CN109575060A - The synthesis and its application in hydrogenation of the double B catalysts of loop coil - Google Patents
The synthesis and its application in hydrogenation of the double B catalysts of loop coil Download PDFInfo
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- CN109575060A CN109575060A CN201811561367.5A CN201811561367A CN109575060A CN 109575060 A CN109575060 A CN 109575060A CN 201811561367 A CN201811561367 A CN 201811561367A CN 109575060 A CN109575060 A CN 109575060A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
- C07F5/02—Boron compounds
- C07F5/027—Organoboranes and organoborohydrides
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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
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
- B01J31/146—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of boron
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/04—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms
- C07D215/06—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms having only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, attached to the ring nitrogen atom
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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
- B01J2231/646—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of aromatic or heteroaromatic rings
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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
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention relates to one kind to have C2The synthesis of the loop coil diolefin compound of symmetry, and reacted by it with hydroboron and be prepared for the double B catalysts of a series of chiral spiro.The double B catalysts of these loop coils show very high activity and enantioselectivity in the asymmetric hydrogenation of quinolines, belong to applied technical field.The problems such as present invention mainly solves previous quinoline asymmetric hydrogenation methods need to use noble metal catalyst, functional group tolerance is poor, realizes the reaction of nonmetal catalyzed quinoline asymmetric hydrogenation, the reaction substrate range is wide, and functional group tolerance is strong.The invention will be applied in drug research and Chemical Manufacture.
Description
Technical field
The present invention relates to a kind of novel with C2The synthesis of the loop coil diolefin compound of symmetry, then pass through hydroboration
The double B catalysts of loop coil are prepared in situ, the double B catalysts of this kind of loop coil show very high in the asymmetric hydrogenation of quinoline
Activity and enantioselectivity, belong to organic chemical synthesis methodological study and applied technical field.
Background technique
2006, professor D.W.Stephan of University of Toronto had found B (C6F5)3With the alkali (tri-tert-butylphosphine) of big steric hindrance
Etc. the lewis acid alkali adduct that cannot form classics, but exist in the form of acid-base pair, such acid-base pair at room temperature can
It enough realizes the activation of hydrogen and some unsaturated compounds can be restored.Based on this, some chirality B catalysts are synthesized out
Come and be applied in the asymmetric hydrogenation of various substrates and (is shown below).But the field is in ground zero rank
Section, the chiral B catalyst reported at present is also very limited, and there are no good for the asymmetric hydrogenation of many heterocyclic compounds
It solves, therefore Development of Novel, efficient chiral catalyst are an important contents of the area research.
Summary of the invention
The contents of the present invention include: 1. preparation one kind novel chiral loop coil diolefin compounds；2. passing through loop coil diene chemical combination
The hydroboration of object prepares the double B catalysts of loop coil and identifies its structure；3. the double B catalysts of loop coil are in quinoline asymmetric hydrogenation
Application in reaction.
1. chiral spiro diolefin compound of the invention have following structural formula (absolute configuration of spirocyclic ring scaffold be R or
Person S):
The characteristics of this kind of chiral spiro diene is that molecule has spiral shell [4.4]-nonane skeleton, and the R group in structural formula is virtue
Base and alkyl.Its synthetic method is as follows:
Step 1: spiral shell [4.4] -1,6- nonyl diketone rac-1 (it prepares bibliography: Synth.Commun.1999, and 29,
3829.) and (R)-phenyl ethylamine base oxalyl hydrazine is under catalysis of iodine, is refluxed overnight reaction and obtains double hydrazones of a pair of of diastereoisomer
Compound intermediate, by recrystallize in ethanol twice can isolated single configuration (R)-bis- hydrazone compounds, it is intermediate
The double hydrazone compounds of body hydrolyze in iodine-potassium iodide system obtains optics pure products (R) -1.Wherein spiral shell [4.4] -1,6- nonyl diketone
The molar ratio of rac-1 and (R)-phenyl ethylamine base oxalyl hydrazine is 1: 1, and elemental iodine is catalytic amount.
Step 2: alkali is made with KHMDS under the conditions of -78 DEG C of temperature, (R) -1 and 2-PyNTf240 are reacted in tetrahydrofuran
Minute produces product 2.Wherein (R) -1,2-PyNTf2, the molar ratio of KHMDS is 1: 3: 3.
Step 3: with toluene: ethyl alcohol (3: 1) is mixed solvent, under heated reflux condition, trifluoromethanesulfonic acid enol ester chemical combination
Suzuki coupling reaction occurs in the presence of tetra-triphenylphosphine palladium and alkali with aryl (or alkyl) acid reagent for object 2, and reaction 5 is small
When after obtain chiral spiro bifunctional vinyl compound of the present invention.Wherein 2 and the molar ratio of acid reagent be 1: 4, four triphenyls
The dosage of phosphine palladium is 10mol%.The molecular formula of above-mentioned boric acid compound is RB (OH)2。
2. preparation and the Structural Identification of the double B catalysts of chiral spiro:
In glove box, loop coil diene and HB (C6F5)2And solvent toluene is added in reaction flask, is stirred under assigned temperature
It mixes 15 minutes, then restores to room temperature, prepare the double B catalysts of chiral spiro.Add isoquinolin or pyridine (L) and system
Standby double B catalysts reaction, is stirred at room temperature 30 minutes, removes solvent, and recrystallization isolates and purifies to obtain target adduct.Loop coil
Diene, HB (C6F5)2Molar ratio with L (isoquinolin or pyridine) is 1: 2: 4.The structure of the adduct is by X-ray single crystal diffraction
Confirmation, and then determine the double B catalyst structures of the chiral spiro of preparation.Wherein, HB (C6F5)2It can be by other boron containing fluoro aryl
Hydrogen compound substitution.
3. the asymmetric hydrogenation of the double B catalyst catalysis quinoline of chiral spiro:
The double B catalysts of chiral spiro of the present invention can be applied to the asymmetric hydrogenation of quinolines,
2 substituted-tetrahydro quinoline compounds are obtained with high turn over number and high enantioselectivity.
The invention has the advantages that
1. B catalyst has saved cost instead of transition metal, solves the problems, such as heavy-metal residual in pharmaceutical synthesis.
2. the dosage of the double B catalysts of loop coil of the invention is low, and can be amplified to gram-grade experiment, reaction condition is mild.
It is taken 3. the asymmetric hydrogenation developed can obtain 2 with high reactivity and high enantioselectivity
For tetrahydroquinoline, substrate spectrum is wide, and functional group compatibility is strong.
Specific implementation method
Following implementation example will better illustrate the present invention, but it is emphasized that the present invention is by no means limited to these realities
Apply content represented by example.Following examples show not ipsilaterals of the invention.Given data include concrete operations and anti-
Answer condition and product.Product purity is identified by nuclear-magnetism.
Embodiment 1: the synthesis of chiral spiro diene 3a
Step 1: the fractionation of spiral shell [4.4] -1,6- nonyl diketone
(R)-phenyl ethylamine base oxalyl hydrazine (4.15g, 2eq) is added in the dry round-bottomed flask of 250mL, is then added
Spiral shell [4.4] -1, the 6- nonyl diketone and a granule elemental iodine of 1.52g racemization, argon gas protection is lower to be added 120mL anhydrous methylene chloride,
One water segregator and reflux condensing tube, heated overnight at reflux are installed.System is cooled to room temperature after having reacted, and diatomite is filtered to remove not
Molten solid, vacuum rotary steam remove methylene chloride and obtain crude yellow solid, and it is white that dehydrated alcohol recrystallization purifying obtains 3.5g
The double hydrazone compound intermediates of color pulverulent solids, yield 66%.
The double hydrazone compound intermediates of 2.0g spiral shell diketone are added in 500mL eggplant-shape bottle, twice with dehydrated alcohol recrystallization, are obtained
To double hydrazone compounds of 600 mg single configurations, yield 60%.1H NMR (400MHz, CDCl3) δ 9.71 (s, 2H), 8.25 (d, J
=8.3 Hz, 2H), 7.39-7.22 (m, 8H), 7.22-7.12 (m, 2H), 5.17-4.98 (m, 2H), 2.57-2.39 (m, 4H),
2.36-2.26 (m, 2H), 2.24-2.12 (m, 2H), 1.91-1.71 (m, 4H), 1.59 (d, J=6.8Hz, 6H)；13C NMR
(101MHz, CDCl3) δ 172.8,158.7,155.1,142.1,128.7,127.6,126.2,57.8,49.6,37.4,
28.0,21.6,21.5.
The double hydrazone intermediates of 2.0g loop coil are added in 250mL round-bottomed flask, sequentially add potassium iodide (800mg) and elemental iodine
(200mg), is added acetone (80mL) and water (20mL) is used as mixed solvent, and reaction solution is heated to reflux 40 minutes, TLC monitoring.Instead
After answering completely, stirs the lower saturated sodium thiosulfate solution that is added dropwise and iodine is quenched, reaction solution is become colorless by brown color, and vacuum rotary steam removes
Acetone is removed, residue is extracted with dichloromethane three times, and combined organic phase is washed with saturated sodium chloride solution, and anhydrous sodium sulfate is dry
Dry, solvent is removed in rotation, and crude product obtains white solid product (R) -1 (385mg), yield 67% by silica gel column chromatography.1H NMR
(400MHz, CDCl3) δ 2.42-2.13 (m, 8H), 1.93-1.77 (m, 4H)；13C NMR (101MHz, CDCl3) δ 217.0,
64.5,38.6,34.4,19.9.
Step 2: the synthesis of compound 2
Under argon gas protection, (R) -1 (400mg) and PyNTf2(2.4eq, 2.3g) is added to dry 100mL Schlenk
It in reaction flask, substitutes gas 3 times, 30mL anhydrous tetrahydro furan is added.System is cooled to -78 DEG C, to reaction system under argon gas protection
In KHMDS (3eq) is added dropwise dropwise, rear insulation reaction is added dropwise 40 minutes, TLC monitoring reaction.Unsaturated carbonate is used after having reacted
(3 × 20mL) three times is extracted with ethyl acetate in hydrogen sodium solution quenching reaction, reaction solution, and combined organic phase successively uses 5% hydrogen-oxygen
Change sodium solution, saturated sodium chloride solution washing, Anhydrous potassium carbonate is dry, filters and removes desiccant, and vacuum rotary steam removes solvent, slightly
Product passes through the isolated yellow liquid product 2 (915mg) of silica gel column chromatography, yield 83%.1H NMR (400MHz, CDCl3)δ
5.80 (t, J=2.5Hz, 2H), 2.52-2.38 (m, 4H), 2.37-2.29 (m, 2H), 2.04-1.97 (m, 2H)；13C NMR
(101MHz, CDCl3) δ 148.5,123.4,120.2,117.4,117.0,113.8,58.3,33.3,26.2.
Step 3: the synthesis of chiral spiro diene
Under argon gas protection, substrate 2 (500mg), phenyl boric acid (4eq, 585mg) and four are separately added into 100mL three-necked flask
(triphenylphosphine) palladium (10mol%) is substituted gas 3 times, and toluene alcohol mixeding liquid (3: 1,30mL) and carbon that degassing process is crossed is added
Acid sodium solution (15mL), system are deaerated three times with liquid nitrogen frozen, are restored to after room temperature and are heated to reflux 5 hours for 80 DEG C.TLC monitoring is anti-
Progress is answered, after conversion completely, system is cooled to room temperature, and saturated ammonium chloride solution is added, separates organic phase, water phase ethyl acetate
Three times, organic phase is washed twice with saturated common salt for extraction, and anhydrous sodium sulfate dries, filters removing desiccant, and revolving removes solvent,
Crude product is chromatographed to obtain 327mg white powdery solids 3a, yield 55% with n-hexane column.1H NMR (400MHz, CDCl3)δ
7.51-7.49 (m, 4H), 7.23-7.14 (m, 6H), 6.20 (t, J=2.6Hz, 2H), 2.51-2.42 (m, 4H), 2.28-
2.20 (m, 2H), 2.08-2.02 (m, 2H)；13C NMR (101MHz, CDCl3) δ 148.1,136.6,128.4,128.1,
126.7,64.4,37.5,30.2.
Embodiment 2: the synthesis and identification of the double B catalyst 4a of loop coil
3a (13.6mg, 0.05mmol), HB (C are sequentially added in glove box, in reaction flask6F5)2(34.6mg,
0.1mmol) with toluene (1.0mL), 25 DEG C are reacted 15 minutes.Add isoquinolin (25.8mg, 0.2mmol) and toluene
(0.5mL), 25 DEG C the reaction was continued 30 minutes.Vacuum distillation removes toluene after reaction, obtains white powdery solids, adds
Enter internal standard CH2Br2, pass through1H NMR judges that nuclear-magnetism yield is 95%.Crude product is recrystallized with methylene chloride and n-hexane
To product 4a2L.1H NMR (400MHz, CD2Cl2) δ 8.74 (s, 2H), 8.04 (d, J=6.8Hz, 2H), 7.83 (t, J=
7.5Hz, 2H), 7.74 (d, J=8.1Hz, 2H), 7.62 (t, J=7.4Hz, 2H), 7.59-7.30 (m, 8H), 7.16 (t, J=
7.1Hz, 2H), 6.87 (br, 2H), 6.69 (br, 2H), 2.92 (t, J=9.6Hz, 2H), 2.32-2.18 (m, 2H), 2.14
(d, J=9.0Hz, 2H), 1.80-1.54 (m, 4H), 0.86 (dd, J=19.2,11.5Hz, 2H)；13C NMR (101MHz,
CD2Cl2) δ 149.6,137.0,136.0,134.6,131.8,129.9,129.8,129.0,127.8,127.2,127.0,
126.0,125.8,122.7,61.4,53.1,34.5,33.5,27.4.
Embodiment 3:(R) -2-Methyl-1, the synthesis of 2,3,4-tetrahydroquinoline (P1)
The loop coil chiral diene 3a (3.4mg, 0.0125mmol, 5mol%) and HB (C in the glove box full of nitrogen6F5)2
(8.65 mg, 0.025mmol, 10mol%) is added in 10mL small test tube, and the dissolution of 2mL benzotrifluoride is added, reacts at 25 DEG C
15 minutes.System is cooled to room temperature, and 2- methylquinoline S1 (35.8mg, 0.25mmol) and 3mL benzotrifluoride is then added, tightly
Then test tube is transferred in autoclave, replacing hydrogen three times after, be finally filled with hydrogen to 50bar, -20 DEG C of reactions are for 24 hours.Reaction
Hydrogen is discharged after complete, revolving removes solvent, and residue obtains hydrogenated products P1, colorless oil by silica gel column chromatography separating purification
Liquid, yield 97%, enantioselectivity 90%ee.1H NMR (400MHz, CDCl3) δ 7.00-6.95 (m, 2H), 6.68-
6.59 (m, 1H), 6.51 (d, J=6.9Hz, 1H), 3.72 (br, 1H), 3.50-3.30 (m, 1H), 2.87-2.81 (m, 1H),
2.80-2.70 (m, 1H), 2.01-1.87 (m, 1H), 1.69-1.54 (m, 1H), 1.24 (d, J=6.2Hz, 3H)；13C NMR
(101 MHz, CDCl3) δ 144.9,129.4,126.8,121.2,117.1,114.1,47.2,30.2,26.7,22.7.
Claims (5)
1. chiral spiro diene and hydroboron react under conditions of room temperature and high temperature prepares the double boron of chiral spiro
Catalyst obtains acid-base adducts object with isoquinolin (or pyridine) reaction later and determines catalyst structure by X-ray single crystal diffraction,
The double B catalysts of the chiral spiro can be catalyzed the asymmetric hydrogenation of 2 substd quinolines, the specific steps of this method are as follows:
In nitrogen atmosphere, chiral diene and boron hydrogen and toluene are sequentially added in reaction flask, stirs 15 points under assigned temperature
Clock adds isoquinolin (or pyridine) then to room temperature, is stirred at room temperature 30 minutes, removes solvent, recrystallizes isolated target
Adduct；
In nitrogen atmosphere, chiral diene and boron hydrogen and benzotrifluoride are sequentially added in reaction flask, is stirred under assigned temperature
15 minutes, it is cooled to room temperature, adds 2 substd quinolines, be transferred in autoclave and be tamping, hydrogen displacement is charged to reaction pressure afterwards three times
Power is reacted at -20 DEG C, and hydrogen remaining in kettle is carefully discharged after 24 hours for reaction, and reaction system depressurizes after being warmed to room temperature
Solvent is removed, column chromatography for separation obtains 2 substituted-tetrahydro quinoline products.
2. it is involved in the present invention to catalyst be that generated in-situ chiral spiro is double after chiral spiro diene is reacted with boron hydrogen
B catalyst, the catalyst amount are generally 2-5mol%, and R is aryl or alkyl, Ar in chiral dieneFFor containing fluoro aryl.
3. solvent for use of the present invention is benzotrifluoride, dosage is to correspond to use scope for every mM of 2 substd quinolines to be
1.0mL to 2.0mL.
4. the Hydrogen Vapor Pressure involved in the present invention arrived is in 2MPa between 5MPa.
5. R in 2 substd quinolines of the raw materials used in the present invention, R ' can be alkyl, aryl, styryl, alkynyl, conjugated diene
Base, conjugated enynes base etc..
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111171189A (en) * | 2020-01-06 | 2020-05-19 | 万华化学集团股份有限公司 | High-temperature-resistant catalyst system and application thereof |
| CN111499558A (en) * | 2020-05-14 | 2020-08-07 | 南开大学 | Asymmetric reduction method for chiral spiro-bisboron catalyzed substituted pyridine and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111171189A (en) * | 2020-01-06 | 2020-05-19 | 万华化学集团股份有限公司 | High-temperature-resistant catalyst system and application thereof |
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| CN111499558A (en) * | 2020-05-14 | 2020-08-07 | 南开大学 | Asymmetric reduction method for chiral spiro-bisboron catalyzed substituted pyridine and application thereof |
| CN111499558B (en) * | 2020-05-14 | 2022-10-18 | 南开大学 | Asymmetric reduction method of chiral spiro-bis-boron catalytic substituted pyridine and application thereof |
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