CN109331872B - Application of n-butyl lithium in catalyzing imine and borane hydroboration reaction - Google Patents
Application of n-butyl lithium in catalyzing imine and borane hydroboration reaction Download PDFInfo
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- CN109331872B CN109331872B CN201811133200.9A CN201811133200A CN109331872B CN 109331872 B CN109331872 B CN 109331872B CN 201811133200 A CN201811133200 A CN 201811133200A CN 109331872 B CN109331872 B CN 109331872B
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- borane
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- butyllithium
- aniline
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- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 title claims abstract description 102
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 238000006197 hydroboration reaction Methods 0.000 title claims abstract description 33
- 229910000085 borane Inorganic materials 0.000 title claims abstract description 32
- 150000002466 imines Chemical class 0.000 title claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- -1 borate ester Chemical class 0.000 claims abstract description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 61
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 30
- LZPWAYBEOJRFAX-UHFFFAOYSA-N 4,4,5,5-tetramethyl-1,3,2$l^{2}-dioxaborolane Chemical group CC1(C)O[B]OC1(C)C LZPWAYBEOJRFAX-UHFFFAOYSA-N 0.000 claims description 18
- 230000018044 dehydration Effects 0.000 claims description 17
- 238000006297 dehydration reaction Methods 0.000 claims description 17
- UVEWQKMPXAHFST-UHFFFAOYSA-N n,1-diphenylmethanimine Chemical group C=1C=CC=CC=1C=NC1=CC=CC=C1 UVEWQKMPXAHFST-UHFFFAOYSA-N 0.000 claims description 11
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- MJSLSMOBYCYMIM-UHFFFAOYSA-N 1-(4-bromophenyl)-n-phenylmethanimine Chemical compound C1=CC(Br)=CC=C1C=NC1=CC=CC=C1 MJSLSMOBYCYMIM-UHFFFAOYSA-N 0.000 claims description 3
- CFBVFBIZXQEQHX-UHFFFAOYSA-N 1-(4-chlorophenyl)-n-phenylmethanimine Chemical compound C1=CC(Cl)=CC=C1C=NC1=CC=CC=C1 CFBVFBIZXQEQHX-UHFFFAOYSA-N 0.000 claims description 3
- MPRONVWLCPZXOB-UHFFFAOYSA-N 1-(4-fluorophenyl)-n-phenylmethanimine Chemical compound C1=CC(F)=CC=C1C=NC1=CC=CC=C1 MPRONVWLCPZXOB-UHFFFAOYSA-N 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- OEJZOCTWYUFFNN-UHFFFAOYSA-N n-(4-fluorophenyl)-1-phenylmethanimine Chemical compound C1=CC(F)=CC=C1N=CC1=CC=CC=C1 OEJZOCTWYUFFNN-UHFFFAOYSA-N 0.000 claims description 3
- DJGDQBWKJYPZEF-UHFFFAOYSA-N n-(4-bromophenyl)-1-phenylmethanimine Chemical compound C1=CC(Br)=CC=C1N=CC1=CC=CC=C1 DJGDQBWKJYPZEF-UHFFFAOYSA-N 0.000 claims description 2
- NWCAQYVAHZWHIO-UHFFFAOYSA-N n-(4-chlorophenyl)-1-phenylmethanimine Chemical compound C1=CC(Cl)=CC=C1N=CC1=CC=CC=C1 NWCAQYVAHZWHIO-UHFFFAOYSA-N 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- 125000001424 substituent group Chemical group 0.000 abstract 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 abstract 1
- 238000003756 stirring Methods 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N deuterated chloroform Substances [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 33
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 28
- 238000005160 1H NMR spectroscopy Methods 0.000 description 14
- 229910052786 argon Inorganic materials 0.000 description 14
- 238000001228 spectrum Methods 0.000 description 14
- 239000007788 liquid Substances 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 241001289435 Astragalus brachycalyx Species 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 235000002917 Fraxinus ornus Nutrition 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000004705 aldimines Chemical group 0.000 description 1
- 229930013930 alkaloid Natural products 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- KDKHRAVKGIIQHF-UHFFFAOYSA-N methyl n-phenylbenzenecarboximidate Chemical compound C=1C=CC=CC=1C(OC)=NC1=CC=CC=C1 KDKHRAVKGIIQHF-UHFFFAOYSA-N 0.000 description 1
- CBXWICRJSHEQJT-UHFFFAOYSA-N n,1-diphenylethanimine Chemical compound C=1C=CC=CC=1C(C)=NC1=CC=CC=C1 CBXWICRJSHEQJT-UHFFFAOYSA-N 0.000 description 1
- MSFVFFZPHJPOHP-UHFFFAOYSA-N n-(4-methylphenyl)-1-phenylmethanimine Chemical compound C1=CC(C)=CC=C1N=CC1=CC=CC=C1 MSFVFFZPHJPOHP-UHFFFAOYSA-N 0.000 description 1
- 102000039446 nucleic acids Human genes 0.000 description 1
- 108020004707 nucleic acids Proteins 0.000 description 1
- 150000007523 nucleic acids Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- 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 Table
- C07F5/02—Boron compounds
- C07F5/022—Boron compounds without C-boron linkages
-
- 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
- B01J31/122—Metal aryl or alkyl compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
Abstract
The invention relates to application of n-butyllithium, in particular to application of n-butyllithium in catalyzing hydroboration reaction of imine and borane. And stirring and mixing the catalyst, borane and imine uniformly in sequence, reacting for 1-2 hours, exposing the mixture to air to terminate the reaction, and decompressing the reaction solution to remove the solvent to obtain the borate with different substituent groups. The n-butyllithium disclosed by the invention can catalyze the hydroboration reaction of imine and borane with high activity at room temperature, the using amount of the catalyst is only 4-5 mol% of the molar weight of imine, the reaction yield can reach more than 90%, compared with the existing catalytic system, the commercial reagent n-butyllithium is utilized, the reaction condition is mild, and the yield of borate ester of different substituents under the limited condition can reach 99%.
Description
Technical Field
The invention relates to application of a commercial reagent n-butyllithium, in particular to application of n-butyllithium in catalyzing synthesis of imine and borane.
Technical Field
The amine compounds and derivatives thereof are ubiquitous in nature, especially widely exist in the biological world, and have extremely important physiological effects. They are important organic compounds in the fields of biology, chemistry, medicine, etc., and many drugs contain amine functional groups, i.e., amino groups, such as those found in proteins, nucleic acids, antibiotics, and alkaloids. The amine compound has various use values and wide application range, and is often used for synthesizing textiles, dyes, polymers, pigments, pesticides and the like. In the prior art, a hydroboration reaction related to a C = O bond is existed, and the hydroboration reaction related to a carbonyl group is far easier to occur than that related to imine, so that the conditions related to the hydroboration reaction related to a C = N bond in the prior art are very harsh, and a high-efficiency catalytic system for the hydroboration reaction related to an unsaturated C = N bond is developed, and the catalyst system has important significance for modern industry and organic synthetic chemistry.
The hydroboration reaction of imine has become a research hotspot in recent years, and the reported catalyst applied to the hydroboration reaction of imine mainly comprises a catalytic system of main group elements: magnesium, calcium, sodium, rhenium, zinc, etc. (see Manna, k.; Ji, p.; Greene, f. x.; Lin, W.).J. Am. Chem. Soc.2016,138, 7488−7491；Lin, Y-C.; Hatzakis, E.;McCarthy, S. M.; Reichl, K. D.; Lai, T-Y.; Yennawar, H. P.; Radosevich, A. T.J. Am. Chem. Soc.2017,139, 6008-6016). However, the catalyst systems reported at present are relatively expensive or difficult to prepare, or have long reaction time and are required to react at high temperature, and some catalytic systems have low yield. Therefore, it is very important to develop a catalytic system for efficiently catalyzing the hydroboration reaction of imine under mild conditions.
Disclosure of Invention
The invention aims to provide application of n-butyllithium, namely application of n-butyllithium serving as a high-efficiency catalyst for catalyzing imine and borane to perform hydroboration reaction.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows: the application of n-butyl lithium in catalyzing the hydroboration reaction of imine and borane; the n-butyllithium is a commercial n-butyllithium reagent.
The invention also discloses a method for catalyzing imine and borane to perform hydroboration reaction by using n-butyllithium, which comprises the following steps: under the anhydrous and oxygen-free environment and the inert gas atmosphere, adding imine into a reaction bottle subjected to dehydration and deoxidation treatment, adding an organic solvent, then adding borane, uniformly mixing, adding a catalyst n-butyllithium, reacting for 1-2 h, and exposing the mixture to air to terminate the reaction to obtain a product.
The invention further discloses a method for preparing boric acid ester by carrying out hydroboration reaction on imine and borane, which comprises the following steps: under an anhydrous and oxygen-free environment and in an inert gas atmosphere, adding imine into a reaction bottle subjected to dehydration and deoxidation treatment, adding an organic solvent, then adding borane, uniformly mixing, adding a catalyst n-butyllithium, reacting for 1-2 h, and exposing the mixture to air to terminate the reaction to obtain the product boric acid ester.
In the above technical scheme, the imine is selected from aldimine; the chemical structural general formula of the imine is as follows:
wherein R is1Or R2Is one of electron withdrawing group or electron donating group, and can be selected from halogen, methyl and methoxy; the borane is selected from pinacol borane.
In the technical scheme, the using amount of the catalyst can be 4-5% of the mole number of the imine, and the mole ratio of the imine to the pinacol borane is 1: 1-1: 1.2.
In the technical scheme, the reaction temperature is room temperature, and the reaction time is 1-2 h.
In the above technical scheme, the organic solvent is tetrahydrofuran.
The above technical solution can be expressed as follows:
due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
1. the invention discovers for the first time that commercial n-butyllithium can efficiently catalyze imine and borane to carry out hydroboration reaction, and the method highly conforms to the atom economic synthesis.
2. The method disclosed by the invention has the advantages of high catalytic activity (4-5% of the mole number of the catalyst), mild reaction conditions (room temperature), short reaction time (1-2 h), high reaction yield, simple and controllable reaction, simple post-treatment and low-cost THF (tetrahydrofuran) used as a solvent.
3. The catalyst disclosed by the invention has better universality for imines with different substitution positions and different electronic effects.
Detailed Description
The invention is further described below with reference to examples:
the first embodiment is as follows: n-butyl lithium catalyzed benzyl idene aniline and pinacol borane hydroboration reaction
Adding 0.5 mmol of benzylidene aniline into a reaction bottle subjected to dehydration and deoxidation treatment under the protection of argon, adding 100ul of THF, adding 0.5 mmol (0.0726 mL) of borane into a liquid transfer gun, uniformly mixing, finally adding 25 ul of n-butyllithium tetrahydrofuran solution (1M) (5 mol% dosage, the same below), reacting for 2 hours, sucking one drop of the solution into a nuclear magnetic tube by a dropper, and adding CDCl3Preparing a solution. Is calculated by1The yield of the H spectrum is 90%. Nuclear magnetic data of the product:1H NMR (CDCl3, 400 MHz) δ:7.29~7.12(m, 9H), 6.88~6.84 (t, 1H), 4.69 (s, 2H), 1.29 (s, 12H)。
example two: n-butyl lithium catalyzed benzyl idene aniline and pinacol borane hydroboration reaction
Adding 0.5 mmol of benzylidene aniline into a reaction bottle subjected to dehydration and deoxidation treatment under the protection of argon, adding 100ul of THF, adding 0.55 mmol (0.0798 mL) of borane into a liquid transfer gun, uniformly mixing, finally adding 25 ul of n-butyllithium tetrahydrofuran solution (1M) (5 mol% dosage, the same below), reacting for 2 hours, sucking one drop of the solution into a nuclear magnetic tube by a dropper, adding CDCl3Preparing a solution. Is calculated by1The yield of the H spectrum is 95%. Nuclear magnetic data of the product:1H NMR (CDCl3, 400 MHz) δ:7.29~7.12(m, 9H), 6.88~6.84 (t, 1H), 4.69 (s, 2H), 1.29 (s, 12H)。
EXAMPLE III N-butyl lithium catalyzed hydroboration of benzylidene aniline with pinacol borane
Adding 0.5 mmol of benzylidene aniline into a reaction bottle subjected to dehydration and deoxidation treatment under the protection of argon, adding 100ul of THF, adding 0.6 mmol (0.0871 mL) of borane into a liquid transfer gun, uniformly mixing, finally adding 25 ul of n-butyllithium tetrahydrofuran solution (1M) (5 mol% dosage, the same below), reacting for 1 h, sucking one drop of the solution into a nuclear magnetic tube by a dropper, and adding CDCl3Preparing a solution. Is calculated by1The yield of the H spectrum is 96%. Nuclear magnetic data of the product:1H NMR (CDCl3, 400 MHz)δ:7.29~7.12(m, 9H), 6.88~6.84 (t, 1H), 4.69 (s, 2H), 1.29 (s, 12H)。
example four: n-butyl lithium catalyzed benzyl idene aniline and pinacol borane hydroboration reaction
Adding 0.5 mmol of benzylidene aniline into a reaction bottle subjected to dehydration and deoxidation treatment under the protection of argon, adding 100ul of THF, adding 0.6 mmol (0.0871 mL) of borane into a liquid transfer gun, uniformly mixing, finally adding 20ul of n-butyllithium tetrahydrofuran solution (1M) (4 mol% dosage), reacting for 2 hours, absorbing one drop of solution into a nuclear magnetic tube by a dropper, adding CDCl3Preparing a solution. Is calculated by1The yield of the H spectrum is 97%. Nuclear magnetic data of the product:1H NMR (CDCl3, 400 MHz) δ: 7.29~7.12(m, 9H), 6.88~6.84 (t, 1H), 4.69 (s, 2H), 1.29 (s, 12H)。
example five: n-butyl lithium catalyzed benzyl idene aniline and pinacol borane hydroboration reaction
Adding 0.5 mmol of benzylidene aniline into a reaction bottle subjected to dehydration and deoxidation treatment under the protection of argon, adding 100ul of THF, adding 0.6 mmol (0.0871 mL) of borane into a liquid transfer gun, uniformly mixing, finally adding 25 ul of n-butyllithium tetrahydrofuran solution (1M) (5 mol% dosage), reacting for 2 hours, absorbing one drop of the solution into a nuclear magnetic tube by a dropper, adding CDCl3Preparing a solution. Is calculated by1The yield of the H spectrum is 99%. Nuclear magnetic data of the product:1H NMR (CDCl3, 400 MHz)δ: 7.29~7.12(m, 9H), 6.88~6.84 (t, 1H), 4.69 (s, 2H), 1.29 (s, 12H)。
the product was not obtained by replacing n-butyllithium with an aminolithium compound of formula i.
Example six: n-, (ii) N-butyl lithium catalysispHydroboration of (methylbenzylidene) aniline with pinacol borane
Adding 0.5 mmol of N-, (N) into a reaction bottle subjected to dehydration and deoxidation treatment under the protection of argonp-methylbenzylidene) aniline, 100ul THF and then 0.6 mmol (0.0) by pipette871 mL) borane, adding 25 ul n-butyllithium tetrahydrofuran solution (1M) (5 mol% dosage, the same below), reacting for 2h, dropping into a nuclear magnetic tube, adding CDCl3Preparing a solution. Is calculated by1The yield of the H spectrum is 99%. Nuclear magnetic data of the product:1H NMR (CDCl3,400 MHz)δ: 7.23~7.08(m, 8H), 6.89~6.85 (t, 1H), 4.66 (s, 2H), 2.31 (s, 3H),1.30 (s, 12H)。
example seven: n-, (ii) N-butyl lithium catalysispHydroboration of (methoxy benzylidene) aniline with pinacol borane
Adding 0.5 mmol of N-, (N) into a reaction bottle subjected to dehydration and deoxidation treatment under the protection of argonp-methoxybenzylidene) aniline, 100ul THF, 0.6 mmol (0.0871 mL) borane by pipette tip, mixing well, 20ul n-butyllithium in tetrahydrofuran (1M) (4 mol% amount, the same applies below), reaction for 2h, pipette one drop into a nuclear magnetic tube, CDCl was added3Preparing a solution. Is calculated by1The yield of the H spectrum is 99%. Nuclear magnetic data of the product:1H NMR(CDCl3, 400 MHz)δ: 7.22~7.13(d, 6H), 6.89~6.80 (d, 3H), 4.63 (s, 2H), 3.77(s, 3H), 1.30 (s, 12H)。
example eight: n- (4-fluorobenzylidene) aniline and pinacol borane hydroboration reaction catalyzed by N-butyl lithium
Adding 0.5 mmol of N- (4-fluorobenzylidene) aniline into a reaction bottle subjected to dehydration and deoxidation treatment under the protection of argon, adding 100ul of THF, then adding 0.6 mmol (0.0871 mL) of borane into a pipette gun, uniformly mixing, finally adding 25 ul of N-butyllithium tetrahydrofuran solution (1M) (5 mol% dosage, the same below), reacting for 2 hours, sucking one drop of nuclear magnetic tube by a dropper, adding CDCl3Preparing a solution. Is calculated by1The yield of the H spectrum is 99%. Nuclear magnetic data of the product:1H NMR (CDCl3, 400MHz)δ: 7.22~7.15(d, 6H), 6.98~6.94 (d, 3H), 4.66 (s, 2H), 1.30 (s, 12H)。
example nine: n- (4-chlorobenzylidene) aniline and pinacol borane hydroboration reaction catalyzed by N-butyl lithium
After dehydration and dehydrationIn an oxygen-treated reaction bottle, adding 0.5 mmol of N- (4-chlorobenzylidene) aniline under the protection of argon, adding 100ul of THF, then adding 0.6 mmol (0.0871 mL) of borane by using a pipette gun, uniformly mixing, finally adding 25 ul of N-butyllithium tetrahydrofuran solution (1M) (5 mol% dosage, the same below), reacting for 2 hours, sucking one drop by using a dropper into a nuclear magnetic tube, adding CDCl3Preparing a solution. Is calculated by1The yield of the H spectrum is 99%. Nuclear magnetic data of the product:1H NMR (CDCl3, 400MHz)δ: 7.20~7.14(d, 6H), 6.99~6.93 (d, 3H), 4.64 (s, 2H), 1.30 (s, 12H)。
example ten: n- (4-bromobenzylidene) aniline and pinacol borane hydroboration reaction catalyzed by N-butyl lithium
Adding 0.5 mmol of N- (4-bromobenzylidene) aniline into a reaction bottle subjected to dehydration and deoxidation treatment under the protection of argon, adding 100ul of THF, then adding 0.6 mmol (0.0871 mL) of borane into a liquid-transferring gun, uniformly mixing, finally adding 25 ul of N-butyllithium tetrahydrofuran solution (1M) (5 mol% dosage, the same below), reacting for 2 hours, sucking one drop of solution into a nuclear magnetic tube by a dropper, adding CDCl3Preparing a solution. Is calculated by1The yield of the H spectrum is 99%. Nuclear magnetic data of the product:1H NMR (CDCl3, 400MHz)δ: 7.24~7.16(d, 6H), 6.97~6.93 (d, 3H), 4.63 (s, 2H), 1.31 (s, 12H)。
example eleven: hydroboration reaction of benzylidene p-toluidine and pinacol borane catalyzed by n-butyl lithium
Adding 0.5 mmol of benzylidene p-toluene into a reaction bottle subjected to dehydration and deoxidation treatment under the protection of argon, adding 100ul of THF, then adding 0.6 mmol (0.0871 mL) of borane into a liquid transfer gun, uniformly mixing, finally adding 25 ul of n-butyllithium tetrahydrofuran solution (1M) (5 mol% dosage, the same below), reacting for 2 hours, sucking one drop by a dropper into a nuclear magnetic tube, adding CDCl3Preparing a solution. Is calculated by1The yield of the H spectrum is 99%. Nuclear magnetic data of the product:1H NMR (CDCl3, 400 MHz)δ: 7.32~7.28(d, 5H), 7.10~7.08 (d, 2H), 6.64~6.60 (d, 2H), 4.62 (s, 2H), 1.31(s, 12H)。
example twelve: n- (benzylidene) -4-fluoroaniline and pinacol borane hydroboration reaction catalyzed by N-butyllithium
Adding 0.5 mmol of N- (benzylidene) -4-fluoroaniline into a reaction bottle subjected to dehydration and deoxidation treatment under the protection of argon, adding 100ul of THF, then adding 0.6 mmol (0.0871 mL) of borane into a pipette gun, uniformly mixing, finally adding 25 ul of tetrahydrofuran solution (1M) of N-butyllithium (5 mol% dosage, the same below), reacting for 2 hours, sucking one drop of nuclear magnetic tube by a dropper, adding CDCl3Preparing a solution. Is calculated by1The yield of the H spectrum is 99%. Nuclear magnetic data of the product:1H NMR (CDCl3,400 MHz)δ: 7.24~7.02(d, 7H), 6.75~6.70 (d, 2H), 4.66 (s, 2H), 1.32 (s, 12H)。
example thirteen: n- (benzylidene) -4-chloroaniline and pinacol borane hydroboration reaction catalyzed by N-butyl lithium
Adding 0.5 mmol of N- (benzylidene) -4-chloroaniline into a reaction bottle subjected to dehydration and deoxidation treatment under the protection of argon, adding 100ul of THF, then adding 0.6 mmol (0.0871 mL) of borane into a pipette gun, uniformly mixing, finally adding 25 ul of tetrahydrofuran solution (1M) of N-butyllithium (5 mol% dosage, the same below), reacting for 2 hours, sucking one drop of nuclear magnetic tube by a dropper, adding CDCl3Preparing a solution. Is calculated by1The yield of the H spectrum is 99%. Nuclear magnetic data of the product:1H NMR (CDCl3,400 MHz)δ: 7.26~7.05(d, 7H), 6.74~6.69 (d, 2H), 4.61 (s, 2H), 1.30 (s, 12H)。
example fourteen: n- (benzylidene) -4-bromoaniline and pinacol borane hydroboration reaction catalyzed by N-butyl lithium
Adding 0.5 mmol of N- (benzylidene) -4-bromoaniline into a reaction bottle subjected to dehydration and deoxidation treatment under the protection of argon, adding 100ul of THF, then adding 0.6 mmol (0.0871 mL) of borane into a pipette gun, uniformly mixing, finally adding 25 ul of tetrahydrofuran solution (1M) of N-butyllithium (5 mol% dosage, the same below), reacting for 2 hours, sucking one drop of nuclear magnetic tube by a dropper, adding CDCl3Preparing a solution. Is calculated by1The yield of the H spectrum is 99%. Nuclear magnetic data of the product:1H NMR (CDCl3,400 MHz)δ: 7.27~7.03(d, 7H), 6.76~6.71 (d, 2H), 4.62 (s, 2H), 1.30 (s, 12H)。
the reaction temperature in the above examples was room temperature; the invention discovers for the first time that a commercial reagent n-butyllithium can catalyze the hydroboration reaction of imine under mild reaction conditions, has high yield, wide substrate application range, cheap catalyst and mild catalysis conditions, and provides possibility for industrial application.
Claims (1)
1. The application of n-butyl lithium in catalyzing imine and borane hydroboration reaction is characterized in that the method for catalyzing imine and borane hydroboration reaction by using n-butyl lithium comprises the following steps: under the anhydrous and oxygen-free environment and the inert gas atmosphere, adding imine into a reaction bottle subjected to dehydration and deoxidation treatment, adding an organic solvent, then adding borane, uniformly mixing, adding a catalyst n-butyllithium, reacting at room temperature for 1-2 h, and exposing the reaction bottle to air to terminate the reaction to obtain a product; the imine is benzylidene aniline and N- (N-)p-methylbenzylidene) aniline, N- (4-fluorobenzylidene) aniline, N- (4-chlorobenzylidene) aniline, N- (4-bromobenzylidene) aniline, N- (benzylidene) -4-fluoroaniline, N- (benzylidene) -4-chloroaniline, or N- (benzylidene) -4-bromoaniline; the borane is selected from pinacol borane; the organic solvent is tetrahydrofuran; the dosage of the n-butyllithium is 4-5% of the mole number of the imine, and the mole ratio of the imine to the pinacol borane is 1: 1-1: 1.2.
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