CN108554446A - Application of the open-chain crown ether base lithium in catalysis aldehyde and borine hydroboration - Google Patents
Application of the open-chain crown ether base lithium in catalysis aldehyde and borine hydroboration Download PDFInfo
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- aldehyde
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- hydroboration
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- crown ether
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- 229910000085 borane Inorganic materials 0.000 title claims abstract description 44
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 150000003983 crown ethers Chemical class 0.000 title claims abstract description 40
- 238000006197 hydroboration reaction Methods 0.000 title claims abstract description 33
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 30
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 9
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 title 1
- 150000001299 aldehydes Chemical class 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 230000018044 dehydration Effects 0.000 claims abstract description 14
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 14
- -1 heterocyclic aldehydes Chemical class 0.000 claims abstract description 14
- 238000012545 processing Methods 0.000 claims abstract description 14
- 150000003934 aromatic aldehydes Chemical group 0.000 claims abstract description 11
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011261 inert gas Substances 0.000 claims abstract description 5
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical group CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 claims description 36
- 238000002360 preparation method Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- CNUDBTRUORMMPA-UHFFFAOYSA-N formylthiophene Chemical compound O=CC1=CC=CS1 CNUDBTRUORMMPA-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 3
- 125000006575 electron-withdrawing group Chemical group 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 230000035484 reaction time Effects 0.000 abstract description 3
- 238000012805 post-processing Methods 0.000 abstract description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 36
- 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 29
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 18
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 18
- 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
- 229910052786 argon Inorganic materials 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 230000005311 nuclear magnetism Effects 0.000 description 9
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 5
- 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
- 230000000694 effects Effects 0.000 description 4
- 230000006837 decompression Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- UOQXIWFBQSVDPP-UHFFFAOYSA-N 4-fluorobenzaldehyde Chemical compound FC1=CC=C(C=O)C=C1 UOQXIWFBQSVDPP-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- BTFQKIATRPGRBS-UHFFFAOYSA-N o-tolualdehyde Chemical compound CC1=CC=CC=C1C=O BTFQKIATRPGRBS-UHFFFAOYSA-N 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
- 238000006467 substitution reaction Methods 0.000 description 2
- HIKRJHFHGKZKRI-UHFFFAOYSA-N 2,4,6-trimethylbenzaldehyde Chemical class CC1=CC(C)=C(C=O)C(C)=C1 HIKRJHFHGKZKRI-UHFFFAOYSA-N 0.000 description 1
- FPYUJUBAXZAQNL-UHFFFAOYSA-N 2-chlorobenzaldehyde Chemical class ClC1=CC=CC=C1C=O FPYUJUBAXZAQNL-UHFFFAOYSA-N 0.000 description 1
- CSDSSGBPEUDDEE-UHFFFAOYSA-N 2-formylpyridine Chemical class O=CC1=CC=CC=N1 CSDSSGBPEUDDEE-UHFFFAOYSA-N 0.000 description 1
- SRWILAKSARHZPR-UHFFFAOYSA-N 3-chlorobenzaldehyde Chemical compound ClC1=CC=CC(C=O)=C1 SRWILAKSARHZPR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 150000003935 benzaldehydes Chemical class 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 150000001875 compounds 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
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 238000005935 nucleophilic addition reaction Methods 0.000 description 1
- FXLOVSHXALFLKQ-UHFFFAOYSA-N p-tolualdehyde Chemical compound CC1=CC=C(C=O)C=C1 FXLOVSHXALFLKQ-UHFFFAOYSA-N 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000758 substrate Substances 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 present invention relates to open-chain crown ether base lithiums in catalysis aldehyde and the application in borine hydroboration, under anhydrous and oxygen-free environment, in atmosphere of inert gases, borine is added in the reaction bulb by dehydration and deoxidation processing, catalyst open-chain crown ether base lithium is then added, is uniformly mixed, add aldehyde, hydroboration is carried out, is exposed in air and terminates reaction, obtain product borate；The aldehyde is selected from aromatic aldehyde, heterocyclic aldehydes.The catalytic activity that hydroboration occurs with borine for open-chain crown ether base lithium catalysis aldehyde disclosed by the invention is high (catalyst amount is only 0.1%), reaction condition is mild (room temperature), reaction time is short (10 min), and reaction yield is high, reaction is simple controllable, post-processing is simple, and reaction uses solvent-free system, reduces the pollution to environment.
Description
Technical field
The application of open-chain crown ether base lithium of the present invention, and in particular to open-chain crown ether base lithium is in catalysis aldehyde and borine
Efficient application in hydroboration.
Technical background
Various catalyst have been used for the hydroboration of aldehyde, especially in recent years, about this kind of reaction
It reports many.Since under no catalysts conditions, the hydroboration of carbonyls is difficult to occur.So for this one kind
The research emphasis of reaction exactly develops efficient catalyst system and catalyzing.But the catalyst system and catalyzing reported at present, catalyst are all opposite
Costliness or reaction condition are more harsh.
Although belonging to carbonyls, ketone and aldehyde have different reaction properties, this is common sense, and the prior art exists simultaneously
Using keto-aldehyde as raw material, but only there is a situation where a kind of raw materials to react；Electron donating group can weaken the electropositive of carbonyl carbon, to cut
The nucleophilic addition activity of weak carbonyl, aromatic aldehyde is since conjugation reduces carbonyl activity, to different the position of substitution, different electronic effects
Aromatic compound and fatty compound have and larger react difference.So developing efficient catalytic aldehyde under new temperate condition
Hydroboration catalyst system and catalyzing it is particularly urgent.
Invention content
The goal of the invention of the present invention is to provide the application of open-chain crown ether base lithium, i.e., is efficiently to urge with open-chain crown ether base lithium
Agent is catalyzed the application that hydroboration occurs with borine for aldehyde；Open-chain crown ether base lithium chemical formula of the present invention is：4-Me-
PhNHLi, chemical structural formula are as follows：
To achieve the above object of the invention, the technical solution adopted by the present invention is：Open-chain crown ether base lithium is in catalysis aldehyde and borine boron
Application in hydrogenation；The aldehyde is selected from aromatic aldehyde, heterocyclic aldehydes.
It is catalyzed aldehyde the invention also discloses open-chain crown ether base lithium and the method for hydroboration occurs for borine, including is following
Step：
Under anhydrous and oxygen-free environment, under atmosphere of inert gases, borine is added in the reaction bulb by dehydration and deoxidation processing, then adds
Enter catalyst open-chain crown ether base lithium, be uniformly mixed, add aldehyde, carries out hydroboration.
The present invention further discloses a kind of preparation method of borate, includes the following steps：
Under anhydrous and oxygen-free environment, in atmosphere of inert gases, borine is added in the reaction bulb by dehydration and deoxidation processing, then adds
Enter catalyst open-chain crown ether base lithium, be uniformly mixed, add aldehyde, carry out hydroboration, is exposed in air and terminates reaction,
Obtain product borate；The aldehyde is selected from aromatic aldehyde, heterocyclic aldehydes.
In above-mentioned technical proposal, the chemical structure of general formula of the aromatic aldehyde is as follows：
Wherein R is one kind in electron-withdrawing group or electron donating group, can be selected from halogen, methyl, methoxyl group；
The heterocyclic aldehydes are selected from 2 pyridine carboxaldehydes or 2 thiophene carboxaldehyde；
The borine is selected from pinacol borine.
In above-mentioned technical proposal, the catalyst amount is the 0.1% of aldehyde mole, and the molar ratio of aldehyde and borine is 1:
1.1。
In above-mentioned technical proposal, the temperature of hydroboration is room temperature, and the reaction time is 10 minutes.
Above-mentioned technical proposal can indicate as follows：
R1Come from raw material aldehyde.
Due to the application of the above technical scheme, the present invention has the following advantages compared with prior art：
1. present invention firstly discovers that open-chain crown ether base lithium extremely can efficiently be catalyzed aromatic aldehyde/heterocyclic aldehydes occurs boron hydrogen with borine
Change reaction, new scheme is provided to prepare borate with borine generation hydroboration using carbonyls.
2. the catalytic activity height that hydroboration occurs with borine for open-chain crown ether base lithium catalysis aldehyde disclosed by the invention (is urged
Agent dosage is only that 0.1%), reaction condition is mild (room temperature), and the reaction time is short (10 min), and reaction yield is high, and reaction is simple
Controllably, post-processing is simple, and reaction uses solvent-free system, reduces the pollution to environment.
3. catalyst disclosed by the invention is for the aromatic aldehyde of different the position of substitution, different electronic effects and to heterocyclic aldehydes
There is preferable universality, the boric acid ester compound to obtain different substituents structure provides more selections.
Specific implementation mode
The present invention is described further with reference to embodiment：
Embodiment one：Open-chain crown ether base lithium is catalyzed benzaldehyde and pinacol borine hydroboration
In the reaction bulb by dehydration and deoxidation processing, the lower tetrahydrofuran that 20ul open-chain crown ether base lithiums are added of argon gas protection is molten
Liquid (0.05M) (0.1 mol% dosages, similarly hereinafter), then with syringe be added 0.1596 mL borines, be uniformly mixed, then with inject
0.1016 mL benzaldehydes are added in device, and mixture is stirred at room temperature, and after reacting 10 min, nuclear-magnetism yield is 99%, is depressurized later
A small amount of tetrahydrofuran and excessive borine are removed to get to 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)。
Open-chain crown ether base lithium is replaced with to the amido lithium compound of formula I, it is virtually impossible to obtain product, yield is less than 3%.
Embodiment two：Open-chain crown ether base lithium is catalyzed 4-Fluorobenzaldehyde and pinacol borine hydroboration
In the reaction bulb by dehydration and deoxidation processing, the lower tetrahydrofuran that 20ul open-chain crown ether base lithiums are added of argon gas protection is molten
Then 0.1596 mL borines are added with syringe in liquid (0.05M) (0.1 mol% dosages), are uniformly mixed, then be added with syringe
0.1072 mL 4-Fluorobenzaldehydes, mixture are stirred at room temperature, and after reacting 10 min, nuclear-magnetism yield is 99%, and decompression later removes
Go a small amount of tetrahydrofuran and excessive borine to get to 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) δ
161.71 (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)。
Embodiment three：Open-chain crown ether base lithium is catalyzed m chlorobenzaldehyde and pinacol borine hydroboration
In the reaction bulb by dehydration and deoxidation processing, the lower tetrahydrofuran that 20ul open-chain crown ether base lithiums are added of argon gas protection is molten
Then 0.1596 mL borines are added with syringe in liquid (0.05M) (0.1 mol% dosages), are uniformly mixed, then be added with syringe
0.0899 mL m chlorobenzaldehydes, mixture are stirred at room temperature, and after reacting 10 min, nuclear-magnetism yield is 99%, and decompression later removes
Go a small amount of tetrahydrofuran and excessive borine to get to 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 IV：Open-chain crown ether base lithium is catalyzed p-tolyl aldehyde and pinacol borine hydroboration
In the reaction bulb by dehydration and deoxidation processing, the lower tetrahydrofuran that 20ul open-chain crown ether base lithiums are added of argon gas protection is molten
Then 0.1596 mL borines are added with syringe in liquid (0.05M) (0.1 mol% dosages), are uniformly mixed, then be added with syringe
0.1184 mL p-tolyl aldehydes, mixture are stirred at room temperature, and after reacting 10 min, nuclear-magnetism yield is 99%, is depressurized later
A small amount of tetrahydrofuran and excessive borine are removed to get to 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). 13C NMR
(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 IV：Open-chain crown ether base lithium is catalyzed o-tolualdehyde and pinacol borine hydroboration
In the reaction bulb by dehydration and deoxidation processing, the lower tetrahydrofuran that 20ul open-chain crown ether base lithiums are added of argon gas protection is molten
Then 0.1596 mL borines are added with syringe in liquid (0.05M) (0.1 mol% dosages), are uniformly mixed, then be added with syringe
0.1156 mL o-tolualdehydes, mixture are stirred at room temperature, and after reacting 10 min, nuclear-magnetism yield is 99%, is depressurized later
A small amount of tetrahydrofuran and excessive borine are removed to get to 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) δ 136.69 (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)。
Embodiment five：Open-chain crown ether base lithium is catalyzed 2,4,6- trimethylbenzaldehydes and pinacol borine hydroboration
In the reaction bulb by dehydration and deoxidation processing, the lower tetrahydrofuran that 20ul open-chain crown ether base lithiums are added of argon gas protection is molten
Then 0.1596 mL borines are added with syringe in liquid (0.05M) (0.1 mol% dosages), are uniformly mixed, then be added with syringe
0.1475 mL2,4,6- trimethylbenzaldehydes, mixture are stirred at room temperature, and after reacting 10 min, nuclear-magnetism yield is 99%, it
A small amount of tetrahydrofuran and excessive borine are removed under reduced pressure afterwards to get to 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)。
Embodiment six：Open-chain crown ether base lithium is catalyzed P-methoxybenzal-dehyde and pinacol borine hydroboration
In the reaction bulb by dehydration and deoxidation processing, the lower tetrahydrofuran that 20ul open-chain crown ether base lithiums are added of argon gas protection is molten
Then 0.1596 mL borines are added with syringe in liquid (0.05M) (0.1 mol% dosages), are uniformly mixed, then be added with syringe
0.1214 mL P-methoxybenzal-dehyde, mixture are stirred at room temperature, and after reacting 30 min, nuclear-magnetism yield is 99%, is subtracted later
Pressure removes a small amount of tetrahydrofuran and excessive borine to get to 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)。
Embodiment seven：Open-chain crown ether base lithium is catalyzed 2- pyridine carboxaldehydes and pinacol borine hydroboration
In the reaction bulb by dehydration and deoxidation processing, the lower tetrahydrofuran that 20ul open-chain crown ether base lithiums are added of argon gas protection is molten
Then 0.1596 mL borines are added with syringe in liquid (0.05M) (0.1 mol% dosages), are uniformly mixed, then be added with syringe
0.095 mL2- pyridine carboxaldehydes, mixture are stirred at room temperature, and after reacting 10 min, nuclear-magnetism yield is more than 99%, and decompression later removes
Go a small amount of tetrahydrofuran and excessive borine to get to 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)。
Embodiment eight：Open-chain crown ether base lithium is catalyzed 2 thiophene carboxaldehyde and pinacol borine hydroboration
In the reaction bulb by dehydration and deoxidation processing, the lower tetrahydrofuran that 20ul open-chain crown ether base lithiums are added of argon gas protection is molten
Then 0.1596 mL borines are added with syringe in liquid (0.05M) (0.1 mol% dosages), are uniformly mixed, then be added with syringe
0.092 mL2- thiophenecarboxaldehydes, mixture are stirred at room temperature, and after reacting 10 min, nuclear-magnetism yield is 99%, is removed under reduced pressure later
A small amount of tetrahydrofuran and excessive borine are to get to 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)。
Present invention firstly discovers that open-chain crown ether base lithium can be catalyzed the hydroboration of aldehyde with high catalytic activity, and
And there is very wide substrate usage range.Cheap catalyst and lower catalyst amount, mild catalysis item
Part provides possibility for industrial applications.
Claims (10)
1. open-chain crown ether base lithium is in catalysis aldehyde and the application in borine hydroboration；The aldehyde is selected from aromatic aldehyde, heterocyclic aldehydes.
2. application according to claim 1, which is characterized in that the hydroboration includes the following steps：
Under anhydrous and oxygen-free environment, under atmosphere of inert gases, borine is added in the reaction bulb by dehydration and deoxidation processing, then adds
Enter catalyst open-chain crown ether base lithium, be uniformly mixed, add aldehyde, carries out hydroboration.
3. application according to claim 1, which is characterized in that the chemical structure of general formula of the aromatic aldehyde is as follows：
Wherein R is one kind in electron-withdrawing group or electron donating group；
The heterocyclic aldehydes are selected from 2 pyridine carboxaldehydes or 2 thiophene carboxaldehyde；
The borine is selected from pinacol borine.
4. application according to claim 1, which is characterized in that the dosage of the open-chain crown ether base lithium is aldehyde mole
0.1%, the molar ratio of aldehyde and borine is 1: 1.1.
5. application according to claim 1, which is characterized in that the temperature of the hydroboration is room temperature, time 10
Minute.
6. a kind of preparation method of borate, includes the following steps：
Under anhydrous and oxygen-free environment, in atmosphere of inert gases, borine is added in the reaction bulb by dehydration and deoxidation processing, then adds
Enter catalyst open-chain crown ether base lithium, be uniformly mixed, add aldehyde, carry out hydroboration, is exposed in air and terminates reaction,
Obtain borate；The aldehyde is selected from aromatic aldehyde, heterocyclic aldehydes.
7. the preparation method of borate according to claim 6, which is characterized in that the chemical structure of general formula of the aromatic aldehyde is such as
Under：
Wherein R is one kind in electron-withdrawing group or electron donating group；
The heterocyclic aldehydes are selected from 2 pyridine carboxaldehydes or 2 thiophene carboxaldehyde；
The borine is selected from pinacol borine.
8. the preparation method of borate according to claim 6, which is characterized in that the dosage of the catalyst is aldehyde mole
0.1%, the molar ratio of aldehyde and pinacol borine is 1: 1.1.
9. the preparation method of borate according to claim 6, which is characterized in that the temperature of hydroboration is room temperature.
10. the preparation method of borate according to claim 6, which is characterized in that the time of hydroboration is 10 minutes.
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