CN107602595B - A kind of beta-diimine monovalence magnesium compound and preparation method thereof and the application in aldehyde ketone hydroboration - Google Patents
A kind of beta-diimine monovalence magnesium compound and preparation method thereof and the application in aldehyde ketone hydroboration Download PDFInfo
- Publication number
- CN107602595B CN107602595B CN201710892796.XA CN201710892796A CN107602595B CN 107602595 B CN107602595 B CN 107602595B CN 201710892796 A CN201710892796 A CN 201710892796A CN 107602595 B CN107602595 B CN 107602595B
- Authority
- CN
- China
- Prior art keywords
- beta
- magnesium compound
- diimine
- monovalence magnesium
- nuclear magnetic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
Application the invention discloses a kind of beta-diimine monovalence magnesium compound and preparation method thereof and in aldehyde ketone hydroboration.The preparation method comprises the following steps: under the conditions of anhydrous and oxygen-free, beta-diimine ligand and Grignard Reagent reaction generate the iodide of magnesium, then with sodium reduction, obtain yellow crystals, as beta-diimine monovalence magnesium compound.The synthesis of beta-diimine monovalence magnesium compound of the invention is simple, and separating-purifying is convenient, and structure is clear, and high income；It is high as the activity that catalyst aldehyde or ketone are reacted with pinacol borine, and substrate universality is wide.
Description
Technical field
The present invention relates to metallo-organic compound preparation technical fields, and in particular to a kind of beta-diimine monovalence magnesium compound
And preparation method thereof and the application in aldehyde ketone hydroboration.
Background technique
It is well known that hydroboration is critically important reaction [Chong C.C., Kinjo a R.ACS in catalysis reaction
Catal.2015,5,3238；Geier S.J.,Vogels C.M.,Westcott S.A.ACS Symp.Ser.2016,1236,
209.].Although traditional transition-metal catalyst has certain reactivity, price is relatively expensive, so honest and clean with other
Valence catalyst replace conventional precious metal catalyst it is imperative [Vasilenko V., Blasius C.K., Wadepohl H.,
Gade L.H.,Angew.Chem.Int.Ed.2017,56,8393；Arévalo R.,Vogels C.M.,MacNeil G.A.,
Riera L.,Péreza J.,Westcott S.A.Dalton Trans.2017,46,7750.].Main group metal because its just
Preferably, the advantages that environmentally friendly, show clear superiority [Hill M.S., Liptrot D.J., Weetman C.Chem.Soc.Rev,
2016,45,972；Revunova K.,Nikonov G.I.Dalton Trans.2015,44,840.].Reported aldehyde ketone boron
In main group metal used in hydrogenation, the first main group alkali metal is mainly lithium, sodium and potassium metal, such as Okuda synthesis
[(L)M][HBPh3] (M=lithium, sodium, potassium) can be catalyzed the hydroboration of aldehydes or ketones Yu pinacol borine, obtain preferable effect
Fruit [Mukherjee D., Osseili H., Spaniol T.P., Okuda J, Chem.Commun.2016,138,10790].
Second main group alkaline-earth metal be mainly magnesium and calcium metal [Arrowsmith M., Hadlington T.J., Hill M.S.,G.,Chem.Commun.2012,48,4567；Mukherjee D.,Ellern A.,Sadow A.D.,
Chem.Sci.2014,5,959；Mukherjee D.,Shirase S.,Spaniol T.P.,Mashima K.,Okuda J.,
Chem.Commun.2016,52,13155；Barman M.K.,Baishya A.,Nembenna S.,Dalton
Trans.2017,46,4152].Such as Hill is catalyst with the butyl of beta-diimine magnesium, is catalyzed the boron of a variety of aldehyde ketones
Hydrogenation.Third main group metal is mainly aluminium, such as Roesky beta-diimine ligand, has synthesized the hydride of corresponding aluminium,
In aldehyde ketone hydroboration and a kind of efficient catalyst [Yang Z., Zhong M., Ma X., De S., Anusha
C.,Parameswaran P.,Roesky H.W.,Angew.Chem.Int.Ed.2015,127,10363；Jakhar V.K.,
Barman M.K.,Nembenna S.Org.Lett.2016,18,4710.].4th main group is mainly germanium and selenium metal, such as
The secondary amine ligand of the large space steric hindrance such as Jones, has synthesized the hydride of corresponding germanium and selenium, can be with the boron hydrogen of efficient catalytic aldehyde ketone
Change reaction [Hadlington T.J., Hermann M., Frenking G., Jones C., J.Am.Chem.Soc.2014,
136,3028.]。
Another aspect monovalence magnesium compound is widely used [Jones C., Nature in organic and Inorganic synthese
Reviews Chemistry,2017,1,59；Jones C.,Stasch A.Top.Organomet.Chem.2013,45,
73.], it can be used as mild reducing agent, reducing power is between alkali metal and samarium diodide.In some reactions, it uses
Traditional reducing agent, such as Na, the reducing powers such as K are too strong, it may occur that expected results are not achieved in over reduction, can be suitable with reproducibility
In monovalence magnesium compound.Monovalence magnesium compound can be reacted with a variety of small organic molecules, such as azobenzene, carbodiimides, ring
Octatetraene, anthracene, azide, isocyanates, nitrile compound and isonitrile compound etc..Monovalence magnesium can also be reacted with some gas molecules,
Such as sulfur dioxide, carbon dioxide, carbon monoxide etc..
The application of the related monovalence magnesium compound of existing report is all stoichiometry, but monovalence magnesium compound catalytic amount
Application do not report still.
Summary of the invention
Goal of the invention: the deficiencies in the prior art are directed to, the object of the present invention is to provide a kind of beta-diimine monovalencies
Magnesium compound meets the use demand of aldehyde ketone hydroboration.It is a further object of the present invention to provide a kind of above-mentioned beta-diimines
The preparation method of monovalence magnesium compound.Further object of the present invention is to provide a kind of answering for above-mentioned beta-diimine monovalence magnesium compound
With.
Technical solution: for achieving the above object, the technical solution adopted by the present invention is that:
A kind of beta-diimine monovalence magnesium compound, for [(XylNacnac)Mg}2], structural formula is as follows:
A kind of preparation method of the beta-diimine monovalence magnesium compound, comprising the following steps:
(1) under the conditions of anhydrous and oxygen-free, in single port reaction tube, beta-diimine ligand is dissolved in diethyl ether solution, -80~-40
DEG C, methylpyridinium iodide magnesium is added dropwise above-mentioned solution, and room temperature reaction 8~for 24 hours.Obtain the iodide of beta-diimine magnesium；Wherein β-two
Imine ligand, methylpyridinium iodide magnesium molar ratio be 1:1-1.2；Its reaction equation is as follows:
(2) under the conditions of anhydrous and oxygen-free, in single port reaction tube, the iodide of beta-diimine magnesium are dissolved in toluene solution, transfer
To sodium mirror, 3~5d is reacted, is filtered, concentration, obtaining yellow crystals is beta-diimine monovalence magnesium compound.Wherein beta-diimine magnesium
Iodide, metallic sodium molar ratio be 1:5-20；Its reaction equation is as follows:
Application of the beta-diimine monovalence magnesium compound as catalyst in the hydroboration of catalysis aldehydes or ketones.
The application, comprising the following steps: under the conditions of anhydrous and oxygen-free, beta-diimine monovalence magnesium compound is dissolved in molten
In agent, pinacol borine is added, adds aldehydes or ketones, reacts at room temperature 10min.
The molar ratio of the application, aldehyde and catalyst is 1000:1.
The molar ratio of the application, ketone and catalyst is 1000:1.
The utility model has the advantages that compared with prior art, the present invention has the advantage that
1) beta-diimine monovalence magnesium compound of the present invention is new compound, and it is sub- to develop new and effective β-two
Amine monovalence magnesium metallic catalyst.
2) preparation method disclosed by the invention, reaction process is simple to operation, required article small toxicity, safety collar in experiment
It protects, product is easily purified, yield is high, and can be stored at room temperature.
3) beta-diimine monovalence magnesium compound of the present invention can effectively be catalyzed the hydroboration of aldehyde and ketone.
Specific embodiment
Below with reference to embodiment, the invention will be further described.In following embodiment, filter, drain, extracting, being concentrated,
The operating procedures such as freezing and crystallizing, separation belong to the prior art, and those skilled in the art can give according to the property of actual product
Selection.
Embodiment 1
The preparation of the iodide of beta-diimine magnesium, process are as follows:
Under anhydrous and oxygen-free, in single port reaction tube, beta-diimine ligand 3.27mmol is dissolved in 25mL diethyl ether solution, and -80
DEG C, above-mentioned solution is added dropwise in methylpyridinium iodide magnesium 3.92mmol, and room temperature reaction is for 24 hours.Filtering, solid are drained, and filtrate is concentrated into
5mL, obtains clear crystal, and solid and crystal quality are 1.63g, yield 94%.M.p.271-273℃.Nuclear magnetic resoance spectrum:1H
NMR(600MHz,C6D6):δ6.99-6.91(m,6H,Ar-H),4.88(s,1H,CH),3.12(s,4H,OCH2CH3),2.65
(s,6H,CH3),2.08(s,6H,CH3),1.55(s,6H,NCCH3),0.48(s,6H,OCH2CH3)ppm.13C{1H}NMR
(151MHz,C6D6):δ168.87(NCCH3), 147.75,131.57,129.56,124.76 (Ar-C), 95.31 (=CH),
65.96(OCH2CH3),23.52(OCH2CH3),21.09(NCCH3),18.89,13.15(CH3)ppm.
Embodiment 2
The preparation of the iodide of beta-diimine magnesium, process are as follows:
Under anhydrous and oxygen-free, in single port reaction tube, beta-diimine ligand 3.27mmol is dissolved in 25mL diethyl ether solution, and -60
DEG C, above-mentioned solution is added dropwise in methylpyridinium iodide magnesium 3.60mmol, reacts at room temperature 15h.Filtering, solid are drained, and filtrate is concentrated into
5mL, obtains clear crystal, and solid and crystal quality are 1.61g, yield 92%.M.p.271-273℃.Nuclear magnetic resoance spectrum:1H
NMR(600MHz,C6D6):δ6.99-6.91(m,6H,Ar-H),4.88(s,1H,CH),3.12(s,4H,OCH2CH3),2.65
(s,6H,CH3),2.08(s,6H,CH3),1.55(s,6H,NCCH3),0.48(s,6H,OCH2CH3)ppm.13C{1H}NMR
(151MHz,C6D6):δ168.87(NCCH3), 147.75,131.57,129.56,124.76 (Ar-C), 95.31 (=CH),
65.96(OCH2CH3),23.52(OCH2CH3),21.09(NCCH3),18.89,13.15(CH3)ppm.
Embodiment 3
The preparation of the iodide of beta-diimine magnesium, process are as follows:
Under anhydrous and oxygen-free, in single port reaction tube, beta-diimine ligand 3.27mmol is dissolved in 25mL diethyl ether solution, and -40
DEG C, above-mentioned solution is added dropwise in methylpyridinium iodide magnesium 3.27mmol, reacts at room temperature 15h.Filtering, solid are drained, and filtrate is concentrated into
5mL, obtains clear crystal, and solid and crystal quality are 1.63g, yield 94%.M.p.271-273℃.Nuclear magnetic resoance spectrum:1H
NMR(600MHz,C6D6):δ6.99-6.91(m,6H,Ar-H),4.88(s,1H,CH),3.12(s,4H,OCH2CH3),2.65
(s,6H,CH3),2.08(s,6H,CH3),1.55(s,6H,NCCH3),0.48(s,6H,OCH2CH3)ppm.13C{1H}NMR
(151MHz,C6D6):δ168.87(NCCH3), 147.75,131.57,129.56,124.76 (Ar-C), 95.31 (=CH),
65.96(OCH2CH3),23.52(OCH2CH3),21.09(NCCH3),18.89,13.15(CH3)ppm.
Embodiment 4
The preparation of beta-diimine monovalence magnesium compound, process are as follows:
Under anhydrous and oxygen-free, in single port reaction tube, the iodide 2.83mmol of beta-diimine magnesium is dissolved in 30mL toluene solution
In, it is transferred in 14.15mmol sodium mirror, reacts 3d.Filtering, filtrate is concentrated into 2mL, obtain yellow crystals [(XylNacnac)
Mg}2], quality 0.56g, yield 60%.M.p.177-179℃.Nuclear magnetic resoance spectrum:1H NMR(600MHz,C6D6):δ
7.03(d,JH-H=7.2Hz, 8H, Ar-H), 6.97 (t, JH-H=7.2Hz, 4H, Ar-H), 4.77 (s, 2H, CH), 1.91 (s,
24H,CH3),1.50(s,12H,NCCH3)ppm.13C{1H}NMR(151MHz,C6D6):166.31(NCCH3),148.04,
(131.81,128.46,124.15 Ar-C), 95.36 (=CH), 23.13 (NCCH3),19.31(CH3)ppm.
Embodiment 5
The preparation of beta-diimine monovalence compound magnesium, process are as follows:
Under anhydrous and oxygen-free, in single port reaction tube, the iodide 2.83mmol of beta-diimine magnesium is dissolved in 30mL toluene solution
In, it is transferred in 28.3mmol sodium mirror, reacts 4d.Filtering, filtrate is concentrated into 2mL, obtain yellow crystals [(XylNacnac)
Mg}2], quality 0.54g, yield 59%.M.p.177-179℃.Nuclear magnetic resoance spectrum:1H NMR(600MHz,C6D6):δ
7.03(d,JH-H=7.2Hz, 8H, Ar-H), 6.97 (t, JH-H=7.2Hz, 4H, Ar-H), 4.77 (s, 2H, CH), 1.91 (s,
24H,CH3),1.50(s,12H,NCCH3)ppm.13C{1H}NMR(151MHz,C6D6):166.31(NCCH3),148.04,
(131.81,128.46,124.15 Ar-C), 95.36 (=CH), 23.13 (NCCH3),19.31(CH3)ppm.
Embodiment 6
The preparation of beta-diimine monovalence magnesium compound, process are as follows:
Under anhydrous and oxygen-free, in single port reaction tube, the iodide 2.83mmol of beta-diimine magnesium is dissolved in 30mL toluene solution
In, it is transferred in 56.6mmol sodium mirror, reacts 5d.Filtering, filtrate is concentrated into 2mL, obtain yellow crystals [(XylNacnac)
Mg}2], quality 0.56g, yield 60%.M.p.177-179℃.Nuclear magnetic resoance spectrum:1H NMR(600MHz,C6D6):δ
7.03(d,JH-H=7.2Hz, 8H, Ar-H), 6.97 (t, JH-H=7.2Hz, 4H, Ar-H), 4.77 (s, 2H, CH), 1.91 (s,
24H,CH3),1.50(s,12H,NCCH3)ppm.13C{1H}NMR(151MHz,C6D6):166.31(NCCH3),148.04,
(131.81,128.46,124.15 Ar-C), 95.36 (=CH), 23.13 (NCCH3),19.31(CH3)ppm.
Embodiment 7
Beta-diimine monovalence magnesium compound catalysis benzaldehyde is reacted with pinacol borine, and process is as follows:
In glove box, 0.5mL C is being housed6D6Nuclear magnetic tube in sequentially add beta-diimine monovalence magnesium compound
Then 0.001mmol, benzaldehyde 1mmol and pinacol borine 1.2mmol are moved out glove box, react 10min, pass through core
Magnetic spectrum figure obtains the rate of output 99%.
Embodiment 8
Beta-diimine monovalence magnesium compound catalysis o-chlorobenzaldehyde is reacted with pinacol borine, and process is as follows:
In glove box, 0.5mL C is being housed6D6Nuclear magnetic tube in sequentially add beta-diimine monovalence magnesium compound
Then 0.001mmol, o-chlorobenzaldehyde 1mmol and pinacol borine 1.2mmol are moved out glove box, react 10min, lead to
It crosses nuclear magnetic spectrogram and obtains the rate of output 99%.
Embodiment 9
Beta-diimine monovalence magnesium compound catalysis 4- chlorobenzaldehyde is reacted with pinacol borine, and process is as follows:
In glove box, 0.5mL C is being housed6D6Nuclear magnetic tube in sequentially add beta-diimine monovalence magnesium compound
Then 0.001mmol, 4- chlorobenzaldehyde 1mmol and pinacol borine 1.2mmol are moved out glove box, react 10min, lead to
It crosses nuclear magnetic spectrogram and obtains the rate of output 99%.
Embodiment 10
Beta-diimine monovalence magnesium compound catalysis o fluorobenzaldehyde is reacted with pinacol borine, and process is as follows:
In glove box, 0.5mL C is being housed6D6Nuclear magnetic tube in sequentially add beta-diimine monovalence magnesium compound
Then 0.001mmol, o fluorobenzaldehyde 1mmol and pinacol borine 1.2mmol are moved out glove box, react 10min, lead to
It crosses nuclear magnetic spectrogram and obtains the rate of output 99%.
Embodiment 11
Beta-diimine monovalence magnesium compound catalysis 4- fluorobenzaldehyde is reacted with pinacol borine, and process is as follows:
In glove box, 0.5mL C is being housed6D6Nuclear magnetic tube in sequentially add beta-diimine monovalence magnesium compound
Then 0.001mmol, 4- fluorobenzaldehyde 1mmol and pinacol borine 1.2mmol are moved out glove box, react 10min, lead to
It crosses nuclear magnetic spectrogram and obtains the rate of output 99%.
Embodiment 12
Beta-diimine monovalence magnesium compound catalysis 4- nitrobenzaldehyde is reacted with pinacol borine, and process is as follows:
In glove box, 0.5mL C is being housed6D6Nuclear magnetic tube in sequentially add beta-diimine monovalence magnesium compound
Then 0.001mmol, 4- nitrobenzaldehyde 1mmol and pinacol borine 1.2mmol are moved out glove box, react 10min,
The rate of output 99% is obtained by nuclear magnetic spectrogram.
Embodiment 13
Beta-diimine monovalence magnesium compound catalysis 4- (dimethylamino) benzaldehyde is reacted with pinacol borine, and process is such as
Under:
In glove box, 0.5mL C is being housed6D6Nuclear magnetic tube in sequentially add beta-diimine monovalence magnesium compound
0.001mmol, 4- (dimethylamino) benzaldehyde 1mmol and pinacol borine 1.2mmol, are then moved out glove box, instead
10min is answered, the rate of output 99% is obtained by nuclear magnetic spectrogram.
Embodiment 14
Beta-diimine monovalence magnesium compound catalysis p-tolyl aldehyde is reacted with pinacol borine, and process is as follows:
In glove box, 0.5mL C is being housed6D6Nuclear magnetic tube in sequentially add beta-diimine monovalence magnesium compound
Then 0.001mmol, p-tolyl aldehyde 1mmol and pinacol borine 1.2mmol are moved out glove box, react 10min,
The rate of output 99% is obtained by nuclear magnetic spectrogram.
Embodiment 15
Beta-diimine monovalence magnesium compound catalysis p-anisaldehyde is reacted with pinacol borine, and process is as follows:
In glove box, 0.5mL C is being housed6D6Nuclear magnetic tube in sequentially add beta-diimine monovalence magnesium compound
Then 0.001mmol, p-anisaldehyde 1mmol and pinacol borine 1.2mmol are moved out glove box, react 10min, pass through
Nuclear magnetic spectrogram obtains the rate of output 99%.
Embodiment 16
Beta-diimine monovalence magnesium compound catalysis cyclohexyl formaldehyde is reacted with pinacol borine, and process is as follows:
In glove box, 0.5mL C is being housed6D6Nuclear magnetic tube in sequentially add beta-diimine monovalence magnesium compound
Then 0.001mmol, cyclohexyl formaldehyde 1mmol and pinacol borine 1.2mmol are moved out glove box, react 10min,
The rate of output 99% is obtained by nuclear magnetic spectrogram.
Embodiment 17
Beta-diimine monovalence magnesium compound spirit catalytic of cinnamaldehyde is reacted with pinacol borine, and process is as follows:
In glove box, 0.5mL C is being housed6D6Nuclear magnetic tube in sequentially add beta-diimine monovalence magnesium compound
Then 0.001mmol, cinnamic acid 1mmol and pinacol borine 1.2mmol are moved out glove box, react 10min, pass through core
Magnetic spectrum figure obtains the rate of output 99%.
Embodiment 18
Beta-diimine monovalence magnesium compound catalysis 9- anthraldehyde is reacted with pinacol borine, and process is as follows:
In glove box, 0.5mL C is being housed6D6Nuclear magnetic tube in sequentially add beta-diimine monovalence magnesium compound
Then 0.001mmol, 9- anthraldehyde 1mmol and pinacol borine 1.2mmol are moved out glove box, react 10min, pass through
Nuclear magnetic spectrogram obtains the rate of output 99%.
Embodiment 19
Beta-diimine monovalence magnesium compound catalysis 2 thiophene carboxaldehyde is reacted with pinacol borine, and process is as follows:
In glove box, 0.5mL C is being housed6D6Nuclear magnetic tube in sequentially add beta-diimine monovalence magnesium compound
Then 0.001mmol, 2 thiophene carboxaldehyde 1mmol and pinacol borine 1.2mmol are moved out glove box, react 10min, lead to
It crosses nuclear magnetic spectrogram and obtains the rate of output 99%.
Embodiment 20
Beta-diimine monovalence magnesium compound catalysis m-hydroxybenzaldehyde is reacted with pinacol borine, and process is as follows:
In glove box, 0.5mL C is being housed6D6Nuclear magnetic tube in sequentially add beta-diimine monovalence magnesium compound
Then 0.001mmol, m-hydroxybenzaldehyde 1mmol and pinacol borine 1.2mmol are moved out glove box, react 10min,
The rate of output 67% is obtained by nuclear magnetic spectrogram.
Embodiment 21
Beta-diimine monovalence magnesium compound catalysis acetophenone is reacted with pinacol borine, and process is as follows:
In glove box, 0.5mL C is being housed6D6Nuclear magnetic tube in sequentially add beta-diimine monovalence magnesium compound
Then 0.001mmol, acetophenone 1mmol and pinacol borine 1.2mmol are moved out glove box, react 10min, pass through core
Magnetic spectrum figure obtains the rate of output 99%.
Embodiment 22
Beta-diimine monovalence magnesium compound catalysis o-fluoro acetophenone is reacted with pinacol borine, and process is as follows:
In glove box, 0.5mL C is being housed6D6Nuclear magnetic tube in sequentially add beta-diimine monovalence magnesium compound
Then 0.001mmol, o-fluoro acetophenone 1mmol and pinacol borine 1.2mmol are moved out glove box, react 10min, lead to
It crosses nuclear magnetic spectrogram and obtains the rate of output 99%.
Embodiment 23
Beta-diimine monovalence magnesium compound catalysis p-nitroacetophenone is reacted with pinacol borine, and process is as follows:
In glove box, 0.5mL C is being housed6D6Nuclear magnetic tube in sequentially add beta-diimine monovalence magnesium compound
Then 0.001mmol, p-nitroacetophenone 1mmol and pinacol borine 1.2mmol are moved out glove box, react 10min,
The rate of output 99% is obtained by nuclear magnetic spectrogram.
Embodiment 24
Beta-diimine monovalence magnesium compound catalysis 4-Acetylbenzonitrile is reacted with pinacol borine, and process is as follows:
In glove box, 0.5mL C is being housed6D6Nuclear magnetic tube in sequentially add beta-diimine monovalence magnesium compound
Then 0.001mmol, 4-Acetylbenzonitrile 1mmol and pinacol borine 1.2mmol are moved out glove box, react 10min,
The rate of output 99% is obtained by nuclear magnetic spectrogram.
Embodiment 25
Beta-diimine monovalence magnesium compound catalysis benzophenone is reacted with pinacol borine, and process is as follows:
In glove box, 0.5mL C is being housed6D6Nuclear magnetic tube in sequentially add beta-diimine monovalence magnesium compound
Then 0.001mmol, benzophenone 1mmol and pinacol borine 1.2mmol are moved out glove box, react 10min, pass through
Nuclear magnetic spectrogram obtains the rate of output 99%.
Embodiment 26
Beta-diimine monovalence magnesium compound catalyzing iso-butane base phenyl ketone is reacted with pinacol borine, and process is as follows:
In glove box, 0.5mL C is being housed6D6Nuclear magnetic tube in sequentially add beta-diimine monovalence magnesium compound
Then 0.001mmol, isobutyl phenyl ketone 1mmol and pinacol borine 1.2mmol are moved out glove box, react 10min,
The rate of output 99% is obtained by nuclear magnetic spectrogram.
Embodiment 27
Beta-diimine monovalence magnesium compound catalysis acetanisole is reacted with pinacol borine, and process is as follows:
In glove box, 0.5mL C is being housed6D6Nuclear magnetic tube in sequentially add beta-diimine monovalence magnesium compound
0.001mmol, acetanisole 1mmol and pinacol borine 1.2mmol, are then moved out glove box, react
10min obtains the rate of output 99% by nuclear magnetic spectrogram.
Embodiment 28
Beta-diimine monovalence magnesium compound is catalyzed 2', 4', and 6'- trimethylacetophenone is reacted with pinacol borine, process
It is as follows:
In glove box, 0.5mL C is being housed6D6Nuclear magnetic tube in sequentially add beta-diimine monovalence magnesium compound
0.001mmol, 2', 4', 6'- trimethylacetophenone 1mmol and pinacol borine 1.2mmol, are then moved out glove box, instead
20h is answered, the rate of output 97% is obtained by nuclear magnetic spectrogram.
Embodiment 29
Beta-diimine monovalence magnesium compound is catalyzed 2', 4', and 6'- trimethylacetophenone is reacted with pinacol borine, process
It is as follows:
In glove box, 0.5mL C is being housed6D6Nuclear magnetic tube in sequentially add beta-diimine monovalence magnesium compound
0.01mmol, 2', 4', 6'- trimethylacetophenone 1mmol and pinacol borine 1.2mmol, are then moved out glove box, instead
6h is answered, the rate of output 98% is obtained by nuclear magnetic spectrogram.
Embodiment 30
Beta-diimine monovalence magnesium compound catalysis of pimelinketone is reacted with pinacol borine, and process is as follows:
In glove box, 0.5mL C is being housed6D6Nuclear magnetic tube in sequentially add beta-diimine monovalence magnesium compound
Then 0.001mmol, cyclohexanone 1mmol and pinacol borine 1.2mmol are moved out glove box, react 10min, pass through core
Magnetic spectrum figure obtains the rate of output 99%.
Embodiment 31
Beta-diimine monovalence magnesium compound catalysis cyclohexyl ketone is reacted with pinacol borine, and process is as follows:
In glove box, 0.5mL C is being housed6D6Nuclear magnetic tube in sequentially add beta-diimine monovalence magnesium compound
Then 0.001mmol, cyclohexyl ketone 1mmol and pinacol borine 1.2mmol are moved out glove box, react 10min, lead to
It crosses nuclear magnetic spectrogram and obtains the rate of output 99%.
Embodiment 32
Beta-diimine monovalence magnesium compound catalysis 4'- aminoacetophenone is reacted with pinacol borine, and process is as follows:
In glove box, 0.5mL C is being housed6D6Nuclear magnetic tube in sequentially add beta-diimine monovalence magnesium compound
Then 0.001mmol, 4'- aminoacetophenone 1mmol and pinacol borine 1.2mmol are moved out glove box, react 10min,
The rate of output 81% is obtained by nuclear magnetic spectrogram.
Claims (4)
1. application of the beta-diimine monovalence magnesium compound as catalyst in the hydroboration of catalysis aldehydes or ketones；The β-two is sub-
The structural formula of amine monovalence magnesium compound is as follows:
。
2. application according to claim 1, it is characterised in that: under the conditions of anhydrous and oxygen-free, by beta-diimine monovalence magnesium
It closes object to be dissolved in solvent, pinacol borine is added, add aldehydes or ketones, react at room temperature 10min.
3. application according to claim 2, it is characterised in that: the molar ratio of aldehyde and catalyst is 1000:1.
4. application according to claim 2, it is characterised in that: the molar ratio of ketone and catalyst is 1000:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710892796.XA CN107602595B (en) | 2017-09-27 | 2017-09-27 | A kind of beta-diimine monovalence magnesium compound and preparation method thereof and the application in aldehyde ketone hydroboration |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710892796.XA CN107602595B (en) | 2017-09-27 | 2017-09-27 | A kind of beta-diimine monovalence magnesium compound and preparation method thereof and the application in aldehyde ketone hydroboration |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107602595A CN107602595A (en) | 2018-01-19 |
| CN107602595B true CN107602595B (en) | 2019-09-03 |
Family
ID=61058723
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710892796.XA Active CN107602595B (en) | 2017-09-27 | 2017-09-27 | A kind of beta-diimine monovalence magnesium compound and preparation method thereof and the application in aldehyde ketone hydroboration |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107602595B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN108707162B (en) * | 2018-05-14 | 2020-09-01 | 南京林业大学 | Keto hydroboration reaction method under catalyst-free and solvent-free conditions |
| CN108569984B (en) * | 2018-05-25 | 2020-08-04 | 南京林业大学 | Asymmetric diimine magnesium monovalence compound, preparation method thereof and application thereof in alkylene oxide hydroboration reaction |
| CN109942610B (en) * | 2019-04-15 | 2021-06-25 | 南京林业大学 | Hydroboration reaction method for catalyzing aldehyde ketone by Grignard reagent |
| CN111763226A (en) * | 2020-06-16 | 2020-10-13 | 苏州大学 | Hydroboration reaction method of carbonic ester |
| CN111747972A (en) * | 2020-06-16 | 2020-10-09 | 苏州大学 | Deprotonated beta-ketimine lithium compound and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
-
2017
- 2017-09-27 CN CN201710892796.XA patent/CN107602595B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
Non-Patent Citations (3)
| Title |
|---|
| Stable Magnesium(I) Compounds with Mg-Mg Bonds;Shaun P. Green et al;《SCIENCE》;20071214;第318卷;1754-1757 |
| Synthesis and Structural Characterization of Magnesium-Substituted Polystibides [(LMg)4Sb8];Chelladurai Ganesamoorthy et al;《Angew. Chem. Int. Ed.》;20161231;第55卷;4204-4209 |
| Synthesis of a Dimeric Magnesium(I) Compound by an MgI/MgII Redox Reaction;Andreas Stasch;《Angew. Chem. Int. Ed.》;20141231;第53卷;10200-10203 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107602595A (en) | 2018-01-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107602595B (en) | A kind of beta-diimine monovalence magnesium compound and preparation method thereof and the application in aldehyde ketone hydroboration | |
| Laszlo | Catalysis of organic reactions by inorganic solids | |
| Gant et al. | The first enantioselective synthesis of the chemotactic factor sirenin by an intramolecular [2+ 1] cyclization using a new chiral catalyst | |
| Yamada et al. | Enantioselective borohydride reduction catalyzed by optically active cobalt complexes | |
| CN102807577B (en) | Chiral compound | |
| CN103706383B (en) | Catalyst for catechol guaiacol and preparation method thereof | |
| Wu et al. | Synthesis of N-α-pyridylmethyl amino alcohols and application in catalytic asymmetric addition of diethylzinc to aromatic aldehydes | |
| Zhou et al. | Catalytic effect and recyclability of imidazolium-tagged bis (oxazoline) based catalysts in asymmetric Henry reactions | |
| AU674067B2 (en) | Enantioselective oxazaborolidine catalysts | |
| Sanjeevakumar et al. | Highly enantioselective Henry reaction catalyzed by a new chiral C2-symmetric N, N′-bis (isobornyl) ethylenediamine–copper complex | |
| WO2021253847A1 (en) | Use of deprotonated phenyl bridged β-ketimine lithium compound in hydroboration reaction | |
| CN107556195B (en) | A kind of beta-diimine monovalence magnesium compound and preparation method thereof and the application in aldehyde ketone silicon cyaniding | |
| CN111763135A (en) | Application of deprotonated phenyl bridged beta-ketimine lithium compound in preparation of alcohol from ester | |
| CN108727161B (en) | Method for preparing phenol by efficient in-situ hydroxylation of phenylboronic acid | |
| WO2021253868A1 (en) | Method for hydroboration of carbonate | |
| CN101402582A (en) | Synthesis of alpha-hydroxyl-beta-aminophenol with optical activity | |
| Yamaguchi et al. | Asymmetric reduction with chiral reagents from lithium aluminum hydride and (S)-(-)-N-(o-substituted benzyl)-. alpha.-phenylethylamines | |
| CN108276433A (en) | A kind of Hydroboronation process of ester | |
| CN109265489B (en) | Method for preparing cyclic carbonate | |
| Hua et al. | Bidentate N, O-aluminum complexes: Synthesis, characterization and catalytic study for MPV reduction reactions | |
| CN108191814B (en) | Method for synthesizing cyclohexanone ethylene ketal under catalysis of titanium ammonium phosphotungstate composite salt | |
| CN103709204B (en) | A kind of cobalt complex, preparation method and its usage | |
| Nishinaga et al. | Mechanism of the formation of cyclopentadienone derivatives from 4-aryl-2, 6-di-tert-butylphenols by base-catalyzed oxygenation | |
| CN108358959A (en) | A kind of Hydroboronation process of isocyanide ester | |
| CN101773856B (en) | Oxazoline Schiff base ligand metal complex catalyst and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information |
Inventor after: Ma Mengtao Inventor after: Lu Kai Inventor after: Wang Weifan Inventor after: Yao Weiwei Inventor before: Ma Mengtao Inventor before: Wang Weifan Inventor before: Lu Kai Inventor before: Yao Weiwei |
|
| CB03 | Change of inventor or designer information | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20180119 Assignee: Nanjing Subang Biological Technology Co., Ltd. Assignor: Nanjing Forestry University|Nanjing University of traditional Chinese Medicine Contract record no.: X2019320000093 Denomination of invention: A u03b2 - diimide monovalent magnesium compound and its preparation and application in the borohydride of aldehydes and ketones Granted publication date: 20190903 License type: Common License Record date: 20191010 Application publication date: 20180119 Assignee: Nanjing Yu Bao new material Co., Ltd. Assignor: Nanjing Forestry University|Nanjing University of traditional Chinese Medicine Contract record no.: X2019320000094 Denomination of invention: A u03b2 - diimide monovalent magnesium compound and its preparation and application in the borohydride of aldehydes and ketones Granted publication date: 20190903 License type: Common License Record date: 20191010 Application publication date: 20180119 Assignee: Jiangsu Hongshan Engineering Technology Co., Ltd. Assignor: Nanjing Forestry University|Nanjing University of traditional Chinese Medicine Contract record no.: X2019320000095 Denomination of invention: A u03b2 - diimide monovalent magnesium compound and its preparation and application in the borohydride of aldehydes and ketones Granted publication date: 20190903 License type: Common License Record date: 20191010 |
|
| EE01 | Entry into force of recordation of patent licensing contract | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210526 Address after: 361101 No.7 Xiangyue Road, Xiamen Torch hi tech Zone (Xiang'an) Industrial Zone, Xiamen City, Fujian Province Patentee after: XIAMEN OURUIJIE BIOTECHNOLOGY Co.,Ltd. Address before: Longpan road Xuanwu District of Nanjing city of Jiangsu Province, No. 159 210037 Patentee before: NANJING FORESTRY University Patentee before: Nanjing University of Chinese Medicine |
|
| TR01 | Transfer of patent right |