CN109232622B - Application of 2, 6-diisopropylaniline lithium in catalyzing imine and borane hydroboration reaction - Google Patents

Application of 2, 6-diisopropylaniline lithium in catalyzing imine and borane hydroboration reaction Download PDF

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CN109232622B
CN109232622B CN201811134465.0A CN201811134465A CN109232622B CN 109232622 B CN109232622 B CN 109232622B CN 201811134465 A CN201811134465 A CN 201811134465A CN 109232622 B CN109232622 B CN 109232622B
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lithium
imine
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CN109232622A (en
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薛明强
颜丹丹
陈素芳
朱章野
蔡玲霞
沈琪
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Suzhou University
Nantong Textile and Silk Industrial Technology Research Institute
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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 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
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0237—Amines
    • B01J31/0238—Amines with a primary amino group
    • 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
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
    • B01J2231/341—1,2-additions, e.g. aldol or Knoevenagel condensations
    • B01J2231/342—Aldol type reactions, i.e. nucleophilic addition of C-H acidic compounds, their R3Si- or metal complex analogues, to aldehydes or ketones
    • B01J2231/344—Boronation, e.g. by adding R-B(OR)2

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Abstract

The invention relates to application of 2, 6-diisopropyl anilino lithium, in particular to application of 2, 6-diisopropyl anilino lithium 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 2, 6-diisopropyl anilino lithium disclosed by the invention can catalyze the hydroboration reaction of imine and borane with high activity at room temperature, the dosage 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 simple 2, 6-diisopropyl anilino lithium is utilized, the reaction condition is mild, and the yield of borate ester with different substituents can reach 99% under the optimized condition.

Description

Application of 2, 6-diisopropylaniline lithium in catalyzing imine and borane hydroboration reaction
Technical Field
The invention relates to application of 2, 6-diisopropyl anilino lithium, in particular to efficient application of 2, 6-diisopropyl anilino lithium in catalyzing imine and borane hydroboration reaction.
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. Since the hydroboration reaction of carbonyl is far easier to occur than that of imine, a high-efficiency catalytic system for the hydroboration reaction of unsaturated C = N bond is developed, and the method 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 2, 6-diisopropylaniline lithium, namely application of 2, 6-diisopropylaniline lithium 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 2, 6-lithium diisopropylanilino in catalyzing hydroboration reaction of aldehyde and borane; the chemical formula of the 2, 6-diisopropylaniline lithium is as follows: 2,6-iPr2PhNHLi。
The invention also discloses a method for catalyzing imine and borane to perform hydroboration reaction by using 2, 6-diisopropyl anilino lithium, 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 2, 6-diisopropylaniline lithium, reacting for 1-2 h, and exposing in the air to terminate the reaction to obtain a product.
The invention further discloses a preparation method of the boric acid ester, which comprises the following steps: under the anhydrous and oxygen-free environment and in 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 2, 6-diisopropylaniline lithium, reacting for 1-2 h, and exposing in the air to terminate the reaction to obtain a product.
In the above technical scheme, the imine is selected from aldimine; the chemical structural general formula of the imine is as follows:
Figure 802975DEST_PATH_IMAGE001
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:
Figure 530235DEST_PATH_IMAGE002
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 simple 2, 6-diisopropyl anilino lithium can efficiently catalyze imine and borane to carry out hydroboration reaction, and is highly in line with atom economic synthesis.
2. The lithium 2, 6-diisopropylanilino catalyzes the hydroboration reaction of imine and borane, and 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 in the reaction.
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:
example I lithium 2, 6-diisopropylanilino catalyzes the hydroboration reaction of benzylidene aniline and 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 100 ul of THF, adding 0.6 mmol (0.0871 mL) of borane into a liquid-transferring gun, uniformly mixing, finally adding 40.9 ul of 2, 6-diisopropylanilino lithium tetrahydrofuran solution (0.6115M) (5 mol% dosage, the same below) into the reaction bottle, reacting for 1h, sucking one drop by a dropper into a nuclear magnetic tube, 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 two: lithium 2, 6-diisopropylanilino for catalyzing benzylidene aniline to perform hydroboration reaction 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 100 ul of THF, adding 0.6 mmol (0.0871 mL) of borane into a liquid-transferring gun, uniformly mixing, finally adding 40.9 ul of 2, 6-diisopropylaniline lithium tetrahydrofuran solution (0.6115M) (5 mol% dosage), reacting for 2 h, 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: 7.29~7.12(m, 9H), 6.88~6.84 (t, 1H), 4.69 (s, 2H), 1.29 (s, 12H)。
the product cannot be obtained by replacing 2, 6-diisopropylanilino lithium with an aminolithium compound of formula i.
Figure 841131DEST_PATH_IMAGE003
Example three: lithium 2, 6-diisopropylanilino for catalyzing benzylidene aniline to perform hydroboration reaction 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 100 ul of THF, adding 0.6 mmol (0.0871 mL) of borane into a liquid-transferring gun, uniformly mixing, finally adding 32.7 ul of 2, 6-diisopropylaniline lithium tetrahydrofuran solution (0.6115M) (4 mol% dosage), reacting for 2 h, sucking one drop of 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 four: lithium 2, 6-diisopropylanilino for catalyzing benzylidene aniline to perform hydroboration reaction 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 100 ul of THF, adding 0.5 mmol (0.0726 mL) of borane into a liquid-transferring gun, uniformly mixing, finally adding 40.9 ul of 2, 6-dimethylanilinium tetrahydrofuran solution (0.6115M) (5 mol% dosage, the same below) into the reaction bottle, 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 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 five: lithium 2, 6-diisopropylanilino for catalyzing benzylidene aniline to perform hydroboration reaction 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 100 ul of THF, and then addingThen 0.55 mmol (0.0798 mL) of borane is added by a pipette and mixed evenly, and finally 40.9 ul of 2, 6-diisopropylaniline lithium tetrahydrofuran solution (0.6115M) (5 mol% dosage, the same below) is added, after 2 hours of reaction, one drop is absorbed by a dropper and put into a nuclear magnetic tube, and CDCl is added3Preparing 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 six: 2, 6-lithium diisopropylanilino catalyzing N-, (pHydroboration 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, 100 ul THF, 0.6 mmol (0.0871 mL) borane by pipette, mixing well, finally 40.9 ul lithium 2, 6-diisopropylanilino (0.6115M) in tetrahydrofuran (5 mol% amount, the same applies below), reaction for 2 h, 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: 7.23~7.08(m, 8H), 6.89~6.85 (t, 1H), 4.66 (s, 2H), 2.31 (s, 3H), 1.30 (s, 12H)。
example seven: 2, 6-lithium diisopropylanilino catalyzing N-, (pHydroboration of (methoxybenzylidene) 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, 100 ul THF, 0.6 mmol (0.0871 mL) borane by pipette, mixing well, 40.9 ul lithium 2, 6-diisopropylanilino (0.6115M) in tetrahydrofuran (5 mol% amount, the same applies below), reaction for 2 h, 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: lithium 2, 6-diisopropylanilino for catalyzing hydroboration reaction of N- (4-fluorobenzylidene) aniline and pinacol borane
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 100 ul of THF, then adding 0.6 mmol (0.0871 mL) of borane into a pipette gun, uniformly mixing, finally adding 40.9 ul of 2, 6-diisopropylanilino lithium tetrahydrofuran solution (0.6115M) (5 mol% dosage, the same below) into the reaction bottle, reacting for 2 hours, sucking one drop by a dropper into a nuclear magnetic tube, and 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: 7.22~7.15(d, 6H), 6.98~6.94 (d, 3H), 4.66 (s, 2H), 1.30 (s, 12H)。
example nine: 2, 6-diisopropyl anilino lithium is used for catalyzing hydroboration reaction of N- (4-chlorobenzylidene) aniline and pinacol borane
Adding 0.5 mmol of N- (4-chlorobenzylidene) aniline into a reaction bottle subjected to dehydration and deoxidation treatment under the protection of argon, adding 100 ul of THF, then adding 0.6 mmol (0.0871 mL) of borane into a pipette gun, uniformly mixing, finally adding 40.9 ul of 2, 6-diisopropylanilino lithium tetrahydrofuran solution (0.6115M) (5 mol% dosage, the same below) into the reaction bottle, reacting for 2 hours, sucking one drop by a dropper into a nuclear magnetic tube, and 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: 7.20~7.14(d, 6H), 6.99~6.93 (d, 3H), 4.64 (s, 2H), 1.30 (s, 12H)。
example ten: lithium 2, 6-diisopropylanilino for catalyzing hydroboration reaction of N- (4-bromobenzyl methylene) aniline and pinacol borane
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 100 ul of THF, then adding 0.6 mmol (0.0871 mL) of borane into a liquid-transferring gun, uniformly mixing, finally adding 40.9 ul of a tetrahydrofuran solution (0.6115M) of 2, 6-diisopropylanilino lithium (5 mol% dosage, the same below), reacting for 2 hours, sucking one drop by a dropper into a nuclear magnetic tube, and 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: 7.24~7.16(d, 6H), 6.97~6.93 (d, 3H), 4.63 (s, 2H), 1.31 (s, 12H)。
example eleven: 2, 6-diisopropylaniline lithium catalyzed benzal p-toluidine and pinacol borane hydroboration reaction
Adding 0.5 mmol of benzylidene p-toluene into a reaction bottle subjected to dehydration and deoxidation treatment under the protection of argon, adding 100 ul of THF, then adding 0.6 mmol (0.0871 mL) of borane into a liquid-transferring gun, uniformly mixing, finally adding 40.9 ul of 2, 6-diisopropylaniline lithium tetrahydrofuran solution (0.6115M) (5 mol% dosage, the same below), reacting for 2 hours, absorbing 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: hydroboration reaction of N- (benzylidene) -4-fluoroaniline and pinacol borane catalyzed by lithium 2, 6-diisopropylanilino
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 100 ul of THF, then adding 0.6 mmol (0.0871 mL) of borane into a pipette gun, uniformly mixing, finally adding 40.9 ul of a tetrahydrofuran solution (0.6115M) of 2, 6-diisopropylanilino lithium (5 mol% dosage, the same below), reacting for 2 hours, sucking one drop by a dropper into a nuclear magnetic tube, and 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: lithium 2, 6-diisopropylanilino for catalyzing hydroboration reaction of N- (benzylidene) -4-chloroaniline and pinacol borane
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 100 ul of THF, and then addingThen 0.6 mmol (0.0871 mL) of borane is added by a pipette and mixed evenly, and finally 40.9 ul of 2, 6-diisopropylaniline lithium tetrahydrofuran solution (0.6115M) (5 mol% dosage, the same below) is added, after 2 h reaction, one drop is absorbed by a dropper and put into a nuclear magnetic tube, and CDCl is 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: 7.26~7.05(d, 7H), 6.74~6.69 (d, 2H), 4.61 (s, 2H), 1.30 (s, 12H)。
example fourteen: hydroboration reaction of N- (benzylidene) -4-bromoaniline and pinacol borane catalyzed by lithium 2, 6-diisopropylanilino
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 100 ul of THF, then adding 0.6 mmol (0.0871 mL) of borane into a pipette gun, uniformly mixing, finally adding 40.9 ul of a tetrahydrofuran solution (0.6115M) of 2, 6-diisopropylanilino lithium (5 mol% dosage, the same below), reacting for 2 hours, sucking one drop by a dropper into a nuclear magnetic tube, and 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 discloses that the commercial reagent 2, 6-diisopropylaniline lithium can catalyze the hydroboration reaction of imine under mild reaction conditions for the first time, 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 2, 6-lithium diisopropylanilino in catalyzing imine and borane hydroboration reaction is characterized in that the method for catalyzing imine and borane hydroboration reaction by using 2, 6-lithium diisopropylanilino comprises the following steps: under the anhydrous and oxygen-free environment and in 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, then adding a catalyst 2, 6-diisopropylaniline lithium, reacting at room temperature for 1-2 h, and exposing the mixture to air to terminate the reaction to obtain a product; the chemical structural general formula of the imine is as follows:
    Figure 401440DEST_PATH_IMAGE001
    wherein R is1Or R2Is one of electron withdrawing group or electron donating group, and is selected from halogen, methyl and methoxyl; the borane is selected from pinacol borane; the organic solvent is tetrahydrofuran;
    the dosage of the 2, 6-diisopropylaniline lithium is 4-5% of the mole number of the imine, and the molar ratio of the imine to the pinacol borane is 1: 1-1: 1.2.
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CN108395447A (en) * 2018-04-16 2018-08-14 苏州大学张家港工业技术研究院 The method for preparing borate based on 2,6- diisopropyl benzene amido lithiums catalysis aldehyde reaction
CN108503659A (en) * 2018-04-16 2018-09-07 苏州大学 The method for preparing borate using 2,6- diisopropyl benzene amido lithiums
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