CN107540700A - The method for preparing borate using three fragrant oxygen rare earth compoundings - Google Patents
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Abstract
The invention discloses the method for preparing borate using three fragrant oxygen rare earth compoundings, i.e., prepares borate using three fragrant oxygen catalyzed by rare-earth complex assimilation compounds and borine hydroboration, catalyst molecule formula is Nd (OAr)3(THF)2, Ar=[2,6 (tBu)2‑4‑MeC6H2], catalyst is used as in borine and assimilation compound reaction generation borate, can be under mild conditions（Room temperature）, with the extremely short time（10 30 minutes）, high yield（99%）It is catalyzed borine and addition reaction occurs with ketone, to be the first using such the metal complex catalyzed reaction of rare earth oxygen key.
Description
Technical field
The present invention relates to the application of three fragrant oxygen rare earth compoundings, and in particular to utilizes three fragrant oxygen catalyzed by rare-earth complex assimilations
The method of the hydroboration generation borate of compound.
Background technology
Organic boric acid ester can be used not only as fluxing agent in plasticizer, welding process, flame retardant for textile, coupling agent, profit
Oil additive etc., and a kind of important raw material in organic synthesis.For example, given birth to using carbonyls and borine equivalent reaction
Into borate, then hydrolysis obtains alcohol, is a kind of method for efficiently synthesizing alcohol.Meanwhile boric acid or borate can change into it
His a variety of functional groups, it is a kind of important reagent in organic synthesis, the research as chiral drug also just progressively deeply in, it is existing
Bortezomib is synthesized using chiral boric acid as medicines structure unit, it is the multiple marrow for the treatment of of first approval
The Protease Inhibitor drugs of cancer and lymph cancer, so the application prospect of chiral boric acid or borate is very vast.Therefore, for
The synthesis of borate, it is still the focus of chemist research.But in the presence of no catalyst, borine be difficult with
Hydroboration occurs for carbonyls.
In existing document report, on be catalyzed hydroboration catalyst relate generally to main group metal catalyst and
Transition-metal catalyst.For rare-earth metal catalyst, different rare earth metal metal complexs shows different even phases
Anti- catalytic performance, for example, Hou Zhao people seminar use rare earth metal alkyl complexes can with efficient catalytic secondary aliphatic amine with
Addition reaction (the Zhang W. X. of carbodiimides; Nishiura, M.; Hou Z. M. Synlett, 2006,
1213).And Wang Shaowu is by rare-earth metal amide, catalysis guanidineization reaction, to secondary aliphatic amine, it is necessary to extremely exacting terms
Guanidine (Zhou, S. L. could be obtained with medium yield above; Wang, S. W.; Yang, G. S.; Li Q.;
Zhang, L. J.; Yao, Z. J.; Zhou, Z.; Song, H. B. Organometallics, 2007, 26,
3755).Rare earth ion belongs to hard Lewis acid, is easy to relative to rare earth-carbon key, rare earth-nitrogen, rare earth ion and containing O atom
Hard base ligands, strong oxytropism is shown, thus reactivity is relatively low；Therefore prior art rarely has the cooperation of rare earth oxygen
The report of thing catalysis, even with rare earth oxygen complex, it is also desirable to harsh reaction condition.
The content of the invention
The goal of the invention of the present invention is to provide the application of a kind of three fragrant oxygen rare earth compoundings, i.e., with three fragrant oxygen rare earth compoundings
Hydroboration occurs for catalyst efficient catalytic assimilation compound and pinacol borine and obtains borate；The present invention is except providing one
The catalyst that kind is efficiently easy to get, the mild condition of simultaneous reactions reduce post processing cost, and catalyst has wider substrate
The scope of application.
To achieve the above object of the invention, the technical solution adopted by the present invention is：One kind utilizes three fragrant oxygen rare earth compounding systems
The method of standby borate, comprises the following steps：
Under anhydrous and oxygen-free environment, in atmosphere of inert gases, the virtue of catalyst three is added in the reaction bulb by dehydration and deoxidation processing
Oxygen rare earth compounding, assimilation compound is then added, be well mixed, add borine, reacted at room temperature 10 ~ 30 min, obtain boric acid
Ester, further, use CDCl3Terminating reaction, reaction solution removal of solvent under reduced pressure and unnecessary borine, raffinate add hexane（3
× 5ml）Washing, obtains borate；
The chemical structural formula of the three fragrant oxygen rare earth compounding is：
The molecular formula of above-mentioned three fragrant oxygen rare earth compounding is represented by：Nd(OAr)3(THF)2, in formula：Ar = [2,6-(tBu)2-
4-MeC6H2]。
The method of hydroboration occurs with borine the invention also discloses three fragrant oxygen catalyzed by rare-earth complex assimilation compounds,
Comprise the following steps：
Under anhydrous and oxygen-free environment, under atmosphere of inert gases, catalyst n d is added in the reaction bulb by dehydration and deoxidation processing
(OAr)3(THF)2, assimilation compound is then added, is well mixed, adds borine, reacts at room temperature 10 ~ 30 min, assimilation is completed and closes
The hydroboration of thing and borine, further, use CDCl3Terminating reaction, reaction solution removal of solvent under reduced pressure, raffinate add
Hexane（3 × 5 ml）Washing, obtains product.
The present invention further discloses application of the three fragrant oxygen rare earth compoundings in borate is prepared；Especially with ketone
Compound prepares the application in borate with borine for raw material.
The further three fragrant oxygen rare earth compoundings that disclose of the invention are in catalysis assimilation compound and borine hydroboration
Application.
In above-mentioned technical proposal, the catalyst amount be assimilation compound mole 0.05-0.1 %, assimilation compound with
The mol ratio of borine is 1：1.1, reaction temperature is room temperature, reaction time 10-30min.
In the present invention, the borine is selected from pinacol borine.
In the present invention, the general structure of the assimilation compound is：
Wherein R1For phenyl, substituted-phenyl, heterocyclic aryl, naphthyl or anthryl, R2For alkyl.
Above-mentioned technical proposal can represent as follows：
Due to the application of above-mentioned technical proposal, the present invention has the following advantages compared with prior art：
1. using three fragrant oxygen catalyzed by rare-earth complex assimilation compounds and borine hydroboration occurs for the present invention first, to use
Assimilation compound prepares borate with borine generation hydroboration and provides new scheme, has expanded three fragrant oxygen rare earth compoundings
Using.
2. the catalysis of hydroboration occurs with borine for three fragrant oxygen catalyzed by rare-earth complex assimilation compound disclosed by the invention
Active height (catalyst amount is only 0.05-0.1%), reaction condition is gentle (room temperature), and the reaction time is short (10-30 min), and instead
Product yield is high, and reaction is simple controllable, and post processing is simple, reduces cost.
3. catalyst disclosed by the invention is for different the position of substitution, the aromatic ketone compound of different electronic effects, miscellaneous
Cyclic ketone compound, aliphatic assimilation compound suffer from preferable universality, to obtain the acid esterification of different substituents structure
Compound provides more selections.
Embodiment
The present invention is described further with reference to embodiment：
Embodiment one： Nd(OAr)3(THF)2It is catalyzed acetophenone and pinacol borine hydroboration
In the reaction bulb by dehydration and deoxidation processing, argon gas protection is lower to add 0.0004 mol (40 μ L) catalyst n d
(OAr)3(THF)2) (0.01 M catalyst stock solution, solvent THF), then add 0.8 mol (93.3 with syringe
μ L) acetophenone, it is well mixed, then 0.88 mol (127.7 μ L) pinacol borine is added with syringe, mixture is at room temperature
Stirring, after reacting 15 min, add 0.5 mLCDCl3, nuclear-magnetism yield is 99%, and CDCl is removed under reduced pressure afterwards3And tetrahydrofuran, add
Enter n-hexane (3 × 5 mL) washing, drain, obtain corresponding pinacol borate.The nuclear magnetic data of product is：1H NMR
(400 MHz, CDCl3) δ 7.40 – 7.22 (m, 5H), 1.51 – 1.47 (d, J=6.5Hz, 3H), 1.24
(s, 6H), 1.21 (s, 6H)。 11B{1H} NMR (CDCl3, 128 MHz): 22.18 (s, B-O)。
Embodiment two： Nd(OAr)3(THF)2It is catalyzed melilotal and pinacol borine hydroboration
In the reaction bulb by dehydration and deoxidation processing, argon gas protection is lower to add 0.0004 mol (40 μ L) catalyst n d
(OAr)3(THF)2) (0.01 M catalyst stock solution, solvent THF), then add 0.8 mol (106.8 with syringe
μ L) melilotal, it is well mixed, then 0.88 mol (127.7 μ L) pinacol borine is added with syringe, mixture exists
Stir at room temperature, after reacting 15 min, add 0.5 mLCDCl3, nuclear-magnetism yield is 99%, and CDCl is removed under reduced pressure afterwards3And tetrahydrochysene
Furans, n-hexane (3 × 5 mL) washing is added, drains, obtains corresponding pinacol borate.The nuclear magnetic data of product is：1H
NMR (400 MHz, CDCl3) δ 7.31 – 7.25 (m, 2H), 7.16 (t, J = 7.4 Hz, 2H), 5.24
(q, J = 6.4 Hz, 1H), 2.35 (s, 3H), 1.27 (s, 6H), 1.24 (s, 6H)。
Embodiment three： Nd(OAr)3(THF)2It is catalyzed o-methyl-benzene ethyl ketone and pinacol borine hydroboration
In the reaction bulb by dehydration and deoxidation processing, argon gas protection is lower to add 0.0004 mol (40 μ L) catalyst n d
(OAr)3(THF)2) (0.01 M catalyst stock solution, solvent THF), then add 0.8 mol (104.6 with syringe
μ L) o-methyl-benzene ethyl ketone, it is well mixed, then 0.88 mol (127.7 μ L) pinacol borine is added with syringe, mixture exists
Stir at room temperature, after reacting 30 min, add 0.5 mLCDCl3, nuclear-magnetism yield is 99%, and CDCl is removed under reduced pressure afterwards3And tetrahydrochysene
Furans, n-hexane (3 × 5 mL) washing is added, drains, obtains corresponding pinacol borate.The nuclear magnetic data of product is：1H
NMR (400 MHz, CDCl3) δ 7.55 (m,1H), 7.33 – 7.08 (m, 3H), 5.45 (q, J = 6.4 Hz,
1H), 1.48 (d, J = 6.4 Hz, 3H), 1.26 (s, 6H), 1.22 (s, 6H)。
Example IV： Nd(OAr)3(THF)2It is catalyzed acetanisole and pinacol borine hydroboration
In the reaction bulb by dehydration and deoxidation processing, argon gas protection is lower to add 0.0004 mol (40 μ L) catalyst n d
(OAr)3(THF)2) (0.01 M catalyst stock solution, solvent THF), then add 0.8 mol with syringe
(0.1201 g) acetanisole, 0.2 mLTHF is added, dissolving is well mixed, then adds 0.88 mol with syringe
(127.7 μ L) pinacol borine, mixture are stirred at room temperature, and after reacting 30 min, add 0.5 mLCDCl3, nuclear-magnetism yield
For 99%, CDCl is removed under reduced pressure afterwards3And tetrahydrofuran, n-hexane (3 × 5 mL) washing is added, is drained, where obtains corresponding frequency
Alcohol borate.The nuclear magnetic data of product is：1H NMR (400 MHz, CDCl3) δ 7.38 – 7.17 (m, 2H), 6.94
– 6.68 (m, 2H), 5.20 (q, J = 6.4 Hz, 1H), 3.79 (s, 3H), 1.47 (d, J = 6.4 Hz,
3H), 1.24 (s, 6H), 1.22 (s, 6H)。
Embodiment five： Nd(OAr)3(THF)2It is catalyzed parachloroacetophenone and pinacol borine hydroboration
In the reaction bulb by dehydration and deoxidation processing, argon gas protection is lower to add 0.0004 mol (40 μ L) catalyst n d
(OAr)3(THF)2) (0.01 M catalyst stock solution, solvent THF), then add 0.8 mol (103.8 with syringe
μ L) parachloroacetophenone, dissolving is well mixed, then adds 0.88 mol (127.7 μ L) pinacol borine, mixture with syringe
It is stirred at room temperature, after reacting 15 min, adds 0.5 mLCDCl3, nuclear-magnetism yield is 99%, and CDCl is removed under reduced pressure afterwards3With four
Hydrogen furans, n-hexane (3 × 5 mL) washing is added, drains, obtains corresponding pinacol borate.The nuclear magnetic data of product is：1H NMR (400 MHz, CDCl3): δ 7.31-7.26 (m, 4H,), 5.21(q, J=6.4 Hz, 1H ), 1.47
(d, J=6.4 Hz, 3H), 1.24 (s, 6H), 1.21 (s, 6H)。
Embodiment six： Nd(OAr)3(THF)2It is catalyzed parabromoacetophenone and pinacol borine hydroboration
In the reaction bulb by dehydration and deoxidation processing, argon gas protection is lower to add 0.0004 mol (40 μ L) catalyst n d
(OAr)3(THF)2) (0.01 M catalyst stock solution, solvent THF), then add 0.8 mol with syringe
(0.1592 g) parabromoacetophenone, dissolving is well mixed, then adds 0.88 mol (127.7 μ L) pinacol borine with syringe,
Mixture is stirred at room temperature, and after reacting 15 min, adds 0.5 mLCDCl3, nuclear-magnetism yield is 99%, is removed under reduced pressure afterwards
CDCl3And tetrahydrofuran, n-hexane (3 × 5 mL) washing is added, drains, obtains corresponding pinacol borate.The core of product
Magnetic data is：1H NMR (400 MHz, CDCl3) δ 7.41 (m, 2H), 7.21 (m, 2H), 5.16 (q, J =
6.4 Hz, 1H), 1.42 (d, J = 6.5 Hz, 3H), 1.20 (s, 6H), 1.18 (s, 6H)。
Embodiment seven： Nd(OAr)3(THF)2It is catalyzed p-nitroacetophenone and pinacol borine hydroboration
In the reaction bulb by dehydration and deoxidation processing, argon gas protection is lower to add 0.0004 mol (80 μ L) catalyst n d
(OAr)3(THF)2) (0.01 M catalyst stock solution, solvent THF), then add 0.8 mol with syringe
(0.1321 g) p-nitroacetophenone, dissolving is well mixed, then adds 0.88 mol (127.7 μ L) pinacol boron with syringe
Alkane, mixture are stirred at room temperature, and after reacting 15 min, add 0.5 mLCDCl3, nuclear-magnetism yield is 99%, is removed under reduced pressure afterwards
CDCl3And tetrahydrofuran, n-hexane (3 × 5 mL) washing is added, drains, obtains corresponding pinacol borate.The core of product
Magnetic data is：1H NMR (400 MHz, CDCl3) δ 8.16 – 8.08 (m, 2H), 7.47 (m, 2H), 5.26
(q, J = 6.5 Hz, 1H), 1.44 (d, J = 6.5 Hz, 3H), 1.19 (s, 6H), 1.16 (s, 6H)。
Embodiment eight： Nd(OAr)3(THF)2It is catalyzed benzophenone and pinacol borine hydroboration
In the reaction bulb by dehydration and deoxidation processing, argon gas protection is lower to add 0.0004 mol (80 μ L) catalyst n d
(OAr)3(THF)2) (0.01 M catalyst stock solution, solvent THF), then add 0.8 mol with syringe
(0.1458 g) benzophenone, 0.2 mL THF are added, dissolving is well mixed, then adds 0.88 mol (127.7 with syringe
μ L) pinacol borine, mixture is stirred at room temperature, and after reacting 15 min, adds 0.5 mLCDCl3, nuclear-magnetism yield is 99%,
CDCl is removed under reduced pressure afterwards3And tetrahydrofuran, n-hexane (3 × 5 mL) washing is added, drains, obtains corresponding pinacol boric acid
Ester.The nuclear magnetic data of product is：1H NMR (400 MHz, CDCl3) δ 7.37-7.39 (m, 4H), 7.27-7.31 (m,
4H), 7.20-7.24 (m, 2H), 6.18 (s, 1H), 1.19 (s, 12H)。
Embodiment nine： Nd(OAr)3(THF)2It is catalyzed 1- (2- thienyls) ethyl ketones and pinacol borine hydroboration
In the reaction bulb by dehydration and deoxidation processing, argon gas protection is lower to add 0.0004 mol (80 μ L) catalyst n d
(OAr)3(THF)2) (0.01 M catalyst stock solution, solvent THF), then add 0.8 mol (86.4 with syringe
μ L) 1- (2- thienyls) ethyl ketone, dissolving is well mixed, then adds 0.88 mol (127.7 μ L) pinacol borine with syringe,
Mixture is stirred at room temperature, and after reacting 20 min, adds 0.5 mLCDCl3, nuclear-magnetism yield is 99%, is removed under reduced pressure afterwards
CDCl3And tetrahydrofuran, n-hexane (3 × 5 mL) washing is added, drains, obtains corresponding pinacol borate.The core of product
Magnetic data is：1H NMR (400 MHz, CDCl3) δ 7.21 – 7.19 (m, 1H), 6.97 – 6.92 (m, 2H),
5.48 (q, J = 6.4 Hz, 1H), 1.60 (d, J = 6.4 Hz, 3H), 1.25 (d, J = 4.9 Hz,
12H)。
Embodiment ten： Nd(OAr)3(THF)2Catalyzing iso-butane acyl benzene and pinacol borine hydroboration
In the reaction bulb by dehydration and deoxidation processing, argon gas protection is lower to add 0.0008 mol (80 μ L) catalyst n d
(OAr)3(THF)2) (0.01 M catalyst stock solution, solvent THF), then add 0.8 mol (123.5 with syringe
μ L) isobutyrophenone, dissolving is well mixed, then adds 0.88 mol (127.7 μ L) pinacol borine with syringe, and mixture exists
Stir at room temperature, after reacting 15 min, add 0.5 mLCDCl3, nuclear-magnetism yield is 99%, and CDCl is removed under reduced pressure afterwards3And tetrahydrochysene
Furans, n-hexane (3 × 5 mL) washing is added, drains, obtains corresponding pinacol borate.The nuclear magnetic data of product is：1H
NMR (400 MHz, CDCl3) δ 7.34 –7.18 (m, 5H), 4.81 (d, J= 6.2 Hz, 1H), 1.96 (dq,
J= 13.4, 6.7 Hz, 1H), 1.19 (d, J= 16.3 Hz, 12H), 0.90 (d, J= 6.7 Hz, 3H),
0.83 (d, J= 6.8 Hz, 3H)。
Embodiment 11： Nd(OAr)3(THF)2It is catalyzed ALPHA-tetralone and pinacol borine hydroboration
In the reaction bulb by dehydration and deoxidation processing, argon gas protection is lower to add 0.0004 mol (80 μ L) catalyst n d
(OAr)3(THF)2) (0.01 M catalyst stock solution, solvent THF), then add 0.8 mol1- tetrahydrochysenes with syringe
Naphthalenone (106.4 μ L), dissolving is well mixed, then adds 0.88 mol (127.7 μ L) pinacol borine, mixing with syringe
Thing is stirred at room temperature, and after reacting 15 min, adds 0.5 mLCDCl3, nuclear-magnetism yield is 99%, and CDCl is removed under reduced pressure afterwards3With
Tetrahydrofuran, n-hexane (3 × 5 mL) washing is added, drains, obtains corresponding pinacol borate.The nuclear magnetic data of product
For：1H NMR (400 MHz, CDCl3) δ 7.41 – 7.37(m, 1H), 7.19 – 7.14 (m, 2H), 7.11 –
7.04 (m, 1H), 5.20 (t, J= 4.9 Hz, 1H), 2.83 m, 1H), 2.70 (m, 1H), 2.12 – 1.99
(m, 1H), 2.00 –1.91 (m, 2H), 1.82 –1.69 (m, 1H), 1.30 (d, J= 5.8 Hz, 12H)。
Embodiment 12： Nd(OAr)3(THF)2It is catalyzed 3- methyl -2- butanone and pinacol borine hydroboration
In the reaction bulb by dehydration and deoxidation processing, argon gas protection is lower to add 0.0004 mol (80 μ L) catalyst n d
(OAr)3(THF)2) (0.01 M catalyst stock solution, solvent THF), then with syringe add 0.8 mol3- methyl-
2- butanone (86 μ L), dissolving is well mixed, then adds 0.88 mol (127.7 μ L) pinacol borine, mixture with syringe
It is stirred at room temperature, after reacting 15 min, adds 0.5 mLCDCl3, nuclear-magnetism yield is 99%, and CDCl is removed under reduced pressure afterwards3With four
Hydrogen furans, n-hexane (3 × 5 mL) washing is added, drains, obtains corresponding pinacol borate.The nuclear magnetic data of product is：1H NMR (CDCl3, 200 MHz), δ 0.79 (d, J=2.79,3H), 0.81 (d, J=2.8 Hz, 3H),
1.04 (d, J = 6.09Hz, 3H), 1.16 (s,12 H, Bpin-CH3), 1.56(m,1H), 3.87 (q, 1H)。
Claims (10)
1. a kind of method for preparing borate using three fragrant oxygen rare earth compoundings, comprises the following steps：
Under anhydrous and oxygen-free environment, in atmosphere of inert gases, three fragrant oxygen rare earths are added in the reaction bulb by dehydration and deoxidation processing
Complex, assimilation compound is then added, be well mixed, add borine, reacted at room temperature 10 ~ 30 min, obtain borate；
The chemical structural formula of the three fragrant oxygen rare earth compounding is：
。
2. the method for preparing borate using three fragrant oxygen rare earth compoundings according to claim 1, it is characterised in that described three
The dosage of fragrant oxygen rare earth compounding is the 0.05-0.1 % of assimilation compound mole；The mol ratio of the assimilation compound and borine is
1：1.1；The general structure of the assimilation compound is：
Wherein R1For phenyl, substituted-phenyl, heterocyclic aryl, naphthyl or anthryl, R2For alkyl.
3. the method that hydroboration occurs with borine for three fragrant oxygen catalyzed by rare-earth complex assimilation compounds, comprises the following steps：
Under anhydrous and oxygen-free environment, under atmosphere of inert gases, three fragrant oxygen rare earths are added in the reaction bulb by dehydration and deoxidation processing
Complex, then add assimilation compound, be well mixed, add borine, react at room temperature 10 ~ 30 min, complete assimilation compound with
The hydroboration of borine；
The chemical structural formula of the three fragrant oxygen rare earth compounding is：
。
4. according to the method for claim 3, it is characterised in that the dosage of the three fragrant oxygen rare earth compounding is assimilation compound
The 0.05-0.1 % of mole；The mol ratio of the assimilation compound and borine is 1：1.1；The general structure of the assimilation compound
For：
Wherein R1For phenyl, substituted-phenyl, heterocyclic aryl, naphthyl or anthryl, R2For alkyl.
5. application of the three fragrant oxygen rare earth compoundings in borate is prepared；The chemical structural formula of the three fragrant oxygen rare earth compounding
For：
。
6. application according to claim 5, it is characterised in that when preparing borate, using assimilation compound and borine as raw material,
The temperature of reaction is room temperature, and the time of reaction is 10-30min.
7. application according to claim 6, it is characterised in that the general structure of the assimilation compound is：
Wherein R1For phenyl, substituted-phenyl, heterocyclic aryl, naphthyl or anthryl, R2For alkyl；
The borine is selected from pinacol borine；
The dosage of the three fragrant oxygen rare earth compounding is the 0.05-0.1 % of assimilation compound mole；The assimilation compound and borine
Mol ratio be 1：1.1.
8. three fragrant oxygen rare earth compoundings are in catalysis assimilation compound and the application in borine hydroboration.
9. application according to claim 8, it is characterised in that the dosage of the three fragrant oxygen rare earth compounding is assimilation compound
The 0.05-0.1 % of mole；The mol ratio of the assimilation compound and borine is 1：1.1；The temperature of the reaction is room temperature, instead
The time answered is 10-30min.
10. application according to claim 8, it is characterised in that the borine is selected from pinacol borine；The assimilation compound
General structure be：
Wherein R1For phenyl, substituted-phenyl, heterocyclic aryl, naphthyl or anthryl, R2For alkyl.
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| CN111185236A (en) * | 2020-01-18 | 2020-05-22 | 苏州大学 | Application of aryloxy rare earth metal complex and borane in catalyzing carbon dioxide hydrosilation reduction reaction |
| 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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| CN106883256A (en) * | 2017-03-17 | 2017-06-23 | 苏州大学 | A kind of method that utilization triscyclopentadienyl rare earth metal complex prepares borate |
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| CN106040303A (en) * | 2016-06-30 | 2016-10-26 | 苏州大学张家港工业技术研究院 | Application of beta-diimide bivalent rare earth boron hydrogen complex in catalysis of hydroboration reaction of ketone and boron hydride |
| CN106883256A (en) * | 2017-03-17 | 2017-06-23 | 苏州大学 | A kind of method that utilization triscyclopentadienyl rare earth metal complex prepares borate |
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| CN111185236A (en) * | 2020-01-18 | 2020-05-22 | 苏州大学 | Application of aryloxy rare earth metal complex and borane in catalyzing carbon dioxide hydrosilation reduction reaction |
| CN111185236B (en) * | 2020-01-18 | 2023-05-12 | 苏州大学 | Application of aryloxy rare earth metal complex and borane in catalyzing carbon dioxide hydrosilation reduction reaction |
| 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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