CN108554446B - Application of lithium p-methylanilino in catalyzing aldehyde and borane hydroboration reaction - Google Patents
Application of lithium p-methylanilino in catalyzing aldehyde and borane hydroboration reaction Download PDFInfo
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- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 229910000085 borane Inorganic materials 0.000 title claims abstract description 38
- 238000006197 hydroboration reaction Methods 0.000 title claims abstract description 32
- 229910052744 lithium Inorganic materials 0.000 title description 10
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 title 1
- 150000001299 aldehydes Chemical class 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- PPCYTBOJJVULEX-UHFFFAOYSA-N lithium;(4-methylphenyl)azanide Chemical compound [Li+].CC1=CC=C([NH-])C=C1 PPCYTBOJJVULEX-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 230000018044 dehydration Effects 0.000 claims abstract description 13
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 13
- 150000003934 aromatic aldehydes Chemical group 0.000 claims abstract description 9
- 239000011261 inert gas Substances 0.000 claims abstract description 4
- 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 11
- 239000000126 substance Substances 0.000 claims description 4
- 125000006575 electron-withdrawing group Chemical group 0.000 claims description 2
- -1 boric acid ester Chemical class 0.000 abstract description 19
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 239000004327 boric acid Substances 0.000 abstract description 4
- 230000035484 reaction time Effects 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 36
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 28
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- 239000000203 mixture Substances 0.000 description 12
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 description 10
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 9
- 238000005160 1H NMR spectroscopy Methods 0.000 description 9
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 9
- 229910052786 argon Inorganic materials 0.000 description 8
- BMQDAIUNAGXSKR-UHFFFAOYSA-N (3-hydroxy-2,3-dimethylbutan-2-yl)oxyboronic acid Chemical compound CC(C)(O)C(C)(C)OB(O)O BMQDAIUNAGXSKR-UHFFFAOYSA-N 0.000 description 4
- HIKRJHFHGKZKRI-UHFFFAOYSA-N 2,4,6-trimethylbenzaldehyde Chemical compound CC1=CC(C)=C(C=O)C(C)=C1 HIKRJHFHGKZKRI-UHFFFAOYSA-N 0.000 description 4
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- BTFQKIATRPGRBS-UHFFFAOYSA-N o-tolualdehyde Chemical compound CC1=CC=CC=C1C=O BTFQKIATRPGRBS-UHFFFAOYSA-N 0.000 description 4
- CSDSSGBPEUDDEE-UHFFFAOYSA-N 2-formylpyridine Chemical group O=CC1=CC=CC=N1 CSDSSGBPEUDDEE-UHFFFAOYSA-N 0.000 description 3
- 150000001728 carbonyl compounds Chemical class 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- CNUDBTRUORMMPA-UHFFFAOYSA-N formylthiophene Chemical compound O=CC1=CC=CS1 CNUDBTRUORMMPA-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- SRWILAKSARHZPR-UHFFFAOYSA-N 3-chlorobenzaldehyde Chemical compound ClC1=CC=CC(C=O)=C1 SRWILAKSARHZPR-UHFFFAOYSA-N 0.000 description 2
- UOQXIWFBQSVDPP-UHFFFAOYSA-N 4-fluorobenzaldehyde Chemical compound FC1=CC=C(C=O)C=C1 UOQXIWFBQSVDPP-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 description 2
- FXLOVSHXALFLKQ-UHFFFAOYSA-N p-tolualdehyde Chemical compound CC1=CC=C(C=O)C=C1 FXLOVSHXALFLKQ-UHFFFAOYSA-N 0.000 description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- SFEPLPNTWLUBQY-UHFFFAOYSA-N argon furan Chemical compound O1C=CC=C1.[Ar] SFEPLPNTWLUBQY-UHFFFAOYSA-N 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- VILAVOFMIJHSJA-UHFFFAOYSA-N dicarbon monoxide Chemical compound [C]=C=O VILAVOFMIJHSJA-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 1
- 238000005935 nucleophilic addition reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Classifications
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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
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0252—Nitrogen containing compounds with a metal-nitrogen link, e.g. metal amides, metal guanidides
-
- 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
- C07F5/04—Esters of boric acids
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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 p-methylanilino lithium in catalyzing hydroboration reaction of aldehyde and borane, under the anhydrous and oxygen-free environment and in the inert gas atmosphere, adding borane into a reaction bottle subjected to dehydration and deoxidation treatment, then adding a catalyst p-methylanilino lithium, uniformly mixing, adding aldehyde, performing hydroboration reaction, and exposing in the air to terminate the reaction to obtain a product boric acid ester; the aldehyde is selected from aromatic aldehyde and heterocyclic aldehyde. The p-methylanilino lithium disclosed by the invention has high catalytic activity (the dosage of the catalyst is only 0.1%) for catalyzing the hydroboration reaction of aldehyde and borane, mild reaction conditions (room temperature), short reaction time (10 min), high reaction yield, simple and controllable reaction, simple post-treatment, and reduction of environmental pollution due to the adoption of a solvent-free system.
Description
Technical Field
The invention relates to application of p-methylanilino lithium, in particular to high-efficiency application of p-methylanilino lithium in catalyzing hydroboration reaction of aldehyde and borane.
Technical Field
Various catalysts have been used for hydroboration of aldehydes, and particularly in recent years, reports on such reactions have been very high. The hydroboration reaction of the carbonyl compound hardly occurs due to the absence of the catalyst. Therefore, the research on the reactions is focused on developing high-efficiency catalytic systems. However, the catalyst of the catalytic systems reported at present is relatively expensive or the reaction conditions are harsh.
Although the same carbonyl compound, ketone and aldehyde have different reaction properties, which is common knowledge, the prior art has the situation that only one raw material is reacted by taking ketone and aldehyde as raw materials; the electron-donating group can weaken the electropositivity of carbonyl carbon, thereby weakening the nucleophilic addition activity of carbonyl, and the aromatic aldehyde reduces the carbonyl activity due to conjugation, so that aromatic compounds and aliphatic compounds with different substitution positions and different electronic effects have larger reaction difference. Therefore, the development of a new catalytic system for efficiently catalyzing the hydroboration reaction of aldehyde under mild conditions is particularly urgent.
Disclosure of Invention
The invention aims to provide application of p-methylanilino lithium, namely application of p-methylanilino lithium serving as a high-efficiency catalyst for catalyzing aldehyde and borane to perform hydroboration reaction; the chemical formula of the p-methylanilino lithium is as follows: 4-Me-PhNHLi, the chemical formula of which is as follows:
in order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows: the application of p-methylanilino lithium in catalyzing hydroboration reaction of aldehyde and borane; the aldehyde is selected from aromatic aldehyde and heterocyclic aldehyde.
The invention also discloses a method for carrying out hydroboration reaction on aldehyde and borane under catalysis of lithium methylanilino, which comprises the following steps:
under the anhydrous and oxygen-free environment and the inert gas atmosphere, adding borane into a reaction bottle subjected to dehydration and deoxidation treatment, then adding a catalyst p-methylanilino lithium, uniformly mixing, adding aldehyde, and carrying out hydroboration reaction.
The invention further discloses a preparation method of the boric acid ester, which comprises the following steps:
under an anhydrous and oxygen-free environment and in an inert gas atmosphere, adding borane into a reaction bottle subjected to dehydration and deoxidation treatment, then adding a catalyst p-methylanilino lithium, uniformly mixing, then adding aldehyde, performing hydroboration reaction, and exposing the mixture to air to terminate the reaction to obtain a product boric acid ester; the aldehyde is selected from aromatic aldehyde and heterocyclic aldehyde.
In the technical scheme, the chemical structural general formula of the aromatic aldehyde is as follows:
wherein R is one of electron withdrawing group or electron donating group, and can be selected from halogen, methyl and methoxyl;
the heterocyclic aldehyde is selected from 2-pyridinecarboxaldehyde or 2-thiophenecarboxaldehyde;
the borane is selected from pinacol borane.
In the technical scheme, the using amount of the catalyst is 0.1 percent of the molar amount of the aldehyde, and the molar ratio of the aldehyde to the borane is 1: 1.1.
In the technical scheme, the temperature of the hydroboration reaction is room temperature, and the reaction time is 10 minutes.
The above technical solution can be expressed as follows:
R1from the starting aldehyde.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
1. the invention discovers that the p-methylanilino lithium can efficiently catalyze the hydroboration reaction of aromatic aldehyde/heterocyclic aldehyde and borane for the first time, and provides a new scheme for preparing the boric acid ester by adopting the hydroboration reaction of the carbonyl compound and the borane.
2. The p-methylanilino lithium disclosed by the invention has high catalytic activity (the dosage of the catalyst is only 0.1%) for catalyzing the hydroboration reaction of aldehyde and borane, mild reaction conditions (room temperature), short reaction time (10 min), high reaction yield, simple and controllable reaction, simple post-treatment, and reduction of environmental pollution due to the adoption of a solvent-free system.
3. The catalyst disclosed by the invention has better universality on aromatic aldehydes with different substitution positions and different electronic effects and heterocyclic aldehydes, and provides more choices for obtaining borate compounds with different substituent structures.
Detailed Description
The invention is further described below with reference to examples:
the first embodiment is as follows: lithium p-methylanilino for catalyzing hydroboration reaction of benzaldehyde and pinacol borane
Adding 20ul of lithium p-methylanilino into a reaction bottle subjected to dehydration and deoxidation treatment under the protection of argonFuran solution (0.05M) (0.1 mol% dosage, the same below), 0.1596 mL borane added by syringe, mixing well, 0.1016 mL benzaldehyde added by syringe, stirring the mixture at room temperature, reacting for 10 min to obtain a nuclear magnetic yield of 99%, and removing a small amount of tetrahydrofuran and excessive borane under reduced pressure to obtain the corresponding pinacol borate C6H5CH2OB(OC(CH3)2C(CH3)2O)。1H NMR (400 MHz, CDCl3) δ 7.36-7.23 (m, 5H, Ar-H), 4.92 (s, 2H, OCH2),1.26 (s, 12H, CH3).13C NMR (101 MHz, CDCl3) δ 138.76 (Ar-C), 127.81 (Ar-C),126.89 (Ar-C), 126.24 (Ar-C), 82.48 (OC), 66.20 (OCH2), 24.15 (CH3)。
The product can hardly be obtained by replacing the p-methylanilino lithium with the amido lithium compound shown in the formula I, and the yield is less than 3 percent.
Example two: p-methylanilino lithium catalyzed hydroboration reaction of p-fluorobenzaldehyde and pinacol borane
Adding 20ul of p-methylanilino lithium tetrahydrofuran solution (0.05M) (0.1 mol percent of dosage) into a reaction bottle subjected to dehydration and deoxidation treatment under the protection of argon, then adding 0.1596 mL of borane into an injector, uniformly mixing, adding 0.1072 mL of p-fluorobenzaldehyde into the injector, stirring the mixture at room temperature, reacting for 10 min to obtain a nuclear magnetic yield of 99%, and then removing a small amount of tetrahydrofuran and excessive borane under reduced pressure to obtain the corresponding pinacol boratep-F-C6H4CH2OB(OC(CH3)2C(CH3)2O)。1H NMR (400 MHz, CDCl3) δ 7.34-7.29 (m, 2H, Ar-H), 7.04-6.98 (m, 2H,Ar-H), 4.87 (s, 2H, OCH2), 1.26 (s, 12H, CH3).13C NMR (101 MHz, CDCl3) δ161.71 (ds, Ar-C), 134.50 (d,J= 3.2 Hz, Ar-C), 128.14 (d,J= 8.1 Hz, Ar-C), 114.60 (ds, Ar-C), 82.54 (OC), 65.56 (OCH2), 24.11 (CH3)。
Example three: lithium p-methylanilino for catalyzing hydroboration reaction of m-chlorobenzaldehyde and pinacol borane
Adding 20ul of p-methylanilino lithium tetrahydrofuran solution (0.05M) (0.1 mol percent of dosage) into a reaction bottle subjected to dehydration and deoxidation treatment under the protection of argon, then adding 0.1596 mL of borane into an injector, uniformly mixing, adding 0.0899 mL of M-chlorobenzaldehyde into the mixture by the injector, stirring the mixture at room temperature, reacting for 10 min to obtain a nuclear magnetic yield of 99%, and then removing a small amount of tetrahydrofuran and excessive borane under reduced pressure to obtain the corresponding pinacol boratem-Cl-C6H4CH2OB(OC(CH3)2C(CH3)2O)。1H NMR (400 MHz, CDCl3) δ 7.36 (s, 1H, Ar-H), 7.28-7.19 (m, 3H,Ar-H), 4.89 (s, 2H, OCH2), 1.27 (s, 12H,CH3).13C NMR (101 MHz, CDCl3) δ 140.75(Ar-C), 133.75 (Ar-C), 129.08 (Ar-C), 126.99 (Ar-C), 126.30 (Ar-C), 124.17(Ar-C), 82.61 (OC), 65.41 (OCH2), 24.05 (CH3)。
Example four: method for catalyzing hydroboration reaction of p-tolualdehyde and pinacol borane by using lithium p-methylanilide
Adding 20ul of p-methylanilino lithium tetrahydrofuran solution (0.05M) (0.1 mol percent of dosage) into a reaction bottle subjected to dehydration and deoxidation treatment under the protection of argon, then adding 0.1596 mL of borane into an injector, uniformly mixing, adding 0.1184 mL of p-tolualdehyde into the injector, stirring the mixture at room temperature, reacting for 10 min to obtain a nuclear magnetic yield of 99%, and then removing a small amount of tetrahydrofuran and excessive borane under reduced pressure to obtain the corresponding pinacol boratep-Me-C6H4CH2OB(OC(CH3)2C(CH3)2O)。1H NMR (400 MHz, CDCl3) δ 7.24-7.22 (m, 2H,Ar-H), 7.13-7.11 (m,2H, Ar-H), 4.87 (s, 2H, OCH2), 2.32 (s, 3H, Ar-CH3), 1.24 (s, 12H, CH3).13CNMR (101 MHz, CDCl3) δ 136.51 (Ar-C), 135.79 (Ar-C), 128.49 (Ar-C), 126.40(Ar-C), 82.45 (OC), 66.13 (OCH2), 24.14 (CH3), 20.66 (CH3)。
Example four: p-methylanilino lithium catalyst o-methylbenzaldehyde and pinacol borane hydroboration reaction
Adding 20ul of p-methylanilino lithium tetrahydrofuran solution (0.05M) (0.1 mol percent of dosage) into a reaction bottle subjected to dehydration and deoxidation treatment under the protection of argon, then adding 0.1596 mL of borane into an injector, uniformly mixing, adding 0.1156 mL of o-methylbenzaldehyde into the mixture by using the injector, stirring the mixture at room temperature, reacting for 10 min to obtain a nuclear magnetic yield of 99%, and then removing a small amount of tetrahydrofuran and excessive borane under reduced pressure to obtain the corresponding pinacol borateo-Me-C6H4CH2OB(OC(CH3)2C(CH3)2O)。1H NMR (400 MHz, CDCl3) δ 7.39 (dq,J= 7.2, 3.6 Hz, 1H,Ar-H),7.18-7.11 (m, 3H, Ar-H), 4.92 (s, 2H, OCH2), 2.30 (s, 3H, Ar-CH3), 1.26 (s,12H, CH3).13C NMR (101 MHz, CDCl3) δ136.69 (Ar-C), 135.13 (Ar-C), 129.49(Ar-C), 126.86 (d,J= 25.25, Ar-C), 125.35 (Ar-C), 82.45 (OC), 64.49 (OCH2),24.15 (CH3), 18.18 (CH3)。
Example five: lithium p-methylanilino for catalyzing hydroboration reaction of 2,4, 6-trimethylbenzaldehyde and pinacol borane
Adding 20ul of p-methylanilino lithium tetrahydrofuran solution (0.05M) (0.1 mol percent of dosage) into a reaction bottle subjected to dehydration and deoxidation treatment under the protection of argon, then adding 0.1596 mL of borane into a syringe, uniformly mixing, adding 0.1475 mL of 2,4, 6-trimethylbenzaldehyde into the syringe, stirring the mixture at room temperature, reacting for 10 min until the nuclear magnetic yield is 99%, and then removing a small amount of tetrahydrofuran and excessive borane under reduced pressure to obtain the corresponding pinacol borate 2,4,6-Me3-C6H2CH2OB(OC(CH3)2C(CH3)2O)。1H NMR (400 MHz, CDCl3) δ 6.83 (s, 2H,Ar-H), 4.96(s, 2H, OCH2), 2.38 (s, 6H, Ar-CH3), 2.25 (s, 3H, Ar-CH3), 1.26 (s, 12H, CH3).13C NMR (101 MHz, CDCl3) δ 137.25 (Ar-C), 137.08 (Ar-C), 128.67 (Ar-C), 128.41(Ar-C), 82.28 (OC), 60.72 (OCH2), 24.15 (CH3), 20.49 (CH3), 18.95 (CH3)。
Example six: method for catalyzing hydroboration reaction of p-methoxybenzaldehyde and pinacol borane by using lithium p-methylanilide
Adding 20ul of p-methylanilino lithium tetrahydrofuran solution (0.05M) (0.1 mol percent of dosage) into a reaction bottle subjected to dehydration and deoxidation treatment under the protection of argon, then adding 0.1596 mL of borane into an injector, uniformly mixing, adding 0.1214 mL of p-methoxybenzaldehyde into the injector, stirring the mixture at room temperature, reacting for 30 min to obtain a nuclear magnetic yield of 99%, and then removing a small amount of tetrahydrofuran and excessive borane under reduced pressure to obtain the corresponding pinacol boratep-MeO-C6H2CH2OB(OC(CH3)2C(CH3)2O)。1H NMR (400 MHz, CDCl3) δ 7.29-7.25 (m, 2H,Ar-H), 6.87-6.84(m, 2H, Ar-H), 4.84 (s, 2H, OCH2), 3.78 (s, 3H, Ar-CH3), 1.21 (s, 12H, CH3).13C NMR (101 MHz, CDCl3) δ 158.56 (Ar-C), 130.98 (Ar-C), 128.03 (Ar-C), 113.19(Ar-C), 82.38 (OC), 65.95 (OCH2), 54.74 (OCH3), 24.14 (CH3)。
Example seven: p-methylanilino lithium catalysis hydroboration reaction of 2-pyridylaldehyde and pinacol borane
Adding 20ul of p-methylanilino lithium tetrahydrofuran solution (0.05M) (0.1 mol percent of dosage) into a reaction bottle subjected to dehydration and deoxidation treatment under the protection of argon, then adding 0.1596 mL of borane into an injector, uniformly mixing, then adding 0.095 mL of 2-pyridylaldehyde into the injector, stirring the mixture at room temperature, reacting for 10 min until the nuclear magnetic yield is more than 99%, and then removing a small amount of tetrahydrofuran and excessive borane under reduced pressure to obtain the corresponding pinacol borate 2-C5H4NCOCH2OB(OC(CH3)2C(CH3)2O)。1H NMR (400 MHz, CDCl3) δ 8.61 (d,J= 5.4 Hz, 1H, Ar-H), 7.91(t,J= 7.7 Hz, 1H, Ar-H), 7.49-7.41 (m, 2H, Ar-H), 5.10 (s, 2H, OCH2), 1.32(s, 12H, CH3).13C NMR (101 MHz, CDCl3) δ 159.82 (Ar-C), 143.72 (Ar-C), 139.56(Ar-C), 123.39 (Ar-C), 120.09 (Ar-C), 81.04 (OC), 66.47 (OCH2), 25.47 (CH3)。
Example eight: p-methylanilino lithium catalysis hydroboration reaction of 2-thiophenecarboxaldehyde and pinacol borane
Adding 20ul of p-methylanilino lithium tetrahydrofuran solution (0.05M) (0.1 mol percent of dosage) into a reaction bottle subjected to dehydration and deoxidation treatment under the protection of argon, then adding 0.1596 mL of borane into an injector, uniformly mixing, adding 0.092 mL of 2-thiophenecarboxaldehyde into the injector, stirring the mixture at room temperature, reacting for 10 min to obtain a nuclear magnetic yield of 99%, and then removing a small amount of tetrahydrofuran and excessive borane under reduced pressure to obtain the corresponding pinacol borate 2-C4H3NCOCH2OB(OC(CH3)2C(CH3)2O)。1H NMR (400 MHz, CDCl3) δ 7.25 (d,J= 4.3 Hz, 1H, Ar-H), 7.02-6.94(m, 2H, Ar-H), 5.04 (s, 2H, OCH2), 1.27 (s, 12H, CH3).13C NMR (101 MHz, CDCl3)δ 141.97 (Ar-C), 126.59 (Ar-C), 125.89 (Ar-C), 125.51 (Ar-C), 83.14 (OC),61.63 (OCH2), 24.63 (CH3)。
The invention discovers for the first time that the lithium p-methylanilino can catalyze the hydroboration reaction of aldehyde with extremely high catalytic activity and has very wide substrate practical range. The cheap catalyst, the lower catalyst dosage and the mild catalytic condition provide the possibility for industrial application.
Claims (2)
1. The application of p-methylanilino lithium in catalyzing hydroboration reaction of aldehyde and borane; the aldehyde is selected from aromatic aldehydes; the hydroboration reaction comprises the following steps: under the anhydrous and oxygen-free environment and the inert gas atmosphere, adding borane into a reaction bottle subjected to dehydration and deoxidation treatment, then adding a catalyst p-methylanilino lithium, uniformly mixing, adding aldehyde, and performing hydroboration reaction; the dosage of the p-methylanilino lithium is 0.1 percent of the molar weight of aldehyde, and the molar ratio of the aldehyde to the borane is 1: 1.1; the temperature of the hydroboration reaction is room temperature, and the time is 10 minutes.
2. The use according to claim 1, wherein the aromatic aldehyde has the following general chemical structure:
wherein R is one of an electron withdrawing group or an electron donating group;
the borane is selected from pinacol borane.
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| WO2019200523A1 (en) * | 2018-04-17 | 2019-10-24 | 南通纺织丝绸产业技术研究院 | Application of p-methylanilino lithium in catalyzing hydroboration of carbonyl compound and borane |
| CN109289913B (en) * | 2018-09-27 | 2020-04-17 | 苏州大学张家港工业技术研究院 | Application of 4-methoxyanilino lithium in catalysis of imine and borane hydroboration reaction |
| CN109251216B (en) * | 2018-09-27 | 2020-12-18 | 南通纺织丝绸产业技术研究院 | Application of p-methylanilino lithium in catalysis of imine and borane hydroboration reaction |
| CN109251217B (en) * | 2018-09-27 | 2021-07-20 | 南通纺织丝绸产业技术研究院 | Application of o-methoxyanilino lithium in catalysis of imine and borane hydroboration reaction |
| WO2020073182A1 (en) | 2018-10-08 | 2020-04-16 | 南通纺织丝绸产业技术研究院 | Application of 4-mephnhli in catalyzing hydroboration reaction of imine and borane |
| WO2020073179A1 (en) | 2018-10-08 | 2020-04-16 | 南通纺织丝绸产业技术研究院 | Application of lithium 4-methoxyaniline in catalysis of hydroboration reaction of imine and borane |
| CN112500428B (en) * | 2018-12-18 | 2022-04-15 | 苏州大学 | Application of anilino lithium compound in catalyzing reaction of carboxylic acid compound and borane hydroboration |
| CN111747972A (en) * | 2020-06-16 | 2020-10-09 | 苏州大学 | Deprotonated beta-ketimine lithium compound and preparation method thereof |
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| CN106749372A (en) * | 2016-12-07 | 2017-05-31 | 厦门大学 | A kind of preparation method of organic boronic ester compounds |
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| CN106749372A (en) * | 2016-12-07 | 2017-05-31 | 厦门大学 | A kind of preparation method of organic boronic ester compounds |
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