CN109776338A - Salan ligand, metal-Salan complex and prepare chiral alpha-hydroxy-beta -one ester compound method - Google Patents
Salan ligand, metal-Salan complex and prepare chiral alpha-hydroxy-beta -one ester compound method Download PDFInfo
- Publication number
- CN109776338A CN109776338A CN201910178985.XA CN201910178985A CN109776338A CN 109776338 A CN109776338 A CN 109776338A CN 201910178985 A CN201910178985 A CN 201910178985A CN 109776338 A CN109776338 A CN 109776338A
- Authority
- CN
- China
- Prior art keywords
- salan
- beta
- hydroxy
- metal
- reaction
- 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.)
- Pending
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of Salan ligand, metal-Salan complex and preparation are chiralαHydroxyl-βThe method of -one ester compound.Specifically with (1S,2SSalan ligand derived from) -1,2- diphenyl ethylene diamine is chiral source, prepares metal-Salan complex with metallic ion coordination, and gained metal-Salan complex reacts in organic solvent with substrate, oxidant, and chirality is madeαHydroxyl-β-one acid esters, yield highest 99%, enantiomeric excess value highest 99% are highest enantioselectivities so far.Reaction condition of the present invention is mild, and catalyst amount is few, easy to operate, and enantiomeric excess value is high, has a good application prospect.
Description
Technical field
The invention belongs to organic synthesis catalytic fields, and in particular to a kind of Salan ligand, metal-Salan complex and system
The method of standby chiral alpha-hydroxy-beta -one ester compound.
Background technique
Chirality is one of essential attribute of nature.In recent years, with the development of organic synthesis, more and more chiralityizations
Closing object can be obtained by chemical synthesis.Asymmetry catalysis has become the important means of chiral material synthesis, is chiral drug
One of the key technology that industrialized production must be broken through.
The efficient pesticides indoxacarb of DuPont Corporation's research and development, chloro- 2, the 3- dihydro -2- hydroxyl of key intermediate (+) -5-
Base -1- oxygen -2H- indenes -2- carboxylate methyl ester is exactly to carry out 'alpha '-hydroxylation by 5- chlorine indone methyl formate to obtain.In addition to this, hand
Property Alpha-hydroxy-beta-ketoester or various bioactive natural products and drug such as kjellmanianone, hamigeran A and
Generally existing and important structural core in vindoline.So having very for the research of chiral alpha-hydroxy-beta -one acid esters
Good application value.
Forefathers constantly probe under, chiral alpha-hydroxy-beta -one acid esters has had a great development.Document
It is catalyst preparation α-hydroxyl with quinine and its derivative that (J.Org.Chem. 2004,69,8165-8167), which is disclosed directly,
A kind of method of base-beta-ketoester, yield obtained by this method is generally in 80-90%, but enantiomeric excess value is 80% or so,
It is relatively less optimistic.Meng etc. (Org.Lett.2017,19,448-451) is prepared chiral by organotransition metal complex
Alpha-hydroxy-beta-ketoester, yields good result, and yield reaches 99%, and enantiomeric excess value is also up to 98%, still, should
Catalyst amount reported in the literature used is 10mol%, relatively high.
Summary of the invention
The present invention prepares Alpha-hydroxy-beta-ketoester, obtains by synthesizing a kind of metal-Salan complex as catalyst
Chiral alpha-hydroxy-beta -one acid esters yield and enantiomeric excess value be up to 99%, be the selection of highest mapping so far
Property.In addition to this, reaction condition of the present invention is mild, and catalyst amount is few, easy to operate, has a good application prospect.
The present invention is achieved by the following technical solutions:
A kind of Salan ligand, structural formula are as follows:
Wherein, R is aryl, alkyl or silicon substrate.
The preparation method of Salan ligand described above:
Wherein, R is aryl, alkyl or silicon substrate；
Raw material (1S, 2S) -1,2- diphenyl ethylene diamine is dissolved in organic solvent, phenyl salicylic aldehyde derivatives are then added,
Sequentially add 1-10 drop HOAc,Molecular sieve is refluxed overnight, and reducing agent is added, and 10-24h is reacted at room temperature, then by solvent
It is evaporated, is quenched, is extracted, dried, recrystallized and to obtain Salan ligand.The organic solvent is methanol, ethyl alcohol or tetrahydrofuran；Institute
Recrystallization ethyl alcohol, petroleum ether or the ethyl acetate/petroleum ether mixture stated；The reducing agent is sodium borohydride, aluminum hydride
Lithium or Sodium triacetoxyborohydride.
A kind of metal-Salan complex, structural formula are as follows:
Wherein, M is metal ion, and R is aryl, alkyl or silicon substrate.
Metal-Salan complex the preparation method comprises the following steps: Salan ligand is dissolved in organic solvent, metallic compound is added,
Reaction, obtains metal-Salan complex；The organic solvent is acetonitrile, petroleum ether, ethyl alcohol, methanol, methylene chloride, benzene, first
Benzene and dimethylbenzene；The metallic compound is acetylacetone,2,4-pentanedione zirconium, magnesium perchlorate, titanium tetrachloride, tetraisopropyl titanate, ferric perchlorate
And copper chloride；The temperature of the reaction is 0-100 DEG C, the time 0.5-3h of reaction.It is preferred that 0-70 DEG C of reaction 0.5-1h.
A kind of preparation method of chiral alpha-hydroxy-beta -one ester compound, by (1S, 2S) -1,2- diphenyl ethylene diamine is molten
In organic solvent, metallic compound is added, stirring prepares metal-Salan complex, beta-ketoester and oxidant is then added,
Reaction, obtains chiral alpha-hydroxy-beta -one acid esters through column chromatography for separation:
Wherein, R1For hydrogen atom, halogen, alkyl or alkoxy；R2For alkyl or cycloalkyl.
In chiral alpha-hydroxy-beta -one ester compound preparation method, it is preferable that organic solvent is acetonitrile, petroleum ether, second
Alcohol, methanol, methylene chloride, benzene, toluene and dimethylbenzene.
Preferably, the ratio of the amount of the substance of the metal-Salan complex and beta-ketoester is 1-20%:1, more excellent
Selection of land is 2-10%:1.
Preferably, the oxidant is hydrogen peroxide, cumyl hydroperoxide (CHP) or tert-butyl hydroperoxide
(TBHP), the ratio of the amount of substance and beta-ketoester is 1-5:1, more preferably 1-3:1.
Preferably, the temperature of reaction is 0-100 DEG C, and the time of reaction is 2-10h, it is highly preferred that reaction condition is 0-50
DEG C, time 3-6h.
Beneficial effect
The present invention, for chiral source, is matched with Salan ligand derived from (1S, 2S) -1,2- diphenyl ethylene diamine with metal ion
Position prepares metal-Salan complex, and manufactured catalyst reacts in organic solvent with substrate, oxidant, and chiral alpha-hydroxyl is made
Base-beta-ketoester, yield highest 99%, enantiomeric excess value highest 99% are highest enantioselectivities so far.This hair
Bright reaction condition is mild, and catalyst amount is few, easy to operate, and enantiomeric excess value is high, has a good application prospect.
Specific embodiment
It elaborates below to the embodiment of the present invention, the present embodiment carries out under the premise of the technical scheme of the present invention
Implement, the detailed implementation method and specific operation process are given, but protection scope of the present invention is not limited to following implementation
Example.
Embodiment 1
Prepare ligand L 3 (R is 2- methoxyphenyl)
Under argon gas protection, by (1S, 2S) -1,2- diphenyl ethylene diamine (1.0mmol, 212mg, 1.0equiv) is dissolved in 50mL
Then dehydrated alcohol is added 3- (2- methoxyl group) phenyl salicylic aldehyde (2.0mmol, 456mg, 2.0equiv), continues to stir
Then 10min sequentially adds 5 drop acetic acid,Molecular sieve.Reaction solution is refluxed overnight reaction.It is cooled to 0 DEG C, is added portionwise
NaBH4(3.0 mmol, 113mg, 3.0equiv), is stirred overnight at room temperature.After the reaction was completed, gained mixed solution is evaporated, so
Obtained solid adds NH afterwards4Cl is quenched, and stirs 30min, CH2Cl2Extraction 3 times.Saturated common salt water washing 2 times, anhydrous Na SO4It is dry,
Solvent evaporated, ethyl alcohol recrystallization obtain L3 (541mg, 0.85mmol, 85%yield).
(c=0.5, CHCl3)；
1H NMR(600MHz,CDCl3) δ 9.73 (s, 2H), 7.33 (td, J=8.4,1.8Hz, 2H), 7.29 (dd, J=
7.8,1.8Hz, 2H), 7.22-7.17 (m, 6H), 7.14 (dd, J=7.2,1.8Hz, 2H), 7.03 (td, J=7.8,0.6Hz,
2H), 6.99 (d, J=7.8Hz, 2H), 6.97-6.92 (m, 4H), 6.83 (dd, J=7.8,1.8Hz, 2H), 6.77 (t, J=
7.2Hz, 2 H), 3.99 (s, 2H), 3.84 (d, J=13.8Hz, 2H), 3.76 (s, 6H), 3.64 (d, J=13.8Hz, 2H)；
13C NMR(151MHz,CDCl3)δ156.8,154.8,138.0,131.8,130.8,128.7,128.3,128.2,
128.1, 127.8,127.6,126.3,123.3,120.7,118.9,111.3,66.9,55.8,50.2；
HRMS(ESI)m/z calcd for C42H40N2O4H(M+H)+:637.3066,observed 637.3063.
Other structures ligand is all in accordance with above method preparation.
Embodiment 2
Reaction condition optimization
Metallic compound (5.0mol%) and ligand (5.5mol%) is dissolved in 2mL organic solvent, 30min is stirred at room temperature,
Then 5- chlorine indone methyl formate (1.0equiv.) and oxidant (1.5equiv.) are sequentially added, the reaction was continued 4h.It has reacted
Cheng Hou uses CH2Cl2Extraction 3 times, organic phase is with saturated common salt water washing 2 times.Use anhydrous Na2SO4It dries, filters, gained is molten
Liquid is evaporated, and obtains crude product, obtains sterling through column chromatography for separation.
1 condition optimizing of table
a0℃；b50℃；c30%H2O2；dTert-butyl hydroperoxide (TBHP)；eDoping acetic acid；fHPLC:OD-H (5 μm, 250 mm × 4.6mm), 25 DEG C, hexane/i-PrOH=90/10,1mL/min, 254nm, tR1
(major)=12.5min, tR2(minor)=15.7 min.
By table 1 it is known that corresponding selection is best when ligand is selected as L3.
Embodiment 3
The preparation of chiral alpha-hydroxy-beta -one acid esters
As above formula show Alpha-hydroxy-beta-ketoester preparation process: by L3 (5.5mol%, 3.5mg,
2 mL toluene 0.055equiv.) are dissolved in, are added Zr (acac)4(5.0mol%, 2.4mg, 0.05equiv.), is stirred at room temperature
30min prepares Zr (IV)-Salan complex, then sequentially adds I (0.1mmol, 1.0equiv.), cumyl hydroperoxide
(CHP；80%wt, 0.15mmol, 28.5 mg, 1.5equiv.), room temperature continues to stir 4h.After completion of the reaction, column chromatographs (petroleum
Ether/ethyl acetate=8/1) isolated α-hydroxy-beta -one acid esters II.Products therefrom yield, ee value and its detection method such as table
Shown in 2.
2 Alpha-hydroxies of table-beta-ketoester data analysis
By table 2 it was found that under the premise of not considering that substituent group electrophilic, supplied for electronic influence, gained Alpha-hydroxy-β -one
Acid esters yield and ee value are respectively interposed between 92-99% and 90-99%.
Alpha-hydroxy-beta-ketoester nuclear-magnetism is characterized as below:
1H NMR(600MHz,CDCl3) δ 7.73 (d, J=8.4Hz, 1H), 7.50 (s, 1H), 7.42 (d, J=7.8Hz, 1
), H 4.00 (d, J=14.4Hz, 1H), 3.75 (s, 3H), 3.70 (d, J=17.4Hz, 1H), 3.24 (d, J=17.4Hz, 1H)；
13C NMR(151MHz,CDCl3)δ199.4,171.6,153.6,142.9,132.0,129.1,126.8,126.4,
80.4, 53.6,39.0.
1H NMR(600MHz,CDCl3) δ 7.74 (d, J=8.4Hz, 1H), 6.96 (dd, J=8.4,1.8Hz, 1H), 6.91
(d, J=1.8Hz, 1H), 3.92 (s, 3H), 3.74 (s, 3H), 3.68 (d, J=16.8Hz, 1H), 3.20 (d, J=17.4Hz, 1
H)；
13C NMR(151MHz,CDCl3)δ198.7,172.1,166.5,155.4,127.2,126.6,116.3,109.6,
80.7, 55.8,53.4,39.2.
1H NMR(600MHz,CDCl3) δ 7.69 (d, J=7.8Hz, 1H), 7.29 (s, 1H), 7.24 (d, J=7.8Hz, 1
), H 3.96 (s, 1H), 3.74 (s, 3H), 3.68 (d, J=16.8Hz, 1H), 3.20 (d, J=17.4Hz, 1H), 2.47 (s,
3H)；
13C NMR(151MHz,CDCl3)δ200.2,172.1,152.7,147.9,131.2,129.5,126.8,125.2,
80.6, 53.5,39.1,22.3.
1H NMR(600MHz,CDCl3) δ 7.81 (d, J=7.8Hz, 1H), 7.68 (td, J=7.8,0.6Hz, 1H), 7.50
(d, J=7.8Hz, 1H), 7.44 (t, J=7.2Hz, 1H), 3.99-3.93 (m, 1H), 3.79-3.70 (m, 4H), 3.26 (d, J
=17.4 Hz, 1H)；
13C NMR(151MHz,CDCl3)δ200.9,171.9,152.2,136.2,133.5,128.2,126.5,125.4,
80.4, 53.5,39.3.
1H NMR(600MHz,CDCl3) δ 7.82 (dd, J=8.4,4.8Hz, 1H), 7.18-7.12 (m, 2H), 4.08 (s, 1
), H 3.75 (s, 3H), 3.72 (d, J=17.4Hz, 1H), 3.25 (d, J=17.4Hz, 1H)；
13C NMR(151MHz,CDCl3) δ 198.9,171.6,168.0 (d, J=258.0Hz), 155.2 (d, J=
10.5Hz), 129.9 (d, J=1.6Hz), 127.8 (d, J=10.5Hz), 116.7 (d, J=24.0Hz), 113.4 (d, J=
22.6Hz), 80.5,53.6,39.1 (d, J=1.8Hz)
1H NMR(600MHz,CDCl3) δ 7.80 (d, J=7.8Hz, 1H), 7.67 (td, J=7.8,1.2Hz, 1H), 7.50
(d, J=7.2Hz, 1H), 7.43 (t, J=7.2Hz, 1H), 4.25-4.17 (m, 2H), 4.01 (s, 1H), 3.73 (d, J=
16.8Hz, 1 H), 3.25 (d, J=17.4Hz, 1H), 1.18 (t, J=7.2Hz, 3H)；
13C NMR(151MHz,CDCl3)δ201.0,171.5,152.3,136.1,133.6,128.1,126.5,125.3,
80.3, 62.8,39.3,14.0.
1H NMR(600MHz,CDCl3) δ 7.79 (d, J=7.8Hz, 1H), 7.65 (td, J=7.8,1.2Hz, 1H), 7.48
(d, J=7.2Hz, 1H), 7.42 (t, J=7.8Hz, 1H), 4.02 (s, 1H), 3.65 (d, J=16.8Hz, 1H), 3.22 (d, J
=16.8 Hz, 1H), 1.36 (s, 9H)；
13C NMR(151MHz,CDCl3)δ201.4,170.6,152.3,135.9,133.9,127.9,126.3,125.1,
84.0, 80.5,39.4,27.7.
1H NMR(600MHz,CDCl3) δ 7.43-7.37 (m, 2H), 7.11 (dd, J=7.2,1.2Hz, 1H), 3.94 (s, 1
), H 3.92 (s, 3H), 3.74 (s, 3H), 3.66 (d, J=17.4Hz, 1H), 3.11 (d, J=17.4Hz, 1H)；
13C NMR(151MHz,CDCl3)δ201.0,172.1,156.7,141.2,134.9,129.7,116.7,116.3,
80.2, 55.6,53.5,36.2.
1H NMR(600MHz,CDCl3) δ 7.64 (d, J=7.8Hz, 1H), 7.48 (d, J=7.8Hz, 1H), 7.35 (t, J
=7.8Hz, 1H), 4.02 (s, 1H), 3.75 (s, 3H), 3.63 (d, J=17.4Hz, 1H), 3.12 (d, J=17.4Hz, 1H),
2.36 (s,3H)；
13C NMR(151MHz,CDCl3)δ200.2,171.1,150.2,135.7,134.8,132.3,127.3,121.7,
79.2, 52.5,37.2,16.8.
1H NMR(600MHz,CDCl3) δ 7.84 (dd, J=7.8,0.6Hz, 1H), 7.76 (d, J=7.2Hz, 1H), 7.35
(t, J=7.8Hz, 1H), 4.00 (s, 1H), 3.77 (s, 3H), 3.68 (d, J=18.0Hz, 1H), 3.19 (d, J=18.0Hz,
1H)；
13C NMR(151MHz,CDCl3)δ199.2,170.5,150.9,137.9,134.5,128.9,123.1,120.9,
79.0, 52.7,39.4.
1H NMR(600MHz,CDCl3) δ 7.72 (d, J=7.8Hz, 1H), 7.67 (dd, J=7.8,1.2Hz, 1H), 7.42
(t, J=7.8Hz, 1H), 4.00 (s, 1H), 3.77 (s, 3H), 3.73 (d, J=18.0Hz, 1H), 3.22 (d, J=17.4Hz,
1H)；
13C NMR(151MHz,CDCl3)δ200.1,171.6,149.9,135.8,135.4,132.8,129.7,123.5,
80.0, 53.7,38.4.
1H NMR(600MHz,CDCl3) δ 7.38 (d, J=8.4Hz, 1H), 7.27 (dd, J=8.4,2.4Hz, 1H), 7.22
(d, J=2.4Hz, 1H), 3.98 (s, 1H), 3.85 (s, 3H), 3.74 (s, 3H), 3.65 (d, J=16.8Hz, 1H), 3.18 (d,
J=16.8Hz, 1H)；
13C NMR(151MHz,CDCl3)δ200.9,172.0,159.9,145.2,134.7,127.2,125.7,106.2,
81.1, 55.7,53.5,38.7.
1H NMR(600MHz,CDCl3) δ 7.60 (s, 1H), 7.49 (dd, J=7.8,0.6Hz, 1H), 7.38 (d, J=7.8
Hz, 1H), 4.02 (s, 1H), 3.73 (s, 3H), 3.68 (d, J=16.8Hz, 1H), 3.20 (d, J=16.8Hz, 1H), 2.42
(s, 3H)；
13C NMR(151MHz,CDCl3)δ200.9,172.1,149.6,138.3,137.5,133.7,126.2,125.2,
80.7, 53.5,39.0,21.1.
1H NMR(600MHz,CDCl3) δ 7.92 (d, J=1.8Hz, 1H), 7.77 (dd, J=8.4,1.8Hz, 1H), 7.39
(d, J=7.8Hz, 1H), 3.99 (s, 1H), 3.75 (s, 3H), 3.67 (d, J=17.4Hz, 1H), 3.19 (d, J=17.4Hz, 1
H)；
13C NMR(151MHz,CDCl3)δ198.6,170.5,149.7,137.9,134.3,127.1,127.0,121.2,
79.6, 52.6,37.9.
1H NMR(600MHz,CDCl3) δ 7.47 (dd, J=8.4,4.8Hz, 1H), 7.44 (dd, J=7.2,2.4Hz,
1H), 7.40 (td, J=8.4,2.4Hz, 1H), 4.02 (s, 1H), 3.75 (s, 3H), 3.69 (d, J=17.4Hz, 1H), 3.22
(d, J=17.4Hz, 1H)；
13C NMR(151MHz,CDCl3) δ 200.0 (d, J=2.7Hz), 171.6,162.5 (d, J=247.9Hz),
147.6 (d, J=2.1Hz), 135.2 (d, J=7.6Hz), 128.0 (d, J=7.9Hz), 124.0 (d, J=23.6Hz),
111.1 (d, J=22.0 Hz), 81.0,53.6,38.7.
1H NMR(600MHz,CDCl3)δ7.20(s,1H),6.91(s,1H),4.00(s,3H),3.92(s,3H),3.75
(s, 3H), 3.64 (d, J=17.4Hz, 1H), 3.17 (d, J=17.4Hz, 1H)；
13C NMR(151MHz,CDCl3)δ199.1,172.2,156.8,150.0,148.1,126.1,107.3,105.4,
80.8, 56.4,56.2,53.4,39.0.
1H NMR(600MHz,CDCl3) δ 7.61 (t, J=7.8Hz, 1H), 7.03 (dd, J=7.8,0.6Hz, 1H), 6.84
(d, J=7.8Hz, 1H), 3.97 (s, 3H), 3.93 (s, 1H), 3.73 (s, 3H), 3.67 (d, J=17.4Hz, 1H), 3.19
(d, J=16.8Hz, 1H)；
13C NMR(151MHz,CDCl3)δ197.3,170.8,158.1,153.3,137.1,120.7,117.1,108.6,
79.6, 54.9,52.4,37.6.
1H NMR(600MHz,CDCl3) δ 7.66 (td, J=7.8,4.8Hz, 1H), 7.27 (d, J=7.2Hz, 1H), 7.06
(t, J=8.4Hz, 1H), 4.01 (s, 1H), 3.76 (s, 3H), 3.73 (d, J=17.4Hz, 1H), 3.26 (d, J=17.4Hz,
1H)；
13C NMR(151MHz,CDCl3) δ 197.0 (d, J=1.6Hz), 171.4,160.5,158.8,153.7 (d, J=
1.9 Hz), 138.2 (d, J=8.4Hz), 122.3 (d, J=4.2Hz), 115.1 (d, J=18.6Hz), 80.7,53.6,39.0
(d, J=1.2 Hz)
Obviously, various changes and modifications can be made to the invention without departing from essence of the invention by those skilled in the art
Mind and range.In this way, if these modifications and changes of the present invention belongs to the range of the claims in the present invention and its equivalent technologies
Within, then the present invention is also intended to include these modifications and variations.
Claims (10)
1. a kind of Salan ligand, which is characterized in that structural formula are as follows:
Wherein, R is aryl, alkyl or silicon substrate.
2. a kind of preparation method of Salan ligand described in claim 1, which comprises the following steps:
Wherein, R is aryl, alkyl or silicon substrate；
Raw material (1S, 2S) -1,2- diphenyl ethylene diamine is dissolved in organic solvent, phenyl salicylic aldehyde derivatives are then added, successively
The HOAc of addition 1-10 drop,Molecular sieve is refluxed overnight, and reducing agent is added, and is reacted at room temperature 10-24h, is then evaporated solvent,
It is quenched, extracted, being dried, being recrystallized and to be obtained Salan ligand.
3. the preparation method of Salan ligand according to claim 2, which is characterized in that the organic solvent is methanol, ethyl alcohol
Or tetrahydrofuran；Recrystallization ethyl alcohol, petroleum ether or the ethyl acetate/petroleum ether mixture；The reducing agent is boron
Sodium hydride, lithium aluminium hydride reduction or Sodium triacetoxyborohydride.
4. a kind of metal-Salan complex, which is characterized in that structural formula is as follows:
Wherein, M is metal ion, and R is aryl, alkyl or silicon substrate.
5. a kind of preparation method of metal-Salan complex, which is characterized in that Salan ligand is dissolved in organic solvent, is added
Metallic compound, reaction, obtains metal-Salan complex；Wherein, the organic solvent is acetonitrile, petroleum ether, ethyl alcohol, first
Alcohol, methylene chloride, benzene, toluene and dimethylbenzene；The metallic compound is acetylacetone,2,4-pentanedione zirconium, magnesium perchlorate, titanium tetrachloride, metatitanic acid
Tetra-isopropyl, ferric perchlorate and copper chloride；The temperature of the reaction is 0-100 DEG C, the time 0.5-3h of reaction, preferably 0-70 DEG C
React 0.5-1h.
6. a kind of chiral alpha-hydroxy-beta -one ester compound preparation method, which is characterized in that by (1S, 2S) -1,2- diphenyl
Ethylenediamine is dissolved in organic solvent, and metallic compound is added, and stirring prepares metal-Salan complex, beta-ketoester is then added
And oxidant, reaction obtain chiral alpha-hydroxy-beta -one acid esters through column chromatography for separation:
Wherein, R1For hydrogen atom, halogen, alkyl or alkoxy；R2For alkyl or cycloalkyl.
7. a kind of chiral alpha according to claim 6-hydroxy-beta -one ester compound preparation method, which is characterized in that
Organic solvent is acetonitrile, petroleum ether, ethyl alcohol, methanol, methylene chloride, benzene, toluene and dimethylbenzene.
8. a kind of chiral alpha according to claim 6-hydroxy-beta -one ester compound preparation method, which is characterized in that
The mass ratio of the material of the metal-Salan complex and beta-ketoester is 1-20%:1, preferably 2-10%:1.
9. a kind of chiral alpha according to claim 6-hydroxy-beta -one ester compound preparation method, which is characterized in that
The oxidant is hydrogen peroxide, cumyl hydroperoxide (CHP) or tert-butyl hydroperoxide (TBHP), the amount and β -one of substance
The ratio of acid esters is 1-5:1, preferably 1-3:1.
10. a kind of chiral alpha according to claim 6-hydroxy-beta -one ester compound preparation method, which is characterized in that
The temperature of reaction is 0-100 DEG C, and the time of reaction is 2-10h, preferably 0-50 DEG C reaction 3-6h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910178985.XA CN109776338A (en) | 2019-03-11 | 2019-03-11 | Salan ligand, metal-Salan complex and prepare chiral alpha-hydroxy-beta -one ester compound method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910178985.XA CN109776338A (en) | 2019-03-11 | 2019-03-11 | Salan ligand, metal-Salan complex and prepare chiral alpha-hydroxy-beta -one ester compound method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109776338A true CN109776338A (en) | 2019-05-21 |
Family
ID=66487818
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910178985.XA Pending CN109776338A (en) | 2019-03-11 | 2019-03-11 | Salan ligand, metal-Salan complex and prepare chiral alpha-hydroxy-beta -one ester compound method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109776338A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113121338A (en) * | 2021-03-31 | 2021-07-16 | 浙江工业大学 | Synthetic method of alpha-hydroxy-beta-keto acid ester compound |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1630555A (en) * | 2001-06-29 | 2005-06-22 | 纳幕尔杜邦公司 | Hydroxylation of beta-dicarbonyls with zirconium catalysts |
-
2019
- 2019-03-11 CN CN201910178985.XA patent/CN109776338A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1630555A (en) * | 2001-06-29 | 2005-06-22 | 纳幕尔杜邦公司 | Hydroxylation of beta-dicarbonyls with zirconium catalysts |
Non-Patent Citations (1)
| Title |
|---|
| FAN YANG，ET AL.: ""Visible Light-Induced Salan-Copper(II)-Catalyzed Enantioselective Aerobic a-Hydroxylation of b-Keto Esters"", 《ADV. SYNTH. CATAL.》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113121338A (en) * | 2021-03-31 | 2021-07-16 | 浙江工业大学 | Synthetic method of alpha-hydroxy-beta-keto acid ester compound |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | Highly enantioselective phenylacetylene addition to aldehydes catalyzed by a chiral N, O-ferrocene ligand | |
| Xiong et al. | Synthesis of salan (salalen) ligands derived from binaphthol for titanium-catalyzed asymmetric epoxidation of olefins with aqueous H2O2 | |
| CN105753703A (en) | Novel method for asymmetric alpha-hydroxylation of beta-dicarbonyl compound by photo-oxidation under action of quinine derived N-O phase transfer catalyst | |
| CN112354565B (en) | Graphene oxide supported ruthenium catalyst and preparation method and application thereof | |
| CN105521826A (en) | Zirconium catalyst and method for preparing chiral alpha-hydroxy-beta-keto ester compound by use of zirconium catalyst | |
| CN101012187A (en) | Chiral diene ligand, synthesis method and its application in asymmetric reaction | |
| CN111961087A (en) | Semi-sandwich ruthenium complex containing ortho-position carborane-based benzothiazole, and preparation and application thereof | |
| CN108329194A (en) | A kind of citronellal prepares the method for isopulegol and its recovery method of catalyst | |
| CN109956970A (en) | Biphenyl type tridentate ligand ruthenium complex and its preparation method and application | |
| CN102030721A (en) | Method for synthesizing chiral benzosultam via palladium-catalytic asymmetric hydrogenation | |
| CN106748693B (en) | A kind of synthetic method of alpha-hydroxyacetone compounds | |
| CN109776338A (en) | Salan ligand, metal-Salan complex and prepare chiral alpha-hydroxy-beta -one ester compound method | |
| CN109776245A (en) | A kind of method that iridium catalysis asymmetric hydrogenation prepares chiral alcohol | |
| Zong et al. | Ruthenium carbonyl complexes supported by pyridine-alkoxide ligands: synthesis, structure and catalytic oxidation of secondary alcohols | |
| CN103553931A (en) | Method for synthesizing chiral diketone compound | |
| CN114560892A (en) | Chiral tridentate nitrogen phosphine ligand synthesized based on ferrocene skeleton and application thereof | |
| CN114082446A (en) | Chiral zirconium catalyst for preparing chiral alpha-hydroxy-beta-keto ester compound and preparation method thereof | |
| CN115322100A (en) | Delta, epsilon-alkenyl ketone compound and preparation method and application thereof | |
| CN101844980B (en) | Method for preparing chiral alpha-hydroxy-beta-keto ester compound by utilizing chiral beta-alkoxy beta'-alkamine as catalyst | |
| CN114874081A (en) | Preparation method of green efficient alpha-functionalized ketone | |
| CN110590859B (en) | Manganese complex, preparation method and application thereof | |
| CN108794541B (en) | Pyridine-methanol-containing ruthenium carbonyl complex and application thereof | |
| Liu et al. | Efficient Synthesis of Benzimidazole and Quinoline Derivatives Catalyzed by Functionalized Amidato Ruthenium Complexes in Water via Acceptorless Dehydrogenative Coupling Strategy | |
| CN112851652A (en) | Catalytic oxidation synthesis method of 2- (substituted xanthyl) benzofuran compound | |
| CN112979714A (en) | Triplecene carbene tridentate metal complex 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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190521 |