CN109046447B - C2Synthesis of symmetric bicyclic bisboron catalysts - Google Patents
C2Synthesis of symmetric bicyclic bisboron catalysts Download PDFInfo
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- CN109046447B CN109046447B CN201810977699.5A CN201810977699A CN109046447B CN 109046447 B CN109046447 B CN 109046447B CN 201810977699 A CN201810977699 A CN 201810977699A CN 109046447 B CN109046447 B CN 109046447B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
- B01J31/0275—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 also containing elements or functional groups covered by B01J31/0201 - B01J31/0269
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/44—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers
- C07C209/52—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of imines or imino-ethers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/07—Optical isomers
Abstract
The invention synthesizes C with a novel structure2The catalyst can efficiently realize asymmetric hydrogenation of aryl ketimine and synthesize chiral secondary amine with high enantioselectivity, and belongs to the technical field of application. One of the key points of the invention for solving the problems is to provide a simple and practical method, two diboron catalysts with different structures are obtained by controlling the temperature of the hydroboration reaction of the diene; the second point is that the use of noble metal catalysts can be avoided.
Description
Technical Field
The invention relates to a slaveC 2 Preparation of symmetrical dienes by reaction with boron hydridesC 2 A method for synthesizing a symmetric bicyclic diboron catalyst, which is applied to the asymmetric hydrogenation of imine and belongs to the technical field of methodology research and application.
Background
In 2006, professor d.w. Stephan of university of toronto found B (C)6F5)3And sterically hindered tri-tert-butylphosphine, tris-mesitylphosphine, etc. do not form classical lewis acid-base adducts but exist as acid-base pairs that can cleave hydrogen at room temperature, and several classes of chiral boron catalysts are subsequently synthesized and applied in the asymmetric hydrogenation of various imines. As shown in the following figure, many of the currently reported chiral boron catalysts have the problems of difficult synthesis, separation and purification, difficult structure modification, low catalytic efficiency, low enantioselectivity of products and the like.
Disclosure of Invention
The invention aims to synthesize a chiral bicyclic diboron catalyst which is easy to synthesize and modify and is applied to asymmetric hydrogenation of aryl ketimine.
1. The boron catalyst is synthesized by hydroboration reaction of diene and hydroboron and is applied to the hydrogenation of imine, and the method comprises the following specific steps:
sequentially adding diene L, hydroboron and a solvent into a reaction bottle in a nitrogen atmosphere, stirring for 5 minutes at a specified temperature, then cooling to room temperature, adding isoquinoline, stirring for 5 minutes at room temperature, removing the solvent, and performing column chromatography separation to obtain a target product A.
Sequentially adding diene L, hydroboron and a solvent into a reaction bottle in a nitrogen atmosphere, stirring for 5 minutes at a specified temperature, cooling to room temperature, adding 1, transferring into an autoclave, sealing, replacing with hydrogen for three times, filling to reaction pressure, stirring at the specified temperature for reaction for a long time, cooling to room temperature, removing the solvent under reduced pressure, and performing column chromatography separation to obtain a target product 2.
2. The catalyst related by the invention is diene and hydroboron, and the dosage of the catalyst is generally 0.5-4 mol%.
3. The solvent used in the present invention is toluene, and the amount thereof is 1.0 mL to 2.0 mL per mmol of 1 of the starting material.
4. The reaction temperature involved in the present invention may be in the range of-40 deg.CoC to 80oAt temperatures between C.
5. Ar in raw Material 1 used in the present invention1And Ar2All are aryl, R can be methyl, ethyl, n-propyl, benzyl and other substituent groups, Ar in L is aryl or alkyl, ArFIs a fluorine-containing aryl group.
The invention has the advantages that:
1. the chiral boron catalyst synthesized by the method has an easily modified structure and high activity in the asymmetric hydrogenation of imine.
2. The invention carries out gram-magnitude experiments, and the reaction is suitable for mass production.
3. The invention uses non-metal boron catalyst, which avoids the pollution of noble metal catalyst to environment.
Detailed description of the invention
The following examples will better illustrate the invention, but it should be emphasized that the invention is in no way limited to what is shown in these examples. The following examples show different aspects of the invention. The data presented include specific operating and reaction conditions and products. The purity of the product was identified by nuclear magnetism.
Example 1: synthesis of phenyl-substituted boron catalyst A1
In a reaction bottleAdding diene L1 (25.8 mg, 0.1 mmol) and HB (C)6F5)2(69.2 mg, 0.2 mmol) and toluene (0.5 mL) under nitrogen atmosphere 25oC, reacting for 5 minutes. Isoquinoline (27.1 mg, 0.21 mmol) and toluene (0.5 mL), 25, were addedoC the reaction was continued for 5 minutes. After the reaction was completed, toluene was removed, and silica gel column chromatography was performed to obtain 114.8 mg of white powdery solid with an eluent (ethyl acetate/petroleum ether = 1/5) in a yield of 95%.1H NMR (400 MHz, CDCl3) δ 9.15 (s, 2H), 8.14 (d, J = 6.8 Hz, 2H), 7.92-7.82 (m, 4H), 7.78-7.68 (m, 4H), 7.64 (d, J = 6.8 Hz, 2H), 7.29 (d, J = 7.3 Hz, 4H), 7.15 (t, J = 7.5 Hz, 4H), 7.06 (t, J = 7.3 Hz, 2H), 3.42-3.30 (m, 2H), 2.76-2.64 (m, 2H), 2.45-2.32 (m, 2H), 1.88-1.78 (m, 2H), 1.24-1.10 (m, 2H). 13C NMR (101 MHz, CDCl3) δ 150.3, 145.4, 137.8, 136.4, 134.9, 130.0, 129.5, 129.2, 127.9, 127.3, 126.4, 125.7, 122.7, 53.3, 52.9, 34.3, 32.1.19F NMR (377 MHz, CDCl3) δ -127.7 (br, 4F), -129.4 (br, 4F), -158.0 (m, 2F), -158.3 (m, 2F), -163.4 (m, 4F), -163.6 (m, 4F).
Example 2: synthesis of 3, 5-di-tert-butylphenyl substituted boron catalyst A2
Diene L2 (48.2 mg, 0.1 mmol) and HB (C) were added to the reaction flask in this order6F5)2(69.2 mg, 0.2 mmol) and toluene (0.5 mL) under nitrogen atmosphere 25oC, reacting for 5 minutes. Isoquinoline (27.1 mg, 0.21 mmol), toluene (0.5 mL), 25 was addedoC the reaction was continued for 5 minutes. After the reaction was completed, toluene was removed, and silica gel column chromatography was performed to obtain an eluent (ethyl acetate/petroleum ether = 1/5), whereby 137.6 mg of a white powdery solid was obtained in a yield of 96%.1H NMR (400 MHz, CDCl3) δ 8.91 (s, 2H), 8.17 (d, J = 6.5 Hz, 2H), 7.87-7.72 (m, 4H), 7.64-7.47 (m, 4H), 7.38-7.27 (m, 2H), 7.20-7.10 (m, 6H), 3.35-3.15 (m, 2H), 2.95-2.85 (m, 2H), 2.84-2.72 (m, 2H), 1.85-1.70 (m, 2H), 1.50-1.37 (m, 2H), 1.11 (s, 36H). 13C NMR (101 MHz, CDCl3) δ 151.1, 150.1, 137.7, 136.2, 135.4, 134.7, 130.2, 129.0, 127.5, 126.1, 123.4, 122.6, 119.3, 55.0, 52.3, 34.8, 34.7, 32.8, 31.5.19F NMR (376 MHz, CDCl3) δ -128.5 (br, 4F), -130.0 (br, 4F), -158.1 (m, 2F), -158.4 (m, 2F), -163.5 (m, 4F), -163.6 (m, 4F).
Example 3: synthesis of 3, 5-di-tert-butylphenyl substituted boron catalyst A3
Diene L2 (48.2 mg, 0.1 mmol) and HB (C) were added to the reaction flask in this order6F5)2(69.2 mg, 0.2 mmol) and toluene (0.5 mL) under nitrogen atmosphere 80oC, reacting for 5 minutes. Reduced to 25oC, isoquinoline (27.1 mg, 0.21 mmol) and toluene (0.5 mL), 25 were addedoC the reaction was continued for 5 minutes. After the reaction was completed, toluene was removed, and silica gel column chromatography was performed to obtain an eluent (ethyl acetate/petroleum ether = 1/5), whereby 130.4 mg of a white powdery solid was obtained in a yield of 91%.1H NMR (400 MHz, CDCl3) δ 8.95-8.30 (m, 2H), 8.13-8.00 (m, 2H), 7.88-7.44 (m, 12H), 7.21 (s, 2H), 6.88-6.30 (m, 2H), 3.05-2.95 (m, 2H), 2.93-2.80 (m, 2H), 2.50-2.37 (m, 2H), 1.99-1.88 (m, 2H), 1.67-1.42 (m, 18H), 0.96-0.66 (m, 20H). 13C NMR (101 MHz, CDCl3) δ 150.1, 137.4, 136.2, 134.7, 130.3, 129.0, 127.5, 126.2, 122.8, 119.5, 60.8, 53.0, 46.1, 39.5, 34.6, 31.5.19F NMR (376 MHz, CDCl3) δ -127.0 (br, 4F), -131.5 (br, 4F), -157.7 (m, 4F), -163.4 (m, 8F).
Example 4: synthesis of 3, 5-di-tert-butylphenyl substituted boron catalyst A4
Diene L2 (48.2 mg, 0.1 mmol) and HB (HB) (p-C6F5H)2(62.0 mg, 0.2 mmol) and toluene (0.5 mL) under nitrogen atmosphere 80 oCThe reaction was carried out for 5 minutes. Reduced to 25 oCThen, isoquinoline (27.1 mg, 0.21 mmol) and toluene (0.5 mL), 25 were added oCThe reaction was continued for 5 minutes. After the reaction was completed, toluene was removed, and silica gel column chromatography was performed with an eluent (ethyl acetate/petroleum ether = 1/5), whereby 122.5 mg of a white powdery solid was obtained in a yield of 90%.1H NMR (400 MHz, CDCl3) δ 8.99-8.36 (s, 2H), 8.24-8.06 (m, 2H), 7.82 -7.36 (m, 10H), 7.14 (s, 2H), 7.08-6.86 (m, 2H), 6.81-6.49 (s, 4H), 3.05-2.91 (m, 4H), 2.53-2.35 (m, 2H), 2.04-1.94 (m, 2H), 1.81-1.35 (m, 18H), 0.95-0.46 (m, 20H). 13C NMR (101 MHz, CDCl3) δ 150.1, 137.7, 136.2 134.4, 130.3, 128.7, 127.5, 126.1, 122.3, 119.2, 61.1, 52.8, 46.2, 39.5, 34.9, 31.6. 19F NMR (376 MHz, CDCl3) δ -126.8 (br, 8F), -141.3 (m, 8F).
Example 5: (R) Synthesis of (E) -N- (1-phenylethyl) aniline
Diene L2 (2.4 mg, 0.005 mmol) and HB (HB) (p-C6F5H)2(3.1 mg, 0.01 mmol) and toluene (0.5 mL) under nitrogen atmosphere 80 oCThe reaction was carried out for 5 minutes. Reduced to 25 oC1a (195.3 mg, 1.0 mmol) and toluene (1.5 mL) were added. The reaction bottle is put into a high-pressure reaction kettle, sealed, replaced by hydrogen for three times, filled to reaction pressure, reacted for 48 hours at reaction temperature, the hydrogen pressure is carefully removed, and the high-pressure kettle is opened. Toluene was removed and silica gel column chromatography was performed with eluent (ethyl acetate/petroleum ether = 1/20) to give 2a (189.7 mg) as a colorless oily liquid in 96% yield with an enantioselectivity of 94% ee.1H NMR (400 MHz, CDCl3) δ 7.38 (d, J = 7.4 Hz, 2H), 7.34-7.31 (m, 2H), 7.23 (t, J = 7.2 Hz, 1H), 7.10 (t, J = 7.7 Hz, 2H), 6.65 (t, J = 7.3 Hz, 1H), 6.52 (d, J = 8.3 Hz, 2H), 4.49 (q, J = 6.7 Hz, 1H), 4.03 (brs, 1H), 1.53 (d, J = 6.7 Hz, 3H). 13C NMR (101 MHz, CDCl3) δ 147.4, 145.4, 129.2, 128.8, 127.0, 126.0, 117.4, 113.4, 53.6, 25.1.
Example 6: (-) -NSynthesis of- (1-p-tolypropylamine) aniline
Diene L2 (2.4 mg, 0.005 mmol) and HB (HB) (p-C6F5H)2(3.1 mg, 0.01 mmol) and toluene (0.5 mL) under nitrogen atmosphere 80 oCThe reaction was carried out for 5 minutes. Reduced to 25 oC1b (55.8 mg, 0.25 mmol) and toluene (1.5 mL) were added. The reaction bottle is put into a high-pressure reaction kettle, sealed, replaced by hydrogen for three times, filled to reaction pressure, reacted for 17 hours at reaction temperature, the hydrogen pressure is carefully removed, and the high-pressure kettle is opened. Toluene was removed and silica gel column chromatography was performed with eluent (ethyl acetate/petroleum ether = 1/20) to give 2b (53.5 mg) as a pale yellow oily liquid in 95% yield with an enantioselectivity of 95% ee.1H NMR (400 MHz, CDCl3) δ 7.22 (d, J = 8.0 Hz, 2H), 7.12 (d, J = 8.0 Hz, 2H), 7.10 -7.03 (m, 2H), 6.62 (t, J = 7.3 Hz, 1H), 6.51 (d, J= 8.1 Hz, 2H), 4.19 (t, J = 6.9 Hz, 1H), 4.04 (brs, 1H), 2.32 (s, 3H), 1.85-1.76 (m, 2H), 0.95 (t, J = 7.4 Hz, 3H). 13C NMR (101 MHz, CDCl3) δ 147.7, 141.0, 136.5, 129.3, 129.2, 126.5, 117.1, 113.3, 59.5, 31.8, 21.2, 11.0.
Claims (10)
1. C2-a method for synthesizing a symmetric bicyclic diboron catalyst, characterized in that: sequentially adding diene L and a boron hydride HBAr into a reaction bottle in a nitrogen atmosphereF 2And a solvent, stirring for 5 minutes at a specified temperature T, and then cooling to room temperature to obtain a target product A' orA''，
Obtaining a target product A' when the specified temperature T is 25 ℃, and obtaining a target product A ″ when the specified temperature T is 80 ℃;
in the diene L, Ar is aryl or alkyl;
the borohydride HBArF 2The mol ratio of the diene L to the diene L is 2: 1;
the solvent is toluene;
the borohydride HBArF 2In ArFIs a fluorine-containing aryl group.
2. C according to claim 12-a method for synthesizing a symmetric bicyclic diboron catalyst, characterized in that: the aryl is phenyl, 4-fluorophenyl, 4-tert-butylphenyl or 3, 5-di-tert-butylphenyl.
3. C according to claim 12-a method for synthesizing a symmetric bicyclic diboron catalyst, characterized in that: the borohydride HBArF 2Is HB (p-C6F4H)2Or HB (C)6F5)2。
4. C according to claim 12-a method for synthesizing a symmetric bicyclic diboron catalyst, characterized in that: the dosage ratio of the toluene to the diene L is 5 mL: 1 mmol.
5. C according to claim 12-a method for synthesizing a symmetric bicyclic diboron catalyst, characterized in that: the dosage of the diene L is 0.1 mmol, and the boron hydride HBArF 2The amount of (B) was 0.2 mmol, and the amount of toluene was 0.5 mL.
6. A process for the asymmetric hydrogenation of an imine comprising the steps of:
s1, sequentially adding diene L and a boron hydride HBAr into a reaction bottle in a nitrogen atmosphereF 2And a solvent, stirring for 5 minutes at 25 ℃ or 80 ℃, and cooling to room temperature;
s2, adding the raw material 1 and the solvent into the reaction system obtained in the step S1, transferring the mixture into a high-pressure kettle, sealing the high-pressure kettle tightly, replacing the mixture with hydrogen for three times, filling the mixture to reaction pressure, stirring the mixture at a specified temperature T for a long time, cooling the mixture to room temperature, removing the solvent under reduced pressure, performing column chromatography separation to obtain a target product 2,
in step S1, the borohydride HBArF 2Ar in (1)FIs a fluorine-containing aryl group; the diene L has the following structural formula:
wherein Ar is aryl or alkyl;
in step S2, Ar in the raw material 11And Ar2Are all aryl groups, R is methyl, ethyl, n-propyl or benzyl, and the specified temperature T is-40 ℃.
7. The process for the asymmetric hydrogenation of imines of claim 6, characterized in that: in steps S1 and S2, the solvent is toluene.
8. The process for the asymmetric hydrogenation of imines of claim 6, characterized in that: the borohydride HBArF 2Is HB (p-C6F4H)2Or HB (C)6F5)2。
9. The process for the asymmetric hydrogenation of imines of claim 6, characterized in that: the above-mentionedAr in the diene L is 3, 5-di-tert-butylphenyl; the raw material 1 is phenyl- (1-phenylethylene) amine, the dosage of the diene L is 0.005 mmol, and the borohydride HBAr isF 2The amount of (2) was 0.01 mmol, the amount of the raw material 1 was 1.0 mmol, and the reaction time was 48 hours.
10. The process for the asymmetric hydrogenation of imines of claim 6, characterized in that: ar in the diene L is 3, 5-di-tert-butylphenyl; the raw material 1 is phenyl- [1- (4-methyl) phenylpropylene]Amine, the dosage of the diene L is 0.005 mmol, and the borohydride HBArF 2Was 0.01 mmol, the amount of the starting material 1 was 0.25 mmol, and the reaction time was 17 hours.
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