)-configuration γ-nitro-aromatic ketone (R)-configuration γ-nitro-aromatic ketone

(II)

(II) In the formula, R ₁ is -H, or -Me, or -OMe, or -Cl, or -Br, or -F.

_R is -Ph, or -napathyl, or -Cl-Ph, or -Br-Ph, or -F-Ph, or -thiophenyl, or -furanyl, or -Me-Ph, or for -OMe-Ph.

The preparation method of high enantiomeric hands-on synthesis of gamma-nitro-aryl ketone chiral compounds:

Substrate nitroalkene compound and consumption are the dehydroabietic amine-chiral thiourea catalyst of substrate nitroalkene compound 15mol%, and consumption is that substrate nitroalkene compound 15mol% benzoic acid is dissolved in methylene chloride, in Add the aromatic ketone compound in an amount 3 times that of the substrate nitroalkene compound at 0°C, react for 2 hours, and continue the reaction at room temperature for 60 hours. After the reaction was complete, the final product was obtained by column chromatography (H60 silica gel, petroleum ether: ethyl acetate = 8:1). Above-mentioned reaction is expressed as follows with chemical formula:

(3). Gamma-nitro-aromatic heteroketone chiral compounds, the structural formula of which is shown in (III):

(S)-configuration γ-nitro-aromatic heteroketone

(R)-configuration γ-nitro-aromatic heteroketone

(III)

(III) In the formula, X is O, or is S; Y is -CH(-C), or is N.

R ₃ is -Ph, or -napathyl, or -Cl-Ph, or -Br-Ph, or -F-Ph, or -thiophenyl, or -furanyl, or -Me-Ph, or for -OMe-Ph.

R ₄ is -H, or -Me, or -Cl, or -Br, or -F.

R ₅ is -H, or -Me, or -Cl, or -Br, or -F.

R ₆ is -H, or -Me, or -Cl, or -Br, or -F.

R ₇ is -H, or -Me, or -Cl, or -Br, or -F.

R ₈ is -H, or -Me.

The preparation method of high-enantiomeric double-handedly synthesized γ-nitro-aromatic heteroketone chiral compounds:

Substrate nitroalkene compound and consumption are the dehydroabietic amine-chiral thiourea catalyst of substrate nitroalkene compound 15mol%, and consumption is that substrate nitroalkene compound 15mol% benzoic acid is dissolved in methylene chloride, in At 0°C, an aromatic heteroketone compound was added in an amount three times that of the substrate nitroalkene compound. After reacting for 2 hours, the reaction was continued at room temperature for 72 hours. After the reaction was complete, the final product was obtained by column chromatography (H60 silica gel, petroleum ether: ethyl acetate = 8:1). Above-mentioned reaction is expressed as follows with chemical formula:

In the present invention, we have designed and synthesized a new class of dehydroabietamine-thiourea catalysts by utilizing the easily available natural organic product dehydroabietamine-thiourea catalysts by studying the properties and structures of bifunctional thiourea catalysts. γ-nitro-aromatic ketones and γ-nitro-aromatic heteroketone chiral compounds were synthesized by high-enantiomer double-handed catalysis of rosin amine-thiourea catalyst. The advantages of the present invention are reflected in the following points:

(1). We successfully synthesized a new class of dehydroabietic amine-chiral thiourea catalysts with high catalytic activity using natural chiral sources. This type of catalyst is cheap, easy to modify and prepare, simple to handle, easy to separate and recover from products, and can be recycled. It not only expands the range of limited known thiourea catalysts, but also shows the great potential of dehydroabietic amine natural products in the field of asymmetric catalysis.

(2). In the current field of asymmetric synthesis, there are very few same catalysts that can asymmetrically catalyze high-efficiency and high-activity high-enantiomeric products in two configurations (S) and (R) under the same reaction system. , the thiourea catalysts (1a, 2a-2b, 3a, 4a-4b, 5a and 6a-6b) in the background material also cannot achieve the above-mentioned purpose of synthesizing high enantiomeric products. Studies have shown that the dehydroabietic amine-chiral thiourea catalyst of the present invention can catalyze high-enantiomer products of S) and (R) configurations with high efficiency and high activity under the same reaction system. In its thiourea catalyst, the dehydroabietic amine moiety has very low selectivity to the cyclohexanediamine moiety in exerting its catalytic activity. That is to say, when the partial configuration of cyclohexanediamine is (1R, 2R) or (1S, 2S), this type of catalyst can exert its excellent catalytic activity without losing the high yield and high optical purity of the product. In the research, when the configuration of cyclohexanediamine in the dehydroabietic amine-chiral thiourea catalyst is (1R, 2R), the γ-nitro-aromatic ketones and γ-nitro-aromatic ketones synthesized by asymmetric catalysis Heteroketone chiral compounds can achieve 99% yield and greater than 99% enantioselectivity; when the configuration of cyclohexanediamine is (1S, 2S), the asymmetrically catalyzed γ-nitro- Aromatic ketones and γ-nitro-aromatic heteroketone chiral compounds can also achieve 99% yield and greater than 99% enantioselectivity. The different configurations of the cyclohexanediamine moiety in the thiourea catalyst not only do not reduce the activity of the catalyst and the yield of the target product, but also catalyze the formation of products with different configurations in different spatial chiral controls. In short, the dehydroabietic amine-chiral thiourea catalyst can control the formation of products with high enantiomeric chirality under the condition of high efficiency and high catalytic activity. The dehydroabietic amine-chiral thiourea catalyst of the present invention realizes the high-efficiency and high-activity asymmetric catalysis of the same catalyst in the same reaction system in the field of organic synthesis to generate high optically pure target products with different configurations.

(3). In the present invention, we provide an effective preparation method for high enantiomeric hands-on synthesis of γ-nitro-aromatic ketones and γ-nitro-aromatic heteroketone chiral compounds. The method is simple to operate, does not use metal reagents, has less environmental pollution, and is environmentally friendly; the reaction condition is mild, and the reaction can be carried out in the air instead of harsh anhydrous and oxygen-free conditions.

Detailed ways

The invention will be illustrated by the following examples, but not limited thereto.

The product of the present invention is identified by mass spectrometry, NMR and infrared, and the enantioselectivity is determined by high performance liquid phase (HPLC).

Embodiment 1: dehydroabietamine-thiourea catalyst (abbreviation: (1R, 2R)-CHDA-DHATU), [English full name 1-((1R, 2R)-2-aminocyclohexyl)-3-(((1R, 4aS, 10aR)-7-isopropyl-1, 4a-dimethyl-1, 2,3,4,4a,9,10,10a-octahydrophenanthren-1-yl)methyl)thiourea] structural formula is as follows:

Dehydroabietamine-thiourea catalyst (1R, 2R)-CHDA-DHATU preparation method:

Dissolve 2.85g (10mmol) of dehydroabietamine in 50ml of anhydrous ether solution, and add 2.06g (10mmol) of dicyclohexylcarbodiimide (DCC). After stirring for 15 minutes, 4 ml (50 mmol) of carbon disulfide was added dropwise at 0° C., and the reaction was carried out at room temperature for 8 hours. After filtration and concentration of the filtrate, column chromatography (H60 silica gel, n-hexane:ethyl acetate=5:1) gave 3.1 g of isothiocyanate (95% yield).

Dissolve 1.14g (10mmol) (1R, 2R)-cyclohexanediamine in 40ml of anhydrous dichloromethane, and mix 3.1g of isothiocyanate dissolved in 20ml of anhydrous dichloromethane at 0°C The solution was added dropwise into a mixed solution of (1R,2R)-cyclohexanediamine and anhydrous dichloromethane over a period of 1.5 hours. After the addition was complete, the above reaction was continued at room temperature for 12 hours. Concentration and column chromatography (H60 silica gel, ethyl acetate:methanol=6:1) gave 3.3 g of the final product as a white solid (80% yield).

[α] ²⁰ _D = +69 (c = 1.0, CHCl ₃ ); melting point: 88-89°C.

NMR analysis:

¹ H NMR (300MHz, [D ⁶ ]DMSO): δ7.38 (br, 1H), 7.12-7.15 (d, J=8.1Hz, 1H), 6.92-6.94 (d, J=8.1Hz, 1H), 6.83(s, 1H), 3.74(br, 1H), 3.38-3.42(m, 2H), 2.68-2.79(m, 3H), 2.39-2.48(m, 1H), 2.23-2.27(d, J=12.9 Hz, 1H), 1.97-2.00(m, 1H), 1.49-1.81(m, 7H), 1.34-1.38(m, 2H), 1.24-1.28(m, 2H), 1.07-1.19(m, 9H), 0.91-1.04 (m, 7H); ¹³ C NMR (75MHz, [D ⁶ ]DMSO): δ147.0, 144.9, 134.5, 126.4, 124.1, 123.5, 54.2, 44.5, 37.9, 37.3, 36.99, 35.8, 34.2, 32.9, 31.5, 29.6, 25.1, 24.5, 24.3, 23.9, 18.7, 18.5, 18.2.

Infrared spectral analysis: 3259, 3066, 2929, 2860, 2213, 1549, 1452, 1378, 1234, 1202, 1087, 910, 823, 732, 647cm ^-1 .

High-resolution mass spectrometry analysis:

HRMS-ESI(m/z): calcd for C ₂₇ H ₄₃ N ₃ S[M+H] ⁺ : 442.3250; found: 442.3245, 1.1ppm.

Embodiment 2: dehydroabietamine-thiourea catalyst (abbreviation: (1S, 2S)-CHDA-DHATU), [English full name: 1-((1S, 2S)-2-aminocyclohexyl)-3-(((1R , 4aS, 10aR)-7-isopropyl-1, 4a-dimethyl-1, 2,3,4,4a,9,10,10a-octahydrophenanthren-1-yl)methyl)thiourea] structural formula is as follows:

The preparation method of dehydroabietamine-thiourea catalyst (1S, 2S)-CHDA-DHATU is the same as that of Example 1.

[α] ²⁰ _D = -57 (c = 1.1, CHCl ₃ ); melting point: 87-88°C.

NMR analysis:

¹ H NMR (300MHz, [D ⁶ ]DMSO): δ7.40 (br, 1H), 7.14-7.16 (d, J=8.1Hz, 1H), 6.93-6.96 (dd, J=1.5Hz, 8.1Hz, 1H), 6.84(s, 1H), 3.75(br, 1H), 3.35-3.44(m, 2H), 2.71-2.78(m, 3H), 2.40-2.46(m, 1H), 2.24-2.28(d, J=12.9Hz, 1H), 2.00(m, 1H), 1.47-1.87(m, 7H), 1.35-1.40(m, 2H), 1.21-1.25(m, 2H), 1.13-1.16(m, 9H) , 0.95-0.96 (m, 7H); ¹³ C NMR (75MHz, [D ⁶ ]DMSO): δ147.0, 144.9, 134.4, 126.4, 124.0, 123.5, 54.2, 44.5, 38.0, 37.4, 37.0, 34.2, 32.8 , 31.5, 29.7, 25.1, 24.5, 24.3, 23.9, 23.88, 18.7, 18.5, 18.2.

Infrared spectral analysis: 3355, 3114, 3031, 2919, 2851, 1953, 1683, 1549, 1478, 1380, 1233, 1062, 947, 875, 754, 698, 628, 543cm ^-1 .

High-resolution mass spectrometry analysis:

HRMS-ESI(m/z): calcd for C ₂₇ H ₄₃ N ₃ S[M+H] ⁺ : 442.3250; found: 442.3244, 1.3ppm.

Example 3: (S)-4-nitro-1,3-diphenyl-1-butanone and (R)-4-nitro-1,3-diphenyl-1-butanone have the following structural formulas:

a. The method for preparing (S)-4-nitro-1,3-diphenyl-1-butanone with dehydroabietamine-thiourea catalyst (1R, 2R)-CHDA-DHATU:

Dissolve 15mg (0.1mmol) substrate nitrostyrene, 6.6mg (0.015mmol) dehydroabietamine-thiourea catalyst (1R, 2R)-CHDA-DHATU, 1.8mg (0.015mmol) benzoic acid in 0.8ml di In methyl chloride, 35 μl (0.3 mmol) of acetophenone was added at 0° C., and after 2 hours of reaction, the reaction was continued at room temperature for 60 hours. After the reaction was complete, it was extracted three times with dichloromethane (8ml each time), and dried with 2g of anhydrous sodium sulfate. Concentration and column chromatography (H60 silica gel, petroleum ether: ethyl acetate = 8: 1) gave the final product (S)-4-nitro-1,3-diphenyl-1-butanone 26.6 mg (99 %Yield).

[α] ²⁰ _D = -22 (c = 1.0, CHCl ₃ ); melting point: 90-92°C.

High performance liquid phase analysis (HPLC): (chiral column Chiralcel AS-H, isopropanol/n-hexane=15/85, 0.9mL/min, UV absorption 254nm.) t _major =18.41min, enantioselectivity greater than 99%.

b. The method for preparing (R)-4-nitro-1,3-diphenyl-1-butanone with dehydroabietamine-thiourea catalyst (1S, 2S)-CHDA-DHATU:

Dissolve 15mg (0.1mmol) substrate nitrostyrene, 6.6mg (0.015mmol) dehydroabietamine-thiourea catalyst (1S, 2S)-CHDA-DHATU, 1.8mg (0.015mmol) benzoic acid in 0.8ml di In methyl chloride, 35 μl (0.3 mmol) of acetophenone was added at 0° C., and after 2 hours of reaction, the reaction was continued at room temperature for 60 hours. After the reaction was complete, it was extracted three times with dichloromethane (8ml each time), and dried with 2g of anhydrous sodium sulfate. Concentration, column chromatography (H60 silica gel, petroleum ether: ethyl acetate = 8: 1) gave white solid final product (R)-4-nitro-1,3-diphenyl-1-butanone 25.8mg (96 %Yield).

[α] ²⁰ _D = +12 (c = 1.3, CHCl ₃ ); melting point: 91-92°C.

High performance liquid phase analysis (HPLC): (chiral column Chiralcel AS-H, isopropanol/n-hexane = 15/85, 0.9mL/min, UV absorption 254nm.) t _major = 22.91min, t _minor = 17.94min, Enantioselectivity reaches 98%..

NMR analysis:

¹ H NMR (400MHz, CDCl ₃ ): δ7.92-7.94(d, J=8Hz, 2H), 7.57-7.59(m, 1H), 7.45-7.48(m, 2H), 7.26-7.34(m, 5H ), 4.82-4.87(dd, J=6.4Hz, 12.4Hz, 1H), 4.67-4.72(dd, J=8.4Hz, 12.8Hz, 1H), 4.24(m, 1H), 3.45-3.48(m, 2H ); ¹³ CNMR (100MHz, CDCl ₃ ): δ196.8, 139.1, 133.5, 129.1, 128.7, 128.0, 127.9, 127.5, 79.6, 41.5, 39.3.

Infrared spectrum analysis: 3058, 3029, 2920, 1687, 1544, 1440, 1367, 1268, 1224, 1084, 988, 764, 703, 623, 559cm ^-1 .

Mass Spectrometry:

ESI-MS: m/z 270[M ⁺ ].

Example 4: (S)-1-(3-methylphenyl)-4-nitro-3-phenyl-1-butanone and (R)-1-(3-methylphenyl)-4-nitro- The structural formula of 3-phenyl-1-butanone is as follows:

a. Prepare (S)-1-(3-methylphenyl)-4-nitro-3-phenyl-1-butanone with dehydroabietamine-thiourea catalyst (1R, 2R)-CHDA-DHATU, prepare In the process, 40 μl (0.3 mmol) of m-methylacetophenone was used to replace 35 μl (0.3 mmol) of acetophenone in Example 3, and the preparation process was the same as that of Example 3. (S)-1-(3-Tolyl)-4-nitro-3-phenyl-1-butanone was obtained in 91% yield.

[α] ²⁰ _D = -10 (c = 0.6, CHCl ₃ ).

High-performance liquid phase analysis (HPLC): (chiral column Chiralcel AD-H, isopropanol/n-hexane=15/85, 1.0mL/min, UV absorption 254nm.) t _major =9.80min, enantioselectivity greater than 99%.

b. Prepare (R)-1-(3-methylphenyl)-4-nitro-3-phenyl-1-butanone with dehydroabietamine-thiourea catalyst (1S, 2S)-CHDA-DHATU, prepare In the process, 40 μl (0.3 mmol) of m-methylacetophenone was used to replace 35 μl (0.3 mmol) of acetophenone in Example 3, and the preparation process was the same as that of Example 3. (R)-1-(3-Tolyl)-4-nitro-3-phenyl-1-butanone was obtained in 93% yield.

[α] ²⁰ _D = +6 (c = 1.3, CHCl ₃ ).

High performance liquid phase analysis (HPLC): (chiral column Chiralcel AD-H, isopropanol/n-hexane = 15/85, 1.0mL/min, UV absorption 254nm.) t _major = 12.33min, t _minor = 9.90min, Enantioselectivity reaches 98%.

NMR analysis:

¹ H NMR (400MHz, CDCl ₃ ): δ7.71-7.72 (m, 2H), 7.25-7.40 (m, 7H), 4.81-4.86 (dd, J=6.8Hz, 12.8Hz, 1H), 4.67-4.71 (dd, J=8.4Hz, 12.8Hz, 1H), 4.21-4.24(m, 1H), 3.38-3.50(m, 2H), 2.40(s, 3H); ¹³ C NMR (100MHz, CDCl ₃ ): δ196 .99, 139.2, 138.6, 136.5, 134.3, 129.0, 128.6, 128.5, 127.8, 127.4, 125.2, 79.6, 41.6, 39.3, 21.3.

Infrared spectrum analysis: 3031, 2920, 1683, 1551, 1431, 1378, 1273, 1160, 980, 767, 698, 562cm ^-1 .

High-resolution mass spectrometry analysis:

HRMS-ESI(m/z): calcd for C ₁₇ H ₁₇ NO ₃ +NH ₄ ⁺ : 301.1547; found: 301.1547, 0.0ppm.

Example 5: (S)-1-(3-bromophenyl)-4-nitro-3-phenyl-1-butanone and (R)-1-(3-bromophenyl)-4-nitro The structural formula of base-3-phenyl-1-butanone is as follows:

a. Prepare (S)-1-(3-bromophenyl)-4-nitro-3-phenyl-1-butanone with dehydroabietamine-thiourea catalyst (1R, 2R)-CHDA-DHATU, In the preparation process, 40 μl (0.3 mmol) of m-bromoacetophenone was used instead of 35 μl (0.3 mmol) of acetophenone in Example 3, and the preparation process was the same as that of Example 3. (S)-1-(3-Bromophenyl)-4-nitro-3-phenyl-1-butanone was obtained in 96% yield.

[α] ²⁰ _D = -13 (c = 1.7, CHCl ₃ ).

High performance liquid phase analysis (HPLC): (chiral column Chiralcel AD-H, isopropanol/n-hexane = 15/85, 1.0mL/min, UV absorption 254nm.) t _major = 11.65min, t _minor = 13.44min, Enantioselectivity reaches 98%.

b. Prepare (R)-1-(3-bromophenyl)-4-nitro-3-phenyl-1-butanone with dehydroabietamine-thiourea catalyst (1S, 2S)-CHDA-DHATU, In the preparation process, 40 μl (0.3 mmol) of m-bromoacetophenone was used instead of 35 μl (0.3 mmol) of acetophenone in Example 3, and the preparation process was the same as that of Example 3. (R)-1-(3-Bromophenyl)-4-nitro-3-phenyl-1-butanone was obtained in 91% yield.

[α] ²⁰ _D = +8 (c = 1.0, CHCl ₃ ).

High performance liquid phase analysis (HPLC): (chiral column Chiralcel AD-H, isopropanol/n-hexane = 15/85, 1.0mL/min, UV absorption 254nm.) t _major = 13.62min, t _minor = 11.78min, Enantioselectivity greater than 99%..

NMR analysis:

¹ H NMR (400MHz, CDCl ₃ ): δ8.03(s, 1H), 7.83-7.85(d, J=8.0Hz, 1H), 7.69-7.71(m, 1H), 7.24-7.36(m, 6H) , 4.79-4.84(dd, J=7.2Hz, 12.4Hz, 1H), 4.66-4.72(dd, J=8.0Hz, 12.4Hz, 1H), 4.18-4.25(m, 1H), 3.37-3.49(m, 2H); ¹³ C NMR (100MHz, CDCl ₃ ): δ195.5, 138.8, 138.1, 136.4, 131.1, 130.3, 129.1, 128.0, 127.4, 126.5, 123.1, 79.4, 41.6, 39.2.

Infrared spectrum analysis: 3064, 3031, 2922, 2854, 1689, 1551, 1420, 1377, 1201, 1070, 995, 765, 700, 559cm ^-1 .

High-resolution mass spectrometry analysis:

HRMS-ESI(m/z): calcd for C ₁₆ H ₁₄ BrNO ₃ +NH ₄ ⁺ : 365.0495; found: 365.0491, 1.1ppm.

Example 6: (S)-1-(4-chlorophenyl)-4-nitro-3-phenyl-1-butanone and (R)-1-(4-chlorophenyl)-4-nitro The structural formula of base-3-phenyl-1-butanone is as follows:

a. Prepare (S)-1-(4-chlorophenyl)-4-nitro-3-phenyl-1-butanone with dehydroabietamine-thiourea catalyst (1R, 2R)-CHDA-DHATU, In the preparation process, 39 μl (0.3 mmol) of p-chloroacetophenone was used instead of 35 μl (0.3 mmol) of acetophenone in Example 3, and the preparation process was the same as that of Example 3. (S)-1-(4-Chlorophenyl)-4-nitro-3-phenyl-1-butanone was obtained in 98% yield.

[α] ²⁰ _D = -12 (c = 0.6, CHCl ₃ ).

High performance liquid phase analysis (HPLC): (chiral column Chiralcel AD-H, isopropanol/n-hexane = 15/85, 1.0mL/min, UV absorption 254nm.) t _major = 16.80min, t _minor = 21.32min, Enantioselectivity reaches 99%;

b. Prepare (R)-1-(4-chlorophenyl)-4-nitro-3-phenyl-1-butanone with dehydroabietamine-thiourea catalyst (1S, 2S)-CHDA-DHATU, In the preparation process, 39 μl (0.3 mmol) of p-chloroacetophenone was used instead of 35 μl (0.3 mmol) of acetophenone in Example 3, and the preparation process was the same as that of Example 3. (R)-1-(4-Chlorophenyl)-4-nitro-3-phenyl-1-butanone was obtained in 97% yield.

[α] ²⁰ _D = +20 (c = 1.0, CHCl ₃ ).

High performance liquid phase analysis (HPLC): (chiral column Chiralcel AD-H, isopropanol/n-hexane = 15/85, 1.0mL/min, UV absorption 254nm.) t _major = 21.73min, t _minor = 16.52min, Enantioselectivity reaches 99%.

NMR analysis:

¹ H NMR (400MHz, CDCl ₃ ): δ7.85-7.87 (d, J=8Hz, 2H), 7.26-7.44 (m, 7H), 4.80-4.85 (dd, J=7.2Hz, 12.4Hz, 1H) , 4.67-4.71 (dd, J=8.4Hz, 12.8Hz, 1H), 4.18-4.25 (m, 1H), 3.37-3.47 (m, 2H); ¹³ C NMR (100MHz, CDCl ₃ ): δ195.6, 140.1, 138.9, 134.7, 129.4, 129.1, 129.0, 127.9, 127.4, 79.5, 41.5, 39.3. Infrared spectrum analysis: 3064, 2921, 1685, 1589, 1551, 1492, 1378, 1205, 1092, 993, 822, 764, 701,529cm ^-1 .

Mass Spectrometry:

ESI-MS: m/z 304 [M ⁺ ].

Example 7: (S)-1-(4-methoxyphenyl)-4-nitro-3-phenyl-1-butanone and (R)-1-(4-methoxyphenyl)-4 -Nitro-3-phenyl-1-butanone structural formula is as follows:

a. Preparation of (S)-1-(4-methoxyphenyl)-4-nitro-3-phenyl-1-butanone with dehydroabietamine-thiourea catalyst (1R, 2R)-CHDA-DHATU In the preparation process, 45 mg (0.3 mmol) of p-methoxyacetophenone was used to replace 35 μl (0.3 mmol) of acetophenone in Example 3, and the preparation process was the same as in Example 3.

(S)-1-(4-Methoxyphenyl)-4-nitro-3-phenyl-1-butanone was obtained in 80% yield.

[α] ²⁰ _D = -25 (c = 0.7, CHCl ₃ ); melting point: 64-65°C.

High performance liquid phase analysis (HPLC): (chiral column Chiralcel AD-H, isopropanol/n-hexane=35/65, 1.0mL/min, UV absorption 254nm.) t _major =12.82min, enantioselectivity greater than 99%;

b. Preparation of (R)-1-(4-methoxyphenyl)-4-nitro-3-phenyl-1-butanone with dehydroabietamine-thiourea catalyst (1S, 2S)-CHDA-DHATU In the preparation process, 45 mg (0.3 mmol) of p-methoxyacetophenone was used to replace 35 μl (0.3 mmol) of acetophenone in Example 3, and the preparation process was the same as in Example 3.

(R)-1-(4-Methoxyphenyl)-4-nitro-3-phenyl-1-butanone was obtained in 80% yield.

[α] ²⁰ _D = +8 (c = 1.0, CHCl ₃ ); melting point: 65°C.

High performance liquid phase analysis (HPLC): (chiral column Chiralcel AD-H, isopropanol/n-hexane = 35/65, 1.0mL/min, UV absorption 254nm.) t _major = 18.32min, t _minor = 11.96min, Enantioselectivity reaches 98%.

NMR analysis:

¹ H NMR (400MHz, CDCl ₃ ): δ7.89-7.91 (d, J=8.4Hz, 2H), 7.25-7.35 (m, 5H), 6.91-6.93 (d, J=8.8Hz, 2H), 4.82 -4.87(dd, J=6.4Hz, 12.4Hz, 1H), 4.66-4.71(dd, J=8.4Hz, 12.4Hz, 1H), 4.20-4.23(m, 1H), 3.87(s, 3H), 3.33 -3.45 (m, 2H); ¹³ C NMR (100MHz, CDCl ₃ ): δ195.3, 163.9, 139.3, 130.3, 129.5, 129.0, 127.8, 127.4, 79.6, 55.5, 41.2, 39.5.

Infrared spectral analysis: 3062, 2923, 2845, 1675, 1600, 1551, 1511, 1420, 1377, 1262, 1172, 1027, 833, 701, 557cm ^-1 .

High-resolution mass spectrometry analysis:

HRMS-ESI(m/z): calcd for C ₁₇ H ₁₇ NO ₄ [M+H] ⁺ : 300.1230; found: 300.1233, 1.0ppm.

Example 8: (S)-3-(4-chlorophenyl)-4-nitro-1-phenyl-1-butanone and (R)-3-(4-chlorophenyl)-4-nitro The structural formula of base-1-phenyl-1-butanone is as follows:

a. Prepare (S)-3-(4-chlorophenyl)-4-nitro-1-phenyl-1-butanone with dehydroabietamine-thiourea catalyst (1R, 2R)-CHDA-DHATU, In the preparation process, 18.4 mg (0.1 mmol) of nitro-p-chlorostyrene was used to replace 15 mg (0.1 mmol) of nitrostyrene in Example 3, and the preparation process was the same as in Example 3. (S)-3-(4-Chlorophenyl)-4-nitro-1-phenyl-1-butanone was obtained in 92% yield.

[α] ²⁰ _D = -28 (c = 1.2, CHCl ₃ ); melting point: 78-79°C.

High-performance liquid phase analysis (HPLC): (chiral column Chiralcel AD-H, isopropanol/n-hexane=15/85, 1.0mL/min, UV absorption 254nm.) t _major =14.51min, enantioselectivity greater than 99%;

b. Prepare (R)-3-(4-chlorophenyl)-4-nitro-1-phenyl-1-butanone with dehydroabietamine-thiourea catalyst (1S, 2S)-CHDA-DHATU, In the preparation process, 18.4 mg (0.1 mmol) of nitro-p-chlorostyrene was used to replace 15 mg (0.1 mmol) of nitrostyrene in Example 3, and the preparation process was the same as in Example 3. (R)-3-(4-Chlorophenyl)-4-nitro-1-phenyl-1-butanone was obtained in 88% yield.

[α] ²⁰ _D = +10 (c = 1.0, CHCl ₃ ); melting point: 78-79°C.

High performance liquid phase analysis (HPLC): (chiral column Chiralcel AD-H, isopropanol/n-hexane = 15/85, 1.0mL/min, UV absorption 254nm.) t _major = 20.62min, t _minor = 14.72min, Enantioselectivity greater than 99%.

NMR analysis:

¹ H NMR (400MHz, CDCl ₃ ): δ7.88-7.91(m, 2H), 7.55-7.59(m, 1H), 7.43-7.50(m, 2H), 7.28-7.31(m, 2H), 7.19- 7.25(m, 2H), 4.78-4.82(dd, J=6.4Hz, 12.4Hz, 1H), 4.62-4.67(dd, J=8.4Hz, 12.8Hz, 1H), 4.16-4.24(m, 1H), 3.36-3.47 (m, 2H); ¹³ C NMR (100MHz, CDCl ₃ ): δ196.5, 137.5, 136.2, 133.7, 129.2, 128.9, 128.8, 128.0, 79.3, 41.3, 38.7.

Infrared spectral analysis: 3063, 2922, 2853, 2255, 1684, 1551, 1492, 1445, 1376, 1228, 1093, 1008, 909, 828, 733, 688, 546cm ^-1 .

Mass Spectrometry:

ESI-MS: m/z 304 [M ⁺ ].

Example 9: (S)-3-(3-chlorophenyl)-4-nitro-1-phenyl-1-butanone and (R)-3-(3-chlorophenyl)-4-nitro The structural formula of base-1-phenyl-1-butanone is as follows:

a. Prepare (S)-3-(3-chlorophenyl)-4-nitro-1-phenyl-1-butanone with dehydroabietamine-thiourea catalyst (1R, 2R)-CHDA-DHATU, In the preparation process, 18.4 mg (0.1 mmol) of nitro-m-chlorostyrene was used to replace 15 mg (0.1 mmol) of nitrostyrene in Example 3, and the preparation process was the same as in Example 3. (S)-3-(3-Chlorophenyl)-4-nitro-1-phenyl-1-butanone was obtained in 99% yield.

[α] ²⁰ _D = -20 (c = 1.4, CHCl ₃ ).

High-performance liquid phase analysis (HPLC): (chiral column Chiralcel AD-H, isopropanol/n-hexane=15/85, 1.0mL/min, UV absorption 254nm.) t _major =10.11min, enantioselectivity greater than 99%.;

b. Prepare (R)-3-(3-chlorophenyl)-4-nitro-1-phenyl-1-butanone with dehydroabietamine-thiourea catalyst (1S, 2S)-CHDA-DHATU, In the preparation process, 18.4 mg (0.1 mmol) of nitro-m-chlorostyrene was used to replace 15 mg (0.1 mmol) of nitrostyrene in Example 3, and the preparation process was the same as in Example 3. (R)-3-(3-Chlorophenyl)-4-nitro-1-phenyl-1-butanone was obtained in 99% yield.

[α] ²⁰ _D = +14 (c = 1.1, CHCl ₃ ).

High performance liquid phase analysis (HPLC): (chiral column Chiralcel AD-H, isopropanol/n-hexane = 15/85, 1.0mL/min, UV absorption 254nm.) t _major = 12.16min, t _minor = 10.08min, Enantioselectivity reaches 99%.

NMR analysis:

¹ H NMR (400MHz, CDCl ₃ ): δ7.94-7.96 (d, J=7.2Hz, 2H), 7.57-7.61 (m, 1H), 7.41-7.49 (m, 3H), 7.20-7.31 (m, 3H), 4.84-4.90 (m, 2H), 4.66-4.73 (m, 1H) 3.51-3.62 (m, 2H); ¹³ C NMR (100MHz, CDCl ₃ ): δ196.7, 136.2, 133.8, 133.6, 130.5 , 129.0, 128.7, 128.5, 128.0, 127.4, 77.5, 39.9, 36.1.

Infrared spectrum analysis: 3063, 2918, 2852, 1684, 1551, 1477, 1444, 1377, 1228, 1038, 998, 755, 689, 560cm ^-1 .

High-resolution mass spectrometry analysis:

HRMS-ESI (m/z): calcd for C ₁₆ H ₁₄ ClNO ₃ +NH ₄ ⁺ : 321.1000; found: 321.0992, 2.5ppm.

Example 10: (S)-3-(2-chlorophenyl)-4-nitro-1-phenyl-1-butanone and (R)-3-(2-chlorophenyl)-4-nitro The structural formula of base-1-phenyl-1-butanone is as follows:

a. Prepare (S)-3-(2-chlorophenyl)-4-nitro-1-phenyl-1-butanone with dehydroabietamine-thiourea catalyst (1R, 2R)-CHDA-DHATU, In the preparation process, 18.4 mg (0.1 mmol) of nitro-o-chlorostyrene was used to replace 15 mg (0.1 mmol) of nitrostyrene in Example 3, and the preparation process was the same as in Example 3. (S)-3-(2-Chlorophenyl)-4-nitro-1-phenyl-1-butanone was obtained in 99% yield.

[α] ²⁰ _D = -18 (c = 1.4, CHCl ₃ ); melting point: 77-78°C.

High-performance liquid phase analysis (HPLC): (chiral column Chiralcel AD-H, isopropanol/n-hexane=15/85, 1.0mL/min, UV absorption 254nm.) t _major =11.81min, enantioselectivity greater than 99%;

b. Prepare (R)-3-(2-chlorophenyl)-4-nitro-1-phenyl-1-butanone with dehydroabietamine-thiourea catalyst (1S, 2S)-CHDA-DHATU, In the preparation process, 18.4 mg (0.1 mmol) of nitro-o-chlorostyrene was used to replace 15 mg (0.1 mmol) of nitrostyrene in Example 3, and the preparation process was the same as in Example 3. (R)-3-(2-Chlorophenyl)-4-nitro-1-phenyl-1-butanone was obtained in 94% yield.

[α] ²⁰ _D = +8 (c = 1.6, CHCl ₃ ); melting point: 77-79°C.

High performance liquid phase analysis (HPLC): (chiral column Chiralcel AD-H, isopropanol/n-hexane = 15/85, 1.0mL/min, UV absorption 254nm.) t _major = 13.80min, t _minor = 11.68min, Enantioselectivity greater than 99%.

NMR analysis:

¹ H NMR (400MHz, CDCl ₃ ): δ7.92-7.94(m, 2H), 7.55-7.59(m, 1H), 7.39-7.47(m, 3H), 7.19-7.29(m, 3H), 4.85- 4.87 (m, 2H), 4.65-4.71 (m, 1H) 3.50-3.60 (m, 2H); ¹³ C NMR (100MHz, CDCl ₃ ): δ196.7, 136.2, 133.8, 133.6, 130.4, 129.0, 128.7, 128.4, 128.0, 127.4, 77.5, 39.8, 36.1.

Infrared spectrum analysis: 3063, 2918, 1684, 1596, 1551, 1477, 1442, 1376, 1228, 1039, 998, 755, 689, 560cm ^-1 .

Mass Spectrometry:

ESI-MS: m/z 304 [M ⁺ ].

Example 11: (S)-3-(2-methoxyphenyl)-4-nitro-1-phenyl-1-butanone and (R)-3-(2-methoxyphenyl)-4 -Nitro-1-phenyl-1-butanone structural formula is as follows:

a. Preparation of (S)-3-(2-methoxyphenyl)-4-nitro-1-phenyl-1-butanone with dehydroabietamine-thiourea catalyst (1R, 2R)-CHDA-DHATU 15 mg (0.1 mmol) of nitrostyrene in Example 3 was replaced with 17.9 mg (0.1 mmol) of nitro-o-methoxystyrene in the preparation process, and the preparation process was the same as in Example 3. (S)-3-(2-Methoxyphenyl)-4-nitro-1-phenyl-1-butanone was obtained in 86% yield.

[α] ²⁰ _D = -8 (c = 1.2, CHCl ₃ ).

High performance liquid phase analysis (HPLC): (chiral column Chiralcel AD-H, isopropanol/n-hexane = 15/85, 1.0mL/min, UV absorption 254nm.) t _major = 10.98min, t _minor = 14.80min, Enantioselectivity reaches 99%;

b. Preparation of (R)-3-(2-methoxyphenyl)-4-nitro-1-phenyl-1-butanone with dehydroabietamine-thiourea catalyst (1S, 2S)-CHDA-DHATU 15 mg (0.1 mmol) of nitrostyrene in Example 3 was replaced with 17.9 mg (0.1 mmol) of nitro-o-methoxystyrene in the preparation process, and the preparation process was the same as in Example 3. (R)-3-(2-Methoxyphenyl)-4-nitro-1-phenyl-1-butanone was obtained in 82% yield.

[α] ²⁰ _D = +5 (c = 1.4, CHCl ₃ ).

High performance liquid phase analysis (HPLC): (chiral column Chiralcel AD-H, isopropanol/n-hexane = 15/85, 1.0mL/min, UV absorption 254nm.) t _major = 16.65min, t _minor = 12.24min, Enantioselectivity reaches 98%.

NMR analysis:

¹ H NMR (400MHz, CDCl ₃ ): δ7.91-7.93(m, 2H), 7.53-7.57(m, 1H), 7.42-7.46(m, 2H), 7.18-7.25(m, 2H), 6.86- 6.91(m, 2H), 4.83-4.86(m, 2H), 4.38-4.42(m, 1H), 3.85(s, 3H), 3.51-3.53(m, 2H); ¹³ C NMR (100MHz, CDCl ₃ ) : δ197.6, 157.1, 136.6, 133.3, 129.5, 128.9, 128.6, 128.0, 126.6, 120.9, 110.98, 77.8, 55.3, 39.7, 35.9.

Infrared spectrum analysis: 3063, 2923, 2852, 1684, 1598, 1550, 1494, 1445, 1377, 1246, 1120, 1025, 754, 690cm ^-1 .

High-resolution mass spectrometry analysis:

HRMS-ESI(m/z): calcd for C ₁₇ H ₁₇ NO ₄ +NH ₄ ⁺ : 317.1496; found: 317.1498, 0.6ppm.

Example 12: (S)-3-(4-methoxyphenyl)-4-nitro-1-phenyl-1-butanone and (R)-3-(4-methoxyphenyl)-4 -Nitro-1-phenyl-1-butanone structural formula is as follows:

a. Preparation of (S)-3-(4-methoxyphenyl)-4-nitro-1-phenyl-1-butanone with dehydroabietamine-thiourea catalyst (1R, 2R)-CHDA-DHATU 15 mg (0.1 mmol) of nitrostyrene in Example 3 was replaced with 17.9 mg (0.1 mmol) of nitro-p-methoxystyrene in the preparation process, and the preparation process was the same as in Example 3. (S)-3-(4-Methoxyphenyl)-4-nitro-1-phenyl-1-butanone was obtained in 81% yield.

[α] ²⁰ _D = -20 (c = 1.0, CHCl ₃ ); melting point: 71°C.

High performance liquid phase analysis (HPLC): (chiral column Chiralcel AD-H, isopropanol/n-hexane=15/85, 1.0mL/min, UV absorption 254nm.) t _major =15.67min, enantioselectivity greater than 99%;

b. Preparation of (R)-3-(4-methoxyphenyl)-4-nitro-1-phenyl-1-butanone with dehydroabietamine-thiourea catalyst (1S, 2S)-CHDA-DHATU 15 mg (0.1 mmol) of nitrostyrene in Example 3 was replaced with 17.9 mg (0.1 mmol) of nitro-p-methoxystyrene in the preparation process, and the preparation process was the same as in Example 3. (R)-3-(4-Methoxyphenyl)-4-nitro-1-phenyl-1-butanone was obtained in 80% yield.

[α] ²⁰ _D = +12 (c = 1.0, CHCl ₃ ); melting point: 72-73°C.

High performance liquid phase analysis (HPLC): (chiral column Chiralcel AD-H, isopropanol/n-hexane=15/85, 1.0mL/min, UV absorption 254nm.) t _major =21.84min, enantioselectivity greater than 99%.

NMR analysis:

¹ H NMR (400MHz, CDCl ₃ ): δ7.89-7.91(d, J=7.6Hz, 2H), 7.54-7.58(m, 1H), 7.42-7.46(m, 2H), 7.17-7.19(d, J=7.6Hz, 2H), 6.83-6.85(d, J=6.8Hz, 2H), 4.76-4.80(dd, J=6.4Hz, 12.0Hz, 1H), 4.60-4.65(m, 1H), 4.14- 4.18 (m, 1H), 3.75 (s, 3H), 3.39-3.47 (m, 2H); ¹³ C NMR (100MHz, CDCl ₃ ): δ196.9, 159.0, 136.4, 133.5, 130.9, 128.7, 128.5, 127.99 , 114.4, 79.8, 55.2, 41.6, 38.6.

Infrared spectral analysis: 3033, 2919, 2839, 1684, 1610, 1551, 1514, 1446, 1377, 1251, 1181, 1032, 832, 754, 692, 555cm ^-1 .

Mass Spectrometry:

ESI-MS: m/z 300[M ⁺ ].

Example 13: (S)-3-(4-methylphenyl)-4-nitro-1-phenyl-1-butanone and (R)-3-(4-methylphenyl)-4-nitro- The structural formula of 1-phenyl-1-butanone is as follows:

a. Prepare (S)-3-(4-methylphenyl)-4-nitro-1-phenyl-1-butanone with dehydroabietamine-thiourea catalyst (1R, 2R)-CHDA-DHATU, prepare In the process, 16.3 mg (0.1 mmol) of nitro-p-methylstyrene was used to replace 15 mg (0.1 mmol) of nitrostyrene in Example 3, and the preparation process was the same as in Example 3. (S)-3-(4-Tolyl)-4-nitro-1-phenyl-1-butanone was obtained in 81% yield.

[α] ²⁰ _D = -20 (c = 1.8, CHCl ₃ ); melting point: 83-85°C.

High-performance liquid phase analysis (HPLC): (chiral column Chiralcel AD-H, isopropanol/n-hexane=15/85, 1.0mL/min, UV absorption 254nm.) t _major =11.07min, enantioselectivity greater than 99%;

b. Prepare (R)-3-(4-methylphenyl)-4-nitro-1-phenyl-1-butanone with dehydroabietamine-thiourea catalyst (1S, 2S)-CHDA-DHATU, prepare In the process, 16.3 mg (0.1 mmol) of nitro-p-methylstyrene was used to replace 15 mg (0.1 mmol) of nitrostyrene in Example 3, and the preparation process was the same as in Example 3. (R)-3-(4-Tolyl)-4-nitro-1-phenyl-1-butanone was obtained in 82% yield.

[α] ²⁰ _D = +16 (c = 0.8, CHCl ₃ ); melting point: 84-86°C.

High performance liquid phase analysis (HPLC): (chiral column Chiralcel AD-H, isopropanol/n-hexane = 15/85, 1.0mL/min, UV absorption 254nm.) t _major = 14.28min, t _minor = 10.76min, Enantioselectivity reaches 98%.

NMR analysis:

¹ H NMR (400MHz, CDCl ₃ ): δ7.91-7.93 (d, J=8.4Hz, 2H), 7.55-7.59 (m, 1H), 7.47-7.43 (m, 2H), 7.12-7.25 (m, 4H), 4.78-4.83(dd, J=6.4Hz, 12.4Hz, 1H), 4.63-4.68(dd, J=8.0Hz, 12.8Hz, 1H), 4.17-4.22(dd, J=7.2Hz, 14Hz, 1H), 3.37-3.49(m, 2H), 2.307(s, 3H); ¹³ C NMR (100MHz, CDCl ₃ ): δ196.9, 137.5, 136.4, 136.0, 133.5, 129.7, 128.7, 128.0, 127.3, 79.7 , 41.6, 38.9, 21.0.

Infrared spectral analysis: 3058, 2922, 2862, 1685, 1551, 1516, 1446, 1377, 1270, 1225, 998, 817, 755, 691, 551cm ^-1 .

Mass Spectrometry:

ESI-MS: m/z 284[M ⁺ ].

Example 14: (S)-3-(2-naphthyl)-4-nitro-1-phenyl-1-butanone and (R)-3-(2-naphthyl)-4-nitro- The structural formula of 1-phenyl-1-butanone is as follows:

a. Prepare (S)-3-(2-naphthyl)-4-nitro-1-phenyl-1-butanone with dehydroabietamine-thiourea catalyst (1R, 2R)-CHDA-DHATU, prepare In the process, 20 mg (0.1 mmol) of nitro-2-naphthylethylene was used to replace 15 mg (0.1 mmol) of nitrostyrene in Example 3, and the preparation process was the same as in Example 3. (S)-3-(2-Naphthyl)-4-nitro-1-phenyl-1-butanone was obtained in 83% yield.

[α] ²⁰ _D = -14 (c = 1.3, CHCl ₃ ); melting point: 130-132°C.

High performance liquid phase analysis (HPLC): (chiral column Chiralcel AD-H, isopropanol/n-hexane = 15/85, 1.0mL/min, UV absorption 254nm.) t _major = 15.72min, t _minor = 19.32min, Enantioselectivity greater than 99%;

b. Prepare (R)-3-(2-naphthyl)-4-nitro-1-phenyl-1-butanone with dehydroabietamine-thiourea catalyst (1S, 2S)-CHDA-DHATU, prepare In the process, 20 mg (0.1 mmol) of nitro-2-naphthylethylene was used to replace 15 mg (0.1 mmol) of nitrostyrene in Example 3, and the preparation process was the same as in Example 3. (R)-3-(2-Naphthyl)-4-nitro-1-phenyl-1-butanone was obtained in 80% yield.

[α] ²⁰ _D = +16 (c = 1.6, CHCl ₃ ); melting point: 130-132°C.

High performance liquid phase analysis (HPLC): (chiral column Chiralcel AD-H, isopropanol/n-hexane = 15/85, 1.0mL/min, UV absorption 254nm.) t _major = 19.70min, t _minor = 15.70min, Enantioselectivity greater than 99%.

NMR analysis:

¹ H NMR (400MHz, CDCl ₃ ): δ7.90-7.93(m, 2H), 7.77-7.83(m, 3H), 7.72(s, 1H), 7.54-7.58(m, 1H), 7.24-7.49( m, 5H), 4.88-4.93(dd, J=6.8Hz, 12.4Hz, 1H), 4.75-4.80(dd, J=8.0Hz, 12.4Hz, 1H), 4.36-4.43(m, 1H), 3.47- 3.60 (m, 2H); ¹³ C NMR (100MHz, CDCl ₃ ): δ196.8, 136.5, 133.6, 133.4, 132.8, 128.97, 128.7, 128.0, 127.8, 127.7, 126.5, 126.4, 126.2, 125.1, 79.4, 41.6 , 39.4.

Infrared spectral analysis: 3353, 3056, 2921, 2853, 1684, 1550, 1445, 1445, 1377, 1273, 1222, 997, 819, 751, 689, 479cm ^-1 .

Mass Spectrometry:

ESI-MS: m/z 320[M ⁺ ].

Example 15: (S)-3-(2-furyl)-4-nitro-1-phenyl-1-butanone and (R)-3-(2-furyl)-4-nitro- The structural formula of 1-phenyl-1-butanone is as follows:

a. Prepare (S)-3-(2-furyl)-4-nitro-1-phenyl-1-butanone with dehydroabietamine-thiourea catalyst (1R, 2R)-CHDA-DHATU, prepare In the process, 14 mg (0.1 mmol) of nitro-2-furan vinyl was used to replace 15 mg (0.1 mmol) of nitrostyrene in Example 3, and the preparation process was the same as that of Example 3. (S)-3-(2-Furyl)-4-nitro-1-phenyl-1-butanone in 91% yield.

[α] ²⁰ _D = -16 (c = 0.6, CHCl ₃ ); melting point: 33-35°C.

High performance liquid phase analysis (HPLC): (chiral column Chiralcel AD-H, isopropanol/n-hexane = 15/85, 1.0mL/min, UV absorption 254nm.) t _major = 11.05min, t _minor = 13.36min, Enantioselectivity reaches 98%;

b. Prepare (R)-3-(2-furyl)-4-nitro-1-phenyl-1-butanone with dehydroabietamine-thiourea catalyst (1S, 2S)-CHDA-DHATU, prepare In the process, 14 mg (0.1 mmol) of nitro-2-furan vinyl was used to replace 15 mg (0.1 mmol) of nitrostyrene in Example 3, and the preparation process was the same as that of Example 3.

(R)-3-(2-furyl)-4-nitro-1-phenyl-1-butanone was obtained in 93% yield.

[α] ²⁰ _D = +6 (c = 0.8, CHCl ₃ ); melting point: 33-35°C.

High performance liquid phase analysis (HPLC): (chiral column Chiralcel AD-H, isopropanol/n-hexane = 15/85, 1.0mL/min, UV absorption 254nm.) t _major = 13.02min, t _minor = 10.81min, Enantioselectivity reaches 99%.

NMR analysis:

¹ H NMR (400MHz, CDCl ₃ ): δ7.95-7.97(d, J=7.6Hz, 2H), 7.50-7.62(m, 1H), 7.46-7.48(m, 2H), 7.35(m, 1H) , 6.29-6.30(d, J=3.2Hz, 1H), 6.19-6.20(d, J=3.2Hz, 1H), 4.73-4.84(m, 2H), 4.33-4.36(m, 1H), 3.41-3.56 (m, 2H); ¹³ C NMR (100MHz, CDCl ₃ ): δ196.5, 151.9, 142.3, 136.3, 133.6, 128.7, 128.0, 110.5, 107.2, 77.2, 38.96, 33.2.

Infrared spectral analysis: 3121, 3062, 2918, 1685, 1596, 1553, 1505, 1448, 1377, 1213, 1183, 1012, 917, 749, 691, 599cm ^-1 .

High-resolution mass spectrometry analysis:

HRMS-ESI (m/z): calcd for C ₁₄ H ₁₃ NO ₄ +NH ₄ ⁺ : 277.1183; found: 277.1187, 1.4ppm.

Example 16: (S)-1-(2-furyl)-4-nitro-3-phenyl-1-butanone and (R)-1-(2-furyl)-4-nitro- The structural formula of 3-phenyl-1-butanone is as follows:

a. The method for preparing (S)-1-(2-furyl)-4-nitro-3-phenyl-1-butanone with dehydroabietamine-thiourea catalyst (1R, 2R)-CHDA-DHATU :

Dissolve 15mg (0.1mmol) substrate nitrostyrene, 6.6mg (0.015mmol) dehydroabietamine-thiourea catalyst (1R, 2R)-CHDA-DHATU, 1.8mg (0.015mmol) benzoic acid in 0.8ml di In methyl chloride, 34 mg (0.3 mmol) of furanone was added at 0° C., and after 2 hours of reaction, the reaction was continued at room temperature for 72 hours. After the reaction was complete, it was extracted three times with dichloromethane (8ml each time), and dried with 2g of anhydrous sodium sulfate. Concentration and column chromatography (H60 silica gel, petroleum ether: ethyl acetate = 8:1) gave (S)-1-(2-furyl)-4-nitro-3-phenyl-1-butanone 20.0mg (85% yield).

[α] ²⁰ _D = -6 (c = 1.5, CHCl ₃ ).

High performance liquid phase analysis (HPLC): (chiral column Chiralcel AD-H, isopropanol/n-hexane = 15/85, 1.0mL/min, UV absorption 268nm.) t _major = 12.38min, t _minor = 15.92min, Enantioselectivity reaches 98%;

b. The method for preparing (R)-1-(2-furyl)-4-nitro-3-phenyl-1-butanone with dehydroabietamine-thiourea catalyst (1S, 2S)-CHDA-DHATU :

Dissolve 15mg (0.1mmol) substrate nitrostyrene, 6.6mg (0.015mmol) dehydroabietamine-thiourea catalyst (1R, 2R)-CHDA-DHATU, 1.8mg (0.015mmol) benzoic acid in 0.8ml di In methyl chloride, 34 mg (0.3 mmol) of furanone was added at 0° C., and after 2 hours of reaction, the reaction was continued at room temperature for 72 hours. After the reaction was complete, it was extracted three times with dichloromethane (8ml each time), and dried with 2g of anhydrous sodium sulfate. Concentration and column chromatography (H60 silica gel, petroleum ether: ethyl acetate = 8:1) gave (R)-1-(2-furyl)-4-nitro-3-phenyl-1-butanone 21.0 mg (82% yield). [α] ²⁰ _D = +4 (c = 1.5, CHCl ₃ ).

High performance liquid phase analysis (HPLC): (chiral column Chiralcel AD-H, isopropanol/n-hexane = 15/85, 1.0mL/min, UV absorption 268nm.) t _major = 15.81min, t _minor = 12.35min, Enantioselectivity reaches 98%.

NMR analysis:

¹ H NMR (400MHz, CDCl ₃ ): δ7.56(s, 1H), 7.24-7.31(m, 5H), 7.16(m, 1H), 7.35(s, 1H), 4.76-4.81(dd, J= 6.8Hz, 12.4Hz, 1H), 4.64-4.69(m, 1H), 4.15-4.18(m, 1H), 3.22-3.37(m, 2H); ¹³ C NMR (100MHz, CDCl ₃ ): δ185.9, 152.4, 146.6, 138.8, 129.1, 127.9, 127.4, 117.5, 112.5, 79.5, 41.2, 39.1.

Infrared spectral analysis: 3588, 3352, 3126, 2921, 2852, 1959, 1655, 1544, 1464, 1430, 1381, 1238, 1162, 1091, 1032, 919, 762, 702, 548cm ^-1 .

High-resolution mass spectrometry analysis:

HRMS-ESI(m/z): calcd for C ₁₄ H ₁₃ NO ₄ +NH ₄ ⁺ : 277.1183; found: 277.1186, 1.1ppm.

Example 17: (S)-3-(2-chlorophenyl)-1-(2-furyl)-4-nitro-1-butanone and (R)-3-(2-chlorophenyl) -1-(2-furyl)-4-nitro-1-butanone structural formula is as follows:

a. Preparation of (S)-3-(2-chlorophenyl)-1-(2-furyl)-4-nitro-1 with dehydroabietamine-thiourea catalyst (1R,2R)-CHDA-DHATU - butanone, 18.4 mg (0.1 mmol) of nitro-o-chlorostyrene was used to replace 15 mg (0.1 mmol) of nitrostyrene in Example 16 during the preparation process, and the preparation process was the same as in Example 16. (S)-3-(2-Chlorophenyl)-1-(2-furyl)-4-nitro-1-butanone was obtained in 81% yield.

High performance liquid phase analysis (HPLC): (chiral column Chiralcel AD-H, isopropanol/n-hexane = 15/85, 1.0mL/min, UV absorption 265nm.) t _major = 12.45min, t _minor = 13.74min, Enantioselectivity greater than 99%;

b. Preparation of (R)-3-(2-chlorophenyl)-1-(2-furyl)-4-nitro-1 with dehydroabietamine-thiourea catalyst (1S,2S)-CHDA-DHATU - butanone, 18.4 mg (0.1 mmol) of nitro-o-chlorostyrene was used to replace 15 mg (0.1 mmol) of nitrostyrene in Example 16 during the preparation process, and the preparation process was the same as in Example 16. (R)-3-(2-Chlorophenyl)-1-(2-furyl)-4-nitro-1-butanone was obtained in 82% yield.

High performance liquid phase analysis (HPLC): (chiral column Chiralcel AD-H, isopropanol/n-hexane = 15/85, 1.0mL/min, UV absorption 265nm.) t _major = 13.12min, t _minor = 11.91min, Enantioselectivity greater than 99%.

NMR analysis:

¹ H NMR (300MHz, CDCl ₃ ): δ7.59(s, 1H), 7.39-7.42(m, 1H), 7.22-7.26(m, 4H), 6.54-6.55(dd, J=1.5Hz, 3.6Hz , 1H), 4.85-4.88(d, J=6.9Hz, 2H), 4.62-4.67(m, 1H), 3.40-3.43(dd, J=1.8Hz, 7.2Hz, 2H); ¹³ C NMR (75MHz, CDCl ₃ ): δ185.8, 146.7, 135.9, 133.8, 130.4, 129.1, 128.4, 127.4, 117.6, 112.5, 39.6, 35.9.

High-resolution mass spectrometry analysis:

HRMS-ESI(m/z): calcd for C ₁₄ H ₁₂ ClNO ₄ +NH ₄ ⁺ : 311.0793; found: 311.0789, 1.3ppm.

Example 18: (S)-1,3-bis(2-furyl)-4-nitro-1-butanone and (R)-1,3-bis(2-furyl)-4-nitro The structural formula of -1-butanone is as follows:

a. Prepare (S)-1,3-bis(2-furyl)-4-nitro-1-butanone with dehydroabietamine-thiourea catalyst (1R, 2R)-CHDA-DHATU, during the preparation process The 15 mg (0.1 mmol) of nitrostyrene in Example 16 was replaced with 14 mg (0.1 mmol) of nitro-2-furan vinyl, and the preparation process was the same as in Example 16.

(S)-1,3-Bis(2-furyl)-4-nitro-1-butanone was obtained in 83% yield.

High performance liquid phase analysis (HPLC): (chiral column Chiralcel AD-H, isopropanol/n-hexane = 15/85, 1.0mL/min, UV absorption 245nm.) t _major = 20.75min, t _minor = 22.09min, Enantioselectivity greater than 99%;

b. Prepare (R)-1,3-bis(2-furyl)-4-nitro-1-butanone with dehydroabietamine-thiourea catalyst (1S,2S)-CHDA-DHATU, during the preparation process The 15 mg (0.1 mmol) of nitrostyrene in Example 16 was replaced with 14 mg (0.1 mmol) of nitro-2-furan vinyl, and the preparation process was the same as in Example 16.

(R)-1,3-Bis(2-furyl)-4-nitro-1-butanone was obtained in 81% yield.

High performance liquid phase analysis (HPLC): (chiral column Chiralcel AD-H, isopropanol/n-hexane = 15/85, 1.0mL/min, UV absorption 245nm.) t _major = 22.11min, t _minor = 20.89min, Enantioselectivity reaches 98%.

NMR analysis:

¹ H NMR (300MHz, CDCl ₃ ): δ7.60(s, 1H), 7.34(s, 1H), 7.22-7.26(m, 1H), 6.56-6.57(m, 1H), 6.19-6.30(m, 2H), 4.71-4.83 (m, 2H), 4.25-4.34 (m, 1H), 3.24-3.44 (m, 2H); ¹³ C NMR (75MHz, CDCl ₃ ): δ185.5, 152.2, 151.6, 146.8, 142.3, 117.7, 112.5, 110.5, 107.3, 77.1, 38.7, 33.0.

High-resolution mass spectrometry analysis:

HRMS-ESI(m/z): calcd for C ₁₂ H ₁₁ NO ₅ +NH ₄ ⁺ : 267.0975; found: 267.0982, 2.6ppm.

Example 19: (S)-4-nitro-3-phenyl-1-(2-thienyl)-1-butanone and (R)-4-nitro-3-phenyl-1-(2 -Thienyl)-1-butanone structural formula is as follows:

a. Prepare (S)-4-nitro-3-phenyl-1-(2-thienyl)-1-butanone with dehydroabietamine-thiourea catalyst (1R, 2R)-CHDA-DHATU, prepare In the process, 37.8 mg (0.3 mmol) of 2-thienone was used to replace 34 mg (0.3 mmol) of furanone in Example 16, and the preparation process was the same as that of Example 16. (S)-4-Nitro-3-phenyl-1-(2-thienyl)-1-butanone was obtained in 68% yield.

[α] ²⁰ _D = -62 (c = 1.0, CHCl ₃ ).

High performance liquid phase analysis (HPLC): (chiral column Chiralcel AD-H, isopropanol/n-hexane = 15/85, 1.0mL/min, UV absorption 261nm.) t _major = 13.07min, t _minor = 17.72min, Enantioselectivity reaches 98%;

b. Prepare (R)-4-nitro-3-phenyl-1-(2-thienyl)-1-butanone with dehydroabietamine-thiourea catalyst (1S, 2S)-CHDA-DHATU, prepare In the process, 37.8 mg (0.3 mmol) of 2-thienone was used to replace 34 mg (0.3 mmol) of furanone in Example 16, and the preparation process was the same as that of Example 16. (R)-4-Nitro-3-phenyl-1-(2-thienyl)-1-butanone was obtained in 66% yield.

[α] ²⁰ _D = +48 (c = 1.4, CHCl ₃ ).

High-performance liquid phase analysis (HPLC): (chiral column Chiralcel AD-H, isopropanol/n-hexane=15/85, 1.0mL/min, UV absorption 261nm.) t _major =17.74min, enantioselectivity greater than 99%.

NMR analysis:

¹ H NMR (400MHz, CDCl ₃ ): δ7.67-7.68 (dd, J=1.2Hz, 4.0Hz, 1H), 7.63-7.64 (dd, J=1.2Hz, 4.0Hz, 1H), 7.23-7.34( m, 5H), 7.09-7.12 (dd, J = 4Hz, 5.2Hz, 1H), 4.79-4.85 (dd, J = 6.4Hz, 12.4Hz, 1H), 4.66-4.71 (dd, J = 8.0Hz, 12.4 Hz, 1H), 4.16-4.20 (m, 1H), 3.30-3.42 (m, 2H); ¹³ C NMR (100MHz, CDCl ₃ ): δ189.7, 143.6, 138.8, 134.3, 132.2, 129.1, 128.2, 127.96 , 127.4, 79.4, 42.1, 39.5.

Infrared spectral analysis: 3390, 3089, 2921, 2852, 2509, 1954, 1658, 1549, 1413, 1377, 1270, 1235, 1057, 942, 855, 726, ^{699cm -1} .

High-resolution mass spectrometry analysis:

HRMS-ESI(m/z): calcd for C ₁₄ H ₁₃ NO ₃ S+NH ₄ ⁺ : 293.0954; found: 293.0961, 2.4ppm.

Example 20: (S)-4-nitro-3-phenyl-1-(2-thiazolyl)-1-butanone and (R)-4-nitro-3-phenyl-1-(2 -Thiazolyl)-1-butanone structural formula is as follows:

a. Prepare (S)-4-nitro-3-phenyl-1-(2-thiazolyl)-1-butanone with dehydroabietamine-thiourea catalyst (1R, 2R)-CHDA-DHATU, prepare In the process, 38 mg (0.3 mmol) of 2-thiazolone was used to replace 34 mg (0.3 mmol) of furanone in Example 16, and the preparation process was the same as that of Example 16. (S)-4-Nitro-3-phenyl-1-(2-thiazolyl)-1-butanone was obtained in 80% yield.

[α] ²⁰ _D = -18 (c = 3.0, CHCl ₃ );

b. Prepare (R)-4-nitro-3-phenyl-1-(2-thiazolyl)-1-butanone with dehydroabietamine-thiourea catalyst (1S, 2S)-CHDA-DHATU, prepare In the process, 38 mg (0.3 mmol) of 2-thiazolone was used to replace 34 mg (0.3 mmol) of furanone in Example 16, and the preparation process was the same as that of Example 16. (R)-4-Nitro-3-phenyl-1-(2-thiazolyl)-1-butanone was obtained in 80% yield.

[α] ²⁰ _D = +12 (c = 1.6, CHCl ₃ ).

NMR analysis:

¹ H NMR (400MHz, CDCl ₃ ): δ7.97-7.98 (d, J=3.2Hz, 1H), 7.66-7.67 (d, J=2.8Hz, 1H), 7.22-7.33 (m, 5H), 4.74 -4.79(dd, J=7.2Hz, 12.4Hz, 1H), 4.65-4.70(dd, J=8.0Hz, 12.4Hz, 1H), 4.22-4.25(m, 1H), 3.72-3.78(dd, J= 7.2Hz, 17.6Hz, 1H), 3.53-3.59 (dd, J=7.6Hz, 18.0Hz, 1H); ¹³ C NMR (100MHz, CDCl ₃ ): δ190.6, 166.2, 144.8, 138.5, 129.0, 127.9, 127.5, 126.8, 79.6, 41.4, 39.1.

Infrared spectrum analysis: 3418, 2928, 2254, 2128, 1652, 1550, 1449, 1379, 1026, 1001, 826, 765, 629cm ^-1 .

High-resolution mass spectrometry analysis:

HRMS-ESI (m/z): calcd for C ₁₃ H ₁₂ N ₂ O ₃ S[M+H] ⁺ : 277.0641; found: 277.0643, 0.7ppm.

Description of drawings

Figure 1 is a schematic diagram of the chemical structural formulas of thiourea catalysts 1a, 2a-2b, 3a, 4a-4b, 5a and 6a-6b.

Fig. 2 is a schematic diagram of comparative catalytic activity of sugar ring-derived thiourea catalysts 6a-6b in the synthesis of (S)- or (R)-γ-nitroketone.

Claims (3)

1. class dehydroabietylamine-chirality thiourea catalyst, its structural formula is as follows:

2. use the method for synthetic (S)-γ-nitro of dehydroabietylamine-chirality thiourea catalyst high antimer both hands control-fragrant ketone in the claim 1 or (R)-γ-nitro-fragrant ketone chiral compound, it is characterized in that with substrate nitroolefin compound and consumption be dehydroabietylamine-chirality thiourea catalyst of substrate nitroolefin compound 15mol%, consumption is that substrate nitroolefin compound 15mol% benzoic acid is dissolved in the carrene, adding consumption under 0 ℃ of condition is 3 times of amounts of substrate nitroolefin compound aromatic ketone compound, react after 2 hours, at room temperature continue reaction 60 hours, after reacting completely, column chromatography obtains end-product, wherein (S)-γ-nitro-fragrant ketone or (R)-γ-nitro-fragrant ketone chiral compound, the nitroolefin compound, the structural formula of aromatic ketone compound is as follows: a is an aromatic ketone; B is a nitroolefin; C is (S)-γ-nitro-fragrant ketone; D is (R)-γ-nitro-fragrant ketone:

Wherein, R ₁For-H, or be-Me, or be-OMe, or be-Cl, or be-Br, or be-F,

R ₂For-Ph, or be-naphthyl, or be-Cl-Ph, or be-Br-Ph, or be-F-Ph, or be-thienyl, or be-furyl, or be-Me-Ph, or be-OMe-Ph.

3. use the mix method of ketone chiral compound of synthetic (S)-γ-nitro of dehydroabietylamine-chirality thiourea catalyst high antimer both hands control in the claim 1-assorted ketone of fragrance or (R)-γ-nitro-fragrance, it is characterized in that with substrate nitroolefin compound and consumption be dehydroabietylamine-chirality thiourea catalyst of substrate nitroolefin compound 15mol%, consumption is that substrate nitroolefin compound 15mol% benzoic acid is dissolved in the carrene, adding consumption under 0 ℃ of condition is 3 times of assorted ketonic compounds of amount fragrance of substrate nitroolefin compound, react after 2 hours, at room temperature continue reaction 72 hours, after reacting completely, column chromatography obtains end-product, wherein the assorted ketone of (S)-γ-nitro-fragrance or (R)-γ-nitro-fragrance ketone chiral compound of mixing, the nitroolefin compound, the structural formula of the assorted ketonic compound of fragrance is as follows: a is a nitroolefin; B is the assorted ketone of fragrance; C is the assorted ketone of (S)-γ-nitro-fragrance; D is the assorted ketone of (R)-γ-nitro-fragrance:

Wherein, X is O, or is S; Y is C, or is N,

R ₃For-Ph, or be-naphthyl, or be-Cl-Ph, or be-Br-Ph, or be-F-Ph, or be-thienyl, or be-furyl, or be-Me-Ph, or be-OMe-Ph,

R ₄For-H, or be-Me, or be-Cl, or be-Br, or be-F,

R ₅For-H, or be-Me, or be-Cl, or be-Br, or be-F,

R ₆For-H, or be-Me, or be-Cl, or be-Br, or be-F,

R ₇For-H, or be-Me, or be-Cl, or be-Br, or be-F,

R ₈For-H, or be-Me.

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