CN107602594A - A kind of asymmetric beta diimine monovalence magnesium complex and preparation method thereof and the application in the hydroboration of nitrile - Google Patents
A kind of asymmetric beta diimine monovalence magnesium complex and preparation method thereof and the application in the hydroboration of nitrile Download PDFInfo
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Abstract
Application the invention discloses a kind of asymmetric beta diimine monovalence magnesium complex and preparation method thereof and in the hydroboration of nitrile.Preparation method is：First by acetylacetone,2,4-pentanedione and 2, for the condensation of 6 diisopropyl anilines again with 2, the reaction of 4,6 trimethylanilines generates asymmetric beta diimine ligand, then the methylpyridinium iodide reactive magnesium of itself and equivalent is generated to the iodide of magnesium, finally obtain asymmetric beta diimine monovalence magnesium complex with excessive sodium reduction.Preparation method of the present invention is simple, and the asymmetric beta diimine monovalence magnesium complex yield of synthesis is high, has significant effect in the hydroboration of nitrile, reaction condition is gentle, and reaction speed is fast, and yield can reach more than 90%, and catalyst has very high activity.
Description
Technical field
The invention belongs to the synthesis of magnesium metal complex and catalytic reaction technical field, and in particular to a kind of asymmetric β-two
Imines monovalence magnesium complex and preparation method thereof and the application in the hydroboration of nitrile.
Background technology
Because primary amine serves critical effect as reaction intermediate in chemical industry, thus it is how efficient, more
These primary amine of the synthesis of function have become one of emphasis nowadays studied [S.A.Lawrence, In Amines:
Synthesis,Properties,and Application,Cambridge University,Cambridge,2004.].Will
It is one of important channel of many commercial synthesis primary amine that organic nitrile, which is reduced into primary amine, and the catalytic hydrogenation of nitrile can be in heterogeneous conditions
Lower realization.However, these generally selecting property of method are poor, and also result in and form unwanted imines and secondary amine by-product at high temperature
Thing.Dependence for poisonous noble metal is the important factor that these react unsustainable property.Only several reports are good
Good solves above mentioned problem [J.Z.Saavedra, A.Resendez, A.Rovira, S.Eagon, D.Haddenham and
B.Singaram,J.Org.Chem.,2012,77,221；C.Weetman,M.D.Anker,M.Arrowsmith,M.S.Hill,
G.Kociok-D.J.Liptrot and M.F.Mahon,Chem.Sci.,2016,7,628.].Therefore, exploitation is a kind of
Low toxicity, selectivity is good and cheap metallic catalyst is necessary.
In the past decade, the synthesis of monovalence magnesium metallic compound has been achieved for outstanding achievement [C.Jones and
A.Stasch,Topics in Organometallic Chemistry,2013,45,73；A.Stasch and C.Jones,
Dalton Transactions,2011,40,5659.].Although there is a series of monovalence magnesium metallic compound to be closed
Into out, but because generated time is shorter, its application is relatively fewer.These compounds are generally as good reducing agent in nothing
Machine, metal be organic and organic reaction in use.These monovalence magnesium metallic compounds have proven to a kind of safety, selectivity
Good and nontoxic reducing agent, however, the application of compounds all these so far is all stoichiometry, also not by monovalence
Magnesium metallic compound is as the catalyst to the example used.Therefore, the catalytic applications of monovalence magnesium metallic compound are urgently to be resolved hurrily
's.The hydroboration of organonitrile compound is one of important channel that organic nitrile is reduced into primary amine, the boron hydrogen of organonitrile compound
Change product can not only be obtained by way of hydrolysis final resulting primary amine [J.B.Geri and N.K.Szymczak,
J.Am.Chem.Soc., further function dough 2015,137,12808.], can also be carried out to it, it can easily with
Aldehyde reaction generation imines [A.Y.Khalimon, P.F.Lyudmila, G.Kuzmina andG.I.Nikonov,
Chem.Commun.,2012,48,45.]。
In 2011, Jones seminars reduced organonitrile compound with monovalence magnesium metallic compound, under different conditions
Finally give C-C cracking, the product of isomerization and C-C couplings [M.Ma, A.Stasch, C.Jones, Chem.Eur.J.,
2012,18,10669.].These reactions demonstrate monovalence magnesium metallic compound has higher activity for organonitrile compound,
Up to the present, there has been no monovalence magnesium compound catalysis borine and the report of the hydroboration of organonitrile compound.In view of should
The performance of class complex high activity, this kind of complex-catalyzed application not only have great importance to organoboration, simultaneously
Also the application of monovalence magnesium metallic compound has been expanded.
The content of the invention
Goal of the invention：For the deficiencies in the prior art, it is an object of the invention to provide a kind of asymmetric β-two is sub-
Amine monovalence magnesium complex, meets the application in the hydroboration of nitrile.It is above-mentioned not it is a further object of the present invention to provide one kind
The preparation method of symmetrical beta-diimine monovalence magnesium complex.It is sub- that further object of the present invention is to provide a kind of above-mentioned asymmetric β-two
The application of amine monovalence magnesium complex.
Technical scheme：In order to realize foregoing invention purpose, the technical solution adopted by the present invention is：
A kind of asymmetric beta-diimine monovalence magnesium complex, structure are as follows：
A kind of preparation method of described asymmetric beta-diimine monovalence, comprises the following steps：
(1) under argon gas protection, 2,6-DIPA and acetylacetone,2,4-pentanedione are pressed 1：It is molten that 1 mol ratio is added to toluene
In agent, the p-methyl benzenesulfonic acid of catalytic amount is added, flow back 6h, after reaction terminates, drains, adds 2, the 6- tri- of equimolar amounts
Methylaniline and p-methyl benzenesulfonic acid flow back 24h in toluene solvant, drain, are extracted with dichloromethane, dry, after draining, obtain
To solid be exactly asymmetric beta-diimine part.
(2) under the conditions of anhydrous and oxygen-free, in single port reaction tube, methylpyridinium iodide magnesium is slowly dropped to the second of part at -78 DEG C
In ethereal solution, both mol ratios are 1：1, room temperature is to slowly warm up to, is stirred overnight, filtering is stood, obtains the iodide of magnesium.So
The iodide of magnesium are dissolved in 30mL toluene afterwards, inserted by sodium mirror made of excessive metallic sodium, reacting 4 days, filtering, filtrate
Concentration, obtains a large amount of crystal, as asymmetric beta-diimine monovalence magnesium complex.
The reaction equation of the above method is as follows：
Above-mentioned asymmetric beta-diimine monovalence magnesium complex can outline for:[{(DipMesNacnac)Mg}2]。
Above-mentioned asymmetric beta-diimine monovalence magnesium complex is being catalyzed nitrile and application of the borine in hydroboration, including
Following steps：
Under the conditions of anhydrous and oxygen-free, in glove box, asymmetric beta-diimine monovalence magnesium complex, borine and nitrile are added successively
To the C that there are about 0.5mL6D6J-Young nuclear magnetic tubes in be well mixed, be put into 60 DEG C of preheated oil baths, react 1-20h after
Obtain corresponding product.
In above-mentioned technical proposal, the one kind of the nitrile in aromatic nitriles, Arneel SD.
The chemical structure of general formula of the aromatic nitriles is
In formula, R is hydrogen, halogen, nitro, methoxyl group.
The Arneel SD is acetonitrile, isopropyl nitrile, tert-butyl group nitrile, benzene acetonitrile, and borine is pinacol borine.
The dosage of the beta-diimine monovalence magnesium complex is the 10% of nitrile molal quantity.
The mol ratio of borine and nitrile is 2:1, the hydroboration temperature is 60 DEG C, reaction time 1-20h.
The reaction equation of above-mentioned application is as follows：
Wherein R comes from selected nitrile.
Beneficial effect：Compared with prior art, the present invention has following advantages：
1) present invention is catalyzed the addition reaction of nitrile and borine with monovalence magnesium complex first, is new and effective catalytic reaction
Agent, its is simple in construction, is readily synthesized.This kind of complex-catalyzed application not only has great importance to organoboration, together
When also expanded the application of monovalence magnesium metallic compound.
2) monovalence magnesium complex of the invention can the catalysis nitrile of high activity and the hydroboration of borine be anti-in a mild condition
Should, catalyst amount is reasonable, reaction speed quickly, reaction 8h with regard to can reach more than 90% yield, with existing catalyst system and catalyzing
Compare, both improve selectivity, improve yield again, reaction condition is gentle, and catalyst is nontoxic, highly meets the reason of Green Chemistry
Read.
3) monovalence magnesium complex of the invention is wide to the scope of application of substrate, suitable for different substituents position, different electricity
The nitrile of sub- effect, also there is preferable selectivity for different substituents, be combined to provide one kind very well for the industry of primary amine
Selection.
Embodiment
With reference to embodiment, the invention will be further described.
Embodiment 1
(1) asymmetric beta-diimine part (DipMesNacnacH preparation)
Under argon gas protection, 120mL toluene is added in 250mL round-bottomed flask, adds 2,6-DIPA
147mmol, acetylacetone,2,4-pentanedione 147mmol and p-methyl benzenesulfonic acid 1.8mmol 160 DEG C of backflow 9h under Dean-Stark devices, instead
After should terminating, drain, it is molten in 120mL toluene to add 2,4,6- trimethylaniline 147mmol and p-methyl benzenesulfonic acid 147mmol
The lower 160 DEG C of backflows 24h of Dean-Stark devices, is drained, with dichloromethane and saturation NaHCO in agent3Three times, organic phase is used for extraction
Anhydrous MgSO4Dry, after draining, obtained solid be exactly asymmetric beta-diimine part (DipMesNacnacH), yield is
64%.The nuclear magnetic data of product:1H NMR(CDCl3,600MHz):δ12.27(s,1H,NH),7.13(s,3H,Ar-H),6.89
(s, 2H, Ar-H), 4.89 (s, 1H ,=CH), 3.08 (sept,3JHH=6.6Hz, 2H, CH (CH3)2),2.28(s,3H,CH3),
2.16(s,6H,CH3),1.73(s,3H,NCCH3),1.72(s,3H,NCCH3),1.24(d,3JHH=6.6Hz, 6H, CH
(CH3)2),1.14(d,3JHH=6.6Hz, 6H, CH (CH3)2).13C{1H}NMR(CDCl3,151MHz):δ161.7(NCCH3),
160.4(NCCH3), 141.7,141.6,140.4,134.0,132.5,128.5,124.7,122.9 (Ar-C), 93.2 (=
CH),28.3(CH(CH3)2),24.2,22.8,20.9,20.8,20.2,18.1(CH3).
(2) asymmetric beta-diimine monovalence magnesium complex [(DipMesNacnac)Mg}2] preparation
Under the conditions of anhydrous and oxygen-free, methylpyridinium iodide magnesium 6.40mmol is slowly dropped in single port reaction tube, under low temperature above-mentioned
In part 6.40mmol diethyl ether solution, it is stirred overnight at room temperature, stands filtering, obtain the iodide of magnesium.Then by the iodate of magnesium
Thing 2.20mmol is dissolved in 30mL toluene, is inserted by sodium mirror made of excessive metallic sodium 18mmol, reacting 4 days, is filtered, filter
Liquid concentrates, and obtains a large amount of crystal, as asymmetric beta-diimine monovalence magnesium complex [(DipMesNacnac)Mg}2], yield is
41%.The nuclear magnetic data of product:1H NMR(C6D6,600MHz):δ7.10–7.04(m,6H,Ar-H),6.88(s,4H,Ar-H),
4.85 (s, 2H ,=CH), 2.98 (sept,3JHH=6.6Hz, 4H, CH (CH3)2),2.31(s,6H,CH3),1.93(s,12H,
CH3),1.57(s,12H,NCCH3),1.52(s,6H,NCCH3),1.10(d,3JHH=6.6Hz, 12H, CH (CH3)2),0.94(d
,3JHH=6.6Hz, 12H, CH (CH3)2).13C{1H}NMR(C6D6,151MHz):δ167.1(NCCH3),166.4(NCCH3),
(145.4,144.9,141.8,132.4,131.1,129.1,125.0,123.3 Ar-C), 95.3 (=CH), 27.8 (CH
(CH3)2),25.0,23.7,23.3,22.9,20.8,19.0(CH3).
Embodiment 2：[{(DipMesNacnac)Mg}2] it is catalyzed the hydroboration of benzonitrile and pinacol borine
Under the conditions of anhydrous and oxygen-free, in glove box, will [(DipMesNacnac)Mg}2] 0.006mmol is added to and there are about 0.5mL
C6D6J-Young nuclear magnetic tubes in, then with liquid-transfering gun add pinacol borine 1.2mmol be well mixed, be eventually adding benzene first
After nitrile 0.6mmol, 60 DEG C of reaction 8h, nuclear-magnetism is surveyed.It is computed1H spectrum yields are 98%.The nuclear magnetic data of product:1H NMR(C6D6,
600MHz):7.58(m,2H,Ar-H),7.25(m,2H,Ar-H),7.11(m,1H,Ar-H),4.61(s,2H,Ar-CH2),
1.03(s,24H,C(CH3)2)。
Embodiment 3：[{(DipMesNacnac)Mg}2] it is catalyzed the hydroboration of 4- methoxy benzonitriles and pinacol borine
Under the conditions of anhydrous and oxygen-free, in glove box, will [(DipMesNacnac)Mg}2] 0.006mmol is added to and there are about 0.5mL
C6D6J-Young nuclear magnetic tubes in, then with liquid-transfering gun add pinacol borine 1.2mmol be well mixed, be eventually adding 4- first
After epoxide benzonitrile 0.6mmol, 60 DEG C of reaction 24h, nuclear-magnetism is surveyed.It is computed1H spectrum yields are 83%.The nuclear magnetic data of product:1H
NMR(C6D6,600MHz):7.56(d,3JHH=8.4Hz, 2H, Ar-H), 6.87 (d,3JHH=8.4Hz, 2H, Ar-H), 4.58 (s,
2H,Ar-CH2),3.34(s,3H,OCH3),1.05(s,24H,C(CH3)2)。
Embodiment 4：[{(DipMesNacnac)Mg}2] it is catalyzed the hydroboration of p-Fluorophenyl cyanide and pinacol borine
Under the conditions of anhydrous and oxygen-free, in glove box, will [(DipMesNacnac)Mg}2] 0.006mmol is added to and there are about 0.5mL
C6D6J-Young nuclear magnetic tubes in, then with liquid-transfering gun add pinacol borine 1.2mmol be well mixed, be eventually adding to fluorine
After benzonitrile 0.6mmol, 60 DEG C of reaction 4h, nuclear-magnetism is surveyed.It is computed1H spectrum yields are 99%.The nuclear magnetic data of product:1H NMR
(C6D6,600MHz):7.41(m,2H,Ar-H),6.88(m,2H,Ar-H),4.46(s,2H,Ar-CH2),1.02(s,24H,C
(CH3)2)。
Embodiment 5：[{(DipMesNacnac)Mg}2] it is catalyzed the hydroboration of p-nitrobenzonitfile and pinacol borine
Under the conditions of anhydrous and oxygen-free, in glove box, will [(DipMesNacnac)Mg}2] 0.006mmol is added to and there are about 0.5mL
C6D6J-Young nuclear magnetic tubes in, then with liquid-transfering gun add pinacol borine 1.2mmol be well mixed, be eventually adding to nitre
After base benzonitrile 0.6mmol, 60 DEG C of reaction 20h, nuclear-magnetism is surveyed.It is computed1H spectrum yields are 87%.The nuclear magnetic data of product:1H
NMR(C6D6,600MHz):7.91(d,3JHH=8.4Hz, 2H, Ar-H), 7.23 (d,3JHH=8.4Hz, 2H, Ar-H), 4.39 (s,
2H,Ar-CH2),1.03(s,24H,C(CH3)2)。
Embodiment 6：[{(DipMesNacnac)Mg}2] it is catalyzed the hydroboration of benzene acetonitrile and pinacol borine
Under the conditions of anhydrous and oxygen-free, in glove box, will [(DipMesNacnac)Mg}2] 0.006mmol) be added to and there are about
0.5mL C6D6J-Young nuclear magnetic tubes in, then with liquid-transfering gun add pinacol borine 1.2mmol be well mixed, finally plus
After entering benzene acetonitrile 0.6mmol, 60 DEG C of reaction 4h, nuclear-magnetism is surveyed.It is computed1H spectrum yields are 90%.The nuclear magnetic data of product:1H NMR
(C6D6,600MHz):7.33(m,3H,Ar-H),7.23(m,2H,Ar-H),3.77(t,3JHH=7.2Hz, 2H, ArCH2),3.02
(t,3JHH=8.4Hz, 3H, NCH3),1.04(s,24H,C(CH3)2)。
Embodiment 7：[{(DipMesNacnac)Mg}2] Acetonitrile and pinacol borine hydroboration
Under the conditions of anhydrous and oxygen-free, in glove box, will [(DipMesNacnac)Mg}2] 0.006mmol is added to and there are about 0.5mL
C6D6J-Young nuclear magnetic tubes in, then with liquid-transfering gun add pinacol borine 1.2mmol be well mixed, be eventually adding acetonitrile
After 0.6mmol, 60 DEG C of reaction 1h, nuclear-magnetism is surveyed.It is computed1H spectrum yields are 99%.The nuclear magnetic data of product:1H NMR(C6D6,
600MHz):3.77(q,3JHH=7.2Hz, 2H, NCH2),1.33(t,3JHH=7.2Hz, 3H, CH2CH3),1.06(s,24H,C
(CH3)2)。
Embodiment 8：[{(DipMesNacnac)Mg}2] catalyzing iso-butane nitrile and pinacol borine hydroboration
Under the conditions of anhydrous and oxygen-free, in glove box, will [(DipMesNacnac)Mg}2] 0.006mmol is added to and there are about 0.5mL
C6D6J-Young nuclear magnetic tubes in, then with liquid-transfering gun add pinacol borine 1.2mmol be well mixed, be eventually adding isobutyl
After nitrile 0.6mmol, 60 DEG C of reaction 5h, nuclear-magnetism is surveyed.It is computed1H spectrum yields are 99%.The nuclear magnetic data of product:1H NMR(C6D6,
600MHz):3.28(d,3JHH=7.2Hz, 2H, NCH2),2.05(m,1H,CH(CH3)2),1.06(s,24H,C(CH3)2),1.08
(d,3JHH=7.2Hz, 6H, CH (CH3)2)。
Embodiment 9：[{(DipMesNacnac)Mg}2] it is catalyzed the hydroboration of trimethylacetonitrile and pinacol borine
Under the conditions of anhydrous and oxygen-free, in glove box, will [(DipMesNacnac)Mg}2] 0.006mmol is added to and there are about 0.5mL
C6D6J-Young nuclear magnetic tubes in, then with liquid-transfering gun add pinacol borine 1.2mmol be well mixed, be eventually adding front three
After base acetonitrile 0.6mmol, 60 DEG C of reaction 6h, nuclear-magnetism is surveyed.It is computed1H spectrum yields are 99%.The nuclear magnetic data of product:1H NMR
(C6D6,600MHz):3.32(s,2H,NCH2),1.08(s,24H,C(CH3)2),1.04(s,9H,C(CH3)3)。
Claims (9)
1. a kind of asymmetric beta-diimine monovalence magnesium complex, structure are as follows：
A kind of 2. preparation method of the asymmetric beta-diimine monovalence magnesium complex described in claim 1, it is characterised in that including
Following steps：
(1) under argon gas protection, 2,6-DIPA and acetylacetone,2,4-pentanedione are pressed 1：1 mol ratio is added to toluene solvant
In, the p-methyl benzenesulfonic acid of catalytic amount is added, flow back 6h, after reaction terminates, drains, adds 2, the 4,6- tri- of equimolar amounts
Methylaniline and p-methyl benzenesulfonic acid flow back 24h in toluene solvant, drain, are extracted with dichloromethane, dry, after draining, obtain
To solid be exactly asymmetric beta-diimine part；
(2) under the conditions of anhydrous and oxygen-free, in single port reaction tube, methylpyridinium iodide magnesium is slowly dropped to the second of above-mentioned part at -78 DEG C
In ethereal solution, both mol ratios are 1：1, room temperature is to slowly warm up to, is stirred overnight, filtering is stood, obtains the iodide of magnesium；So
The iodide of magnesium are dissolved in 30mL toluene afterwards, inserted by sodium mirror made of excessive metallic sodium, reacting 4 days, filtering, filtrate
Concentration, obtains a large amount of crystal, as asymmetric beta-diimine monovalence magnesium complex.
3. application of the asymmetric beta-diimine monovalence magnesium complex in the hydroboration of nitrile described in claim 1.
4. application according to claim 3, it is characterised in that：The one kind of the nitrile in aromatic nitriles, Arneel SD；Borine
For pinacol borine.
5. application according to claim 4, it is characterised in that：The chemical structure of general formula of the aromatic nitriles is：
In formula, R is hydrogen, halogen, nitro, methoxyl group.
6. application according to claim 4, it is characterised in that：The Arneel SD be acetonitrile, isopropyl nitrile, tert-butyl group nitrile,
Benzene acetonitrile.
7. application according to claim 4, it is characterised in that：The dosage of the asymmetric beta-diimine monovalence magnesium complex
For the 10% of nitrile molal quantity；The mol ratio of borine and nitrile is 2:1.
8. application according to claim 4, it is characterised in that：The hydroboration temperature is 60 DEG C, and the reaction time is
1-20h。
9. application according to claim 4, it is characterised in that：Under the conditions of anhydrous and oxygen-free, in glove box, successively by asymmetry
Beta-diimine monovalence magnesium complex, borine and nitrile are added to C6D6J-Young nuclear magnetic tubes in be well mixed, be put into preheated
In 60 DEG C of oil bath pans, corresponding product is obtained after reacting 1-20h.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108276433A (en) * | 2018-01-26 | 2018-07-13 | 南京林业大学 | A kind of Hydroboronation process of ester |
| CN108358959A (en) * | 2018-01-26 | 2018-08-03 | 南京林业大学 | A kind of Hydroboronation process of isocyanide ester |
| CN108569984A (en) * | 2018-05-25 | 2018-09-25 | 南京林业大学 | A kind of asymmetry diimine monovalence magnesium compound and preparation method thereof and the application in alkylene oxide hydroboration |
| CN110357912A (en) * | 2019-07-15 | 2019-10-22 | 苏州大学 | Three silicon amine rare earth compoundings prepare the application in aminated compounds in catalysis nitrile and borine reaction |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN106040304A (en) * | 2016-06-30 | 2016-10-26 | 苏州大学 | Application of beta-diimine divalent rare earth boron hydrogen complex to hydroboration of catalytic aldehyde and borane |
-
2017
- 2017-09-27 CN CN201710890860.0A patent/CN107602594B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN106040304A (en) * | 2016-06-30 | 2016-10-26 | 苏州大学 | Application of beta-diimine divalent rare earth boron hydrogen complex to hydroboration of catalytic aldehyde and borane |
Non-Patent Citations (3)
| Title |
|---|
| ANDREAS STASCH: "Synthesis of a Dimeric Magnesium(I) Compound by an MgI/MgII Redox Reaction", 《ANGEW. CHEM. INT. ED.》 * |
| CHELLADURAI GANESAMOORTHY ET AL: "Synthesis and Structural Characterization of Magnesium-Substituted Polystibides [(LMg)4Sb8]", 《ANGEW. CHEM. INT. ED.》 * |
| SHAUN P. GREEN ET AL: "Stable Magnesium(I) Compounds with Mg-Mg Bonds", 《SCIENCE》 * |
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| CN108276433A (en) * | 2018-01-26 | 2018-07-13 | 南京林业大学 | A kind of Hydroboronation process of ester |
| CN108358959A (en) * | 2018-01-26 | 2018-08-03 | 南京林业大学 | A kind of Hydroboronation process of isocyanide ester |
| CN108276433B (en) * | 2018-01-26 | 2022-04-19 | 南京林业大学 | Hydroboration method of ester |
| CN108569984A (en) * | 2018-05-25 | 2018-09-25 | 南京林业大学 | A kind of asymmetry diimine monovalence magnesium compound and preparation method thereof and the application in alkylene oxide hydroboration |
| CN110357912A (en) * | 2019-07-15 | 2019-10-22 | 苏州大学 | Three silicon amine rare earth compoundings prepare the application in aminated compounds in catalysis nitrile and borine reaction |
| CN110357912B (en) * | 2019-07-15 | 2022-12-20 | 苏州大学 | Application of trisilamide rare earth complex in preparation of amine compound by catalyzing reaction of nitrile and borane |
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