CN106317094A - Method for synthesizing chiral boron compound containing trifluoromethyl and compound - Google Patents
Method for synthesizing chiral boron compound containing trifluoromethyl and compound Download PDFInfo
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- CN106317094A CN106317094A CN201510378131.8A CN201510378131A CN106317094A CN 106317094 A CN106317094 A CN 106317094A CN 201510378131 A CN201510378131 A CN 201510378131A CN 106317094 A CN106317094 A CN 106317094A
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- 0 *C(C=CC(F)(F)F)=O Chemical compound *C(C=CC(F)(F)F)=O 0.000 description 1
- DMLMXXGRMJZDEI-VOTSOKGWSA-N Cc(cc1)ccc1C(/C=C/C(F)(F)F)=O Chemical compound Cc(cc1)ccc1C(/C=C/C(F)(F)F)=O DMLMXXGRMJZDEI-VOTSOKGWSA-N 0.000 description 1
- VIVHSKGMXVQFTC-UHFFFAOYSA-N Cc(cc1)ccc1C(CCC(F)(F)F)=O Chemical compound Cc(cc1)ccc1C(CCC(F)(F)F)=O VIVHSKGMXVQFTC-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a method for synthesizing a chiral boron compound containing trifluoromethyl and having a potential biological activity. With beta-trifluoromethyl-alpha,beta-unsaturated ketone and bis(pinacolato)diborane as raw materials, and a chiral ligand copper salt as a catalyst, an asymmetric boronizing reaction is carried out for synthesis of the chiral boron compound. Compared with a reported method for synthesizing the chiral boron compound, the method has the advantages of easily obtained raw materials, simple operation, wide application range and mild reaction conditions, the product contains a carbon chiral center connected with trifluoromethyl, and the product has the potential biological activity.
Description
Technical field
The invention discloses a kind of conjunction containing trifluoromethyl chirality boron compound with potential source biomolecule activity
One-tenth method.With β-trifluoromethyl-alpha, alpha, beta-unsaturated ketone and duplex pinacol base diborane are raw material, chirality
Part mantoquita is catalyst, carries out asymmetric boronation and chirality boron compound is synthesized.With report conjunction
The method becoming chirality boron compound compares, and raw material of the present invention is easy to get, easy and simple to handle, applied widely
And reaction condition is gentle, product contains the carbon chiral centre connecting trifluoromethyl, has potential
Biological activity.
Background technology
Chirality boron compound is important organic reagent, has in industry, agricultural and medicine and other fields
Quite varied purposes.Trifluoromethyl group is particularly important functional group, can greatly change chemical combination
The biological activity of thing and physical property, in the drug molecule being widely used in and functional material.
At present, there is multiple method for synthesis of chiral boron compound (Schiffner etc., Angew.Chem.Int.
Ed.2010,49,1194-1196；Calow etc., Org.Biomol.Chem.2012,10,5485-5497).
Wherein, by α, the method for the asymmetric boronation of beta-unsaturated carbonyl compound is to prepare chirality quickly and efficiently
One of approach of boron compound, related manufacturing processes has: 1) copper catalysis α, beta-unsaturated carbonyl compound
The reaction of asymmetric boronation (Kobayashi etc., Angew.Chem.Int.Ed.2012,51,
12763-12766)；2) nickel catalysis alpha, beta-unsaturated carbonyl compound asymmetric boronation reaction (Lillo etc.,
Org.Biomol.Chem.2009,7,4674-4676)；3) rhodium catalysis alpha, beta-unsaturated carbonyl compound is not
Symmetrical boronation reaction (Shiomi etc., Chem.Commun., 2009,5987-5989)；4) organic catalysis
Alpha, beta-unsaturated carbonyl compound asymmetric boronation reaction (Radomkit etc., Angew.Chem.Int.Ed.
2014,53,3387-3391).But, β-trifluoromethyl-alpha, alpha, beta-unsaturated ketone is also not applied to asymmetric
In boronation reaction, containing the carbon chiral centre being connected with trifluoromethyl in its product, there is potential life
Thing activity.
The present invention utilizes β-trifluoromethyl-alpha, alpha, beta-unsaturated ketone 2 and duplex pinacol base diborane 3 to carry out not
Symmetrical boronation reaction, has synthesized a series of chirality boron compound 1 containing trifluoromethyl.
Summary of the invention
It is an object of the invention to provide a kind of raw material be easy to get, reaction condition gentleness, wide adaptability, energy
Synthesize the method with potential source biomolecule activity trifluoromethyl chirality boron compound simply and easily.
To achieve these goals, technical scheme is as follows:
With β-trifluoromethyl-alpha, alpha, beta-unsaturated ketone and duplex pinacol base diborane are initiation material, are urging
Under conditions of agent and chiral ligand exist, heating carries out asymmetric boronation reaction in the basic conditions,
The synthesis chirality boron compound containing trifluoromethyl.
With mantoquita such as Hydro-Giene (Water Science). CuI as catalyst precarsor, add chiral ligand such as (R, S)-Josiphos
With alkali such as potassium phosphate K3PO4, where heating condition carries out β-trifluoromethyl-alpha, alpha, beta-unsaturated ketone and duplex frequency
Asymmetric boronation reaction (reaction equation (1)) of alcohol radical diborane, reaction separates through silicagel column after terminating
Purification carries out product separation and sign, obtains containing trifluoromethyl chirality boron compound.
Described β-trifluoromethyl-alpha, the structure of alpha, beta-unsaturated ketone is as follows:
Wherein R is appointing in aryl, naphthyl or heterocyclic aryl with substituent group on phenyl, phenyl ring
Anticipate one or two or more kinds, on above-mentioned phenyl ring with substituent group be C1-C4Alkyl, methoxyl group,
One or two or more kinds in bromine, chlorine, fluorine, acetyl group, trifluoromethyl or hydroxyl, benzene substitution in ring
The number of base is 1-3；
The structure of described duplex pinacol base diborane is as follows, is abbreviated as B2pin2,
Described initiation material β-trifluoromethyl-alpha, alpha, beta-unsaturated ketone and duplex pinacol base diborane mole
Ratio is 1:1-1:2, and preferred molar ratio is 1:1-1:1.5；
Described catalyst is mantoquita, for the one in Cu-lyt., cuprous bromide or Hydro-Giene (Water Science). or two
Plant or three kinds, preferably Hydro-Giene (Water Science).；Described chiral ligand be (R)-BINAP,
(R)-(S)-NMe2-PPh2-Mandyphos、(R,S)-Josiphos、(S,S)-Me-Duphos、
Any one or two kinds in (S, S, R, R)-Tangphos, (R, R)-Walphos or (S, S)-Taniaphos
Above, preferably (R, S)-Josiphos；β-trifluoromethyl-alpha, alpha, beta-unsaturated ketone with the mol ratio of chiral ligand is
1:0.03-1:0.15, preferred molar ratio is 1:0.05-1:0.10；β-trifluoromethyl-alpha, alpha, beta-unsaturated ketone and mantoquita
Mol ratio be 1:0.02-1:0.10, preferred molar ratio is 1:0.03-1:0.08.
Described alkalescence condition is that in potassium carbonate, sodium carbonate or potassium phosphate, any one or two kinds or three kinds are deposited
Condition, preferably phosphoric acid potassium, β-trifluoromethyl-alpha, the mole of alpha, beta-unsaturated ketone and above-mentioned three kinds of materials
The ratio of integral molar quantity be 1:0.04-1:0.20, be preferably in a proportion of 1:0.05-1:0.15.
The solvent of described asymmetric boronation reaction is 1,4-dioxane, oxolane, the tert-butyl alcohol or special penta
One or two or more kinds in alcohol, preferably tertriary amylo alcohol, β-trifluoromethyl-alpha, alpha, beta-unsaturated ketone is in a solvent
Molar concentration be 0.01-1.0M, preferably molar concentration be 0.05-0.5M；
The response time of described asymmetric boronation reaction is 10-30 hour, and the preferably response time is 12-24
Hour, reaction temperature is 30-120 DEG C, and preferable reaction temperature is 40-100 DEG C.
According to the chirality boron compound containing trifluoromethyl of the synthetic method synthesis that the present invention provides, structure
Formula is as follows:
It is abbreviated as
Wherein R is on phenyl, phenyl ring in aryl, naphthyl or heterocyclic aryl with substituent group
Plant or more than two kinds；On phenyl ring, institute's band substituent group is a length of C of chain1-C4Alkyl, methoxyl group, bromine,
One or two or more kinds in chlorine, fluorine, acetyl group, trifluoromethyl or hydroxyl, benzene ring substituents
Number is 1-3.
The invention have the advantages that
1) reaction raw materials β-trifluoromethyl-alpha, alpha, beta-unsaturated ketone has structure diversity, can be used to close
Become there is the chirality boron compound containing trifluoromethyl of various substituent group.
2) reaction raw materials duplex pinacol base diborane commercially available, it is easy to preparation.
3) the chirality boron compound synthetic reaction condition containing trifluoromethyl is gentle, step is simple, product
Yield and enantioselectivity are high and applied widely.
4) product contains the carbon chiral centre being connected with trifluoromethyl, has potential source biomolecule activity.
In a word, the present invention utilizes β-trifluoromethyl-alpha, alpha, beta-unsaturated ketone and duplex pinacol base diborane
Asymmetric boronation be synthesized have various substituent group containing trifluoromethyl chirality boron compound, raw material is just
Preferably being easy to get, easy and simple to handle, target product yield and enantioselectivity are high.
Detailed description of the invention
The present invention is with β-trifluoromethyl-alpha, and alpha, beta-unsaturated ketone is initiation material and reaction raw materials duplex pinacol
Base diborane carries out asymmetric boronation reaction, the synthesis chirality boron compound containing trifluoromethyl.Under by
State embodiment and contribute to being further appreciated by the present invention, but present disclosure is not limited to that.
Embodiment 1
Under nitrogen protection, in 25mL Schlenk reaction bulb, it is sequentially added into Hydro-Giene (Water Science). CuI (1.9
Mg, 0.01mmol), (R, S)-Josiphos (9.6mg, 0.015mmol), potassium phosphate K3PO4(4.2
Mg, 0.02mmol), tertriary amylo alcohol t-AmOH (1.0mL), stir under room temperature add after 30 minutes double
Connection pinacol base diborane 3 (55.9mg, 0.22mmol) and tertriary amylo alcohol t-AmOH (0.5mL),
Stir 10 minutes under room temperature.It is subsequently adding (E)-4,4,4-three fluoro-1-p-methylphenyl-2-alkene-1-ketone 2a and spy
Amylalcohol t-AmOH (0.5mL), stirs 20 hours at 60 DEG C.Filter through kieselguhr after being cooled to room temperature,
Filter cake ethyl acetate (20mL) is washed, filtrate reduced in volume.(eluting is separated through silica gel column chromatography
Liquid: petroleum ether (60-90 DEG C)/ethyl acetate, v/v=60:1), obtain white solid product 1a (43
Mg, yield 63%, ee value 93%).Target product is measured by nuclear magnetic resoance spectrum and high resolution mass spectrum
To confirming, ee value is measured by chiral high performance liquid chromatography.
Embodiment 2
Reactions steps and operation are with embodiment 1, and difference from Example 1 is, mantoquita is protobromide
Copper.Stopped reaction, post-treated obtains target product 1a (39mg, yield 58%, ee value 93%).
Illustrate that cuprous bromide can also as the catalyst of reaction, but not be optimal catalyst.
Embodiment 3
Reactions steps and operation are with embodiment 1, and difference from Example 1 is, mantoquita is protochloride
Copper.Stopped reaction, post-treated obtains target product 1a (6mg, yield 9%).Protochloride is described
Copper can also as the catalyst of reaction, but not be optimal catalyst.
Embodiment 4
Reactions steps and operation are with embodiment 1, and difference from Example 1 is, alkali is sodium carbonate.
Stopped reaction, post-treated obtains target product 1a (36mg, yield 52%, ee value 94%).Explanation
Sodium carbonate can also as the alkali of reaction, but not be optimal alkali.
Embodiment 5
Reactions steps and operation are with embodiment 1, and difference from Example 1 is, alkali is potassium carbonate.
Stopped reaction, post-treated obtains target product 1a (32mg, yield 47%, ee value 94%).Explanation
Potassium carbonate can also as the alkali of reaction, but not be optimal alkali.
Embodiment 6
Reactions steps and operation are with embodiment 1, and difference from Example 1 is, chiral ligand is
(S,S,R,R)-Tangphos.Stopped reaction, post-treated obtain target product 1a (24mg, yield 35%,
Ee value 21%).Illustrate that (S, S, R, R)-Tangphos can also as the chiral ligand of reaction, but not be
Good chiral ligand.
Embodiment 7
Reactions steps and operation are with embodiment 1, and difference from Example 1 is, used molten in reaction
Agent is the tert-butyl alcohol.Stopped reaction, post-treated obtains target product 1a (35mg, yield 41%, ee
Value 84%).Illustrate that the tert-butyl alcohol can be used as the solvent of reaction, but be not optimal solvent.
Embodiment 8
Reactions steps and operation are with embodiment 1, and difference from Example 1 is, β-trifluoromethyl-alpha,
Alpha, beta-unsaturated ketone (E)-4,4,4-three fluoro-1-p-methylphenyl-2-alkene-1-ketone and duplex pinacol base diborane mole
Ratio is 1:1.Stopped reaction, post-treated obtains target product 1a (21mg, yield 31%, ee value
93%).β-trifluoromethyl-alpha, alpha, beta-unsaturated ketone and duplex pinacol base diborane mol ratio are that this is anti-for 1:1
Should occur, but not be optimal mol ratio.
Embodiment 9
Reactions steps and operation are with embodiment 1, and difference from Example 1 is, the response time is 6
h.Stopped reaction, post-treated obtains target product 1a (20mg, yield 29%, ee value 93%).
Illustrate that shortening the response time is unfavorable for the carrying out of reaction.
Embodiment 10
Reactions steps and operation are with embodiment 1, and difference from Example 1 is, reaction temperature is
50℃.Stopped reaction, post-treated obtains target product 1a (39mg, yield 57%, ee value 94%).
Illustrating that reducing reaction temperature is unfavorable for the carrying out of reaction, 50 DEG C is not the optimum temperature reacted.
Embodiment 11
Reactions steps and operation are with embodiment 1, and difference from Example 1 is, reaction temperature is
80℃.Stopped reaction, post-treated obtains target product 1a (38mg, yield 55%, ee value 93%).
Illustrating that improving reaction temperature is unfavorable for the carrying out of reaction, 80 DEG C is not the optimum temperature reacted.
Embodiment 12
Reactions steps and operation are with embodiment 1, and difference from Example 1 is, adds in reaction system
β-the trifluoromethyl-alpha entered, alpha, beta-unsaturated ketone is 2b (40mg, 0.2mmol).Stopped reaction, through after
Process obtains weak yellow liquid target product 1b (33mg, yield 51%, ee value 94%).Target product
Measured by nuclear magnetic resoance spectrum and high resolution mass spectrum and be confirmed.
Embodiment 13
Reactions steps and operation are with embodiment 1, and difference from Example 1 is, adds in reaction system
β-the trifluoromethyl-alpha entered, alpha, beta-unsaturated ketone is 2c (46mg, 0.2mmol).Stopped reaction, through after
Process obtains faint yellow solid target product 1c (44mg, yield 61%, ee value 95%).Target product
Measured by nuclear magnetic resoance spectrum and high resolution mass spectrum and be confirmed.
Embodiment 14
Reactions steps and operation are with embodiment 1, and difference from Example 1 is, adds in reaction system
β-the trifluoromethyl-alpha entered, alpha, beta-unsaturated ketone is 2d (47mg, 0.2mmol).Stopped reaction, through after
Process obtains faint yellow solid target product 1d (29mg, yield 40%, ee value 80%).Target product
Measured by nuclear magnetic resoance spectrum and high resolution mass spectrum and be confirmed.
Embodiment 15
Reactions steps and operation are with embodiment 1, and difference from Example 1 is, adds in reaction system
β-the trifluoromethyl-alpha entered, alpha, beta-unsaturated ketone is 2e (44mg, 0.2mmol).Stopped reaction, through after
Process obtains faint yellow solid target product 1e (35mg, yield 51%, ee value 91%).Target product
Measured by nuclear magnetic resoance spectrum and high resolution mass spectrum and be confirmed.
Embodiment 16
Reactions steps and operation are with embodiment 1, and difference from Example 1 is, adds in reaction system
β-the trifluoromethyl-alpha entered, alpha, beta-unsaturated ketone is 2f (50mg, 0.2mmol).Stopped reaction, through after
Process obtains faint yellow solid target product 1f (45mg, yield 60%, ee value 92%).Target product
Measured by nuclear magnetic resoance spectrum and high resolution mass spectrum and be confirmed.
Embodiment 17
Reactions steps and operation are with embodiment 1, and difference from Example 1 is, adds in reaction system
β-the trifluoromethyl-alpha entered, alpha, beta-unsaturated ketone is 2g (41mg, 0.2mmol).Stopped reaction, through after
Process obtains colourless liquid target product 1g (43mg, yield 65%, ee value 96%).Target product leads to
Cross nuclear magnetic resoance spectrum and high resolution mass spectrum measures and is confirmed.
Typical compound characterizes data
The white solid 1a that embodiment 1-11 obtains, fusing point: 78-80 DEG C.1H NMR(400MHz,
CDCl3) δ 7.89 (d, J=8.1Hz, 2H, aromatic CH), 7.29 (d, J=8.0Hz, 2H,
aromatic CH),3.44(m,2H,COCH2),2.44(s,3H,PhCH3),2.38(m,1H,CH),
1.32and 1.27(s each,6:6H,4×CH3)；13C{1H}NMR(100MHz,CDCl3)δ197.4
(Cq, C=O), 144.6and 133.5 (Cq each), 129.5and 128.4 (aromatic CH), 128.3
(Cq,JC-F=275.4Hz, CF3),84.3(Cq,2×OC(CH3)2),35.2(JC-F=2.7Hz, CH2),
24.7and 24.5(4×CH3),21.8(PhCH3) .HRMS theoretical value [M+H]+C17H23BF3O3:
343.1692；Measured value: 343.1692.
Claims (7)
1. the synthetic method of chirality boron compound containing trifluoromethyl, it is characterised in that: include with
Lower step:
With β-trifluoromethyl-alpha, alpha, beta-unsaturated ketone and duplex pinacol base diborane are initiation material, are urging
Under conditions of agent and chiral ligand exist, heating carries out asymmetric boronation reaction in the basic conditions,
The synthesis chirality boron compound containing trifluoromethyl.
Synthetic method the most according to claim 1, it is characterised in that: described β-trifluoromethyl
The structure of-alpha, beta-unsaturated ketone is as follows:
Wherein R is appointing in aryl, naphthyl or heterocyclic aryl with substituent group on phenyl, phenyl ring
Anticipate one or two or more kinds, on above-mentioned phenyl ring with substituent group be C1-C4Alkyl, methoxyl group,
One or two or more kinds in bromine, chlorine, fluorine, acetyl group, trifluoromethyl or hydroxyl, benzene substitution in ring
The number of base is 1-3；
The structure of described duplex pinacol base diborane is as follows, is abbreviated as B2pin2,
Described initiation material β-trifluoromethyl-alpha, alpha, beta-unsaturated ketone and duplex pinacol base diborane mole
Ratio is 1:1-1:2, and preferred molar ratio is 1:1-1:1.5.
Synthetic method the most according to claim 1, it is characterised in that: described catalyst is copper
Salt, for the one in Cu-lyt., cuprous bromide or Hydro-Giene (Water Science). or two kinds or three kinds, preferably iodate
Cuprous；Described chiral ligand is (R)-BINAP, (R)-(S)-NMe2-PPh2-Mandyphos、
(R, S)-Josiphos, (S, S)-Me-Duphos, (S, S, R, R)-Tangphos, (R, R)-Walphos or
Any one or more than two kinds in (S, S)-Taniaphos, preferably (R, S)-Josiphos；β-trifluoromethyl
-α, alpha, beta-unsaturated ketone is 1:0.03-1:0.15 with the mol ratio of chiral ligand, and preferred molar ratio is
1:0.05-1:0.10；β-trifluoromethyl-alpha, alpha, beta-unsaturated ketone is 1:0.02-1:0.10 with the mol ratio of mantoquita, excellent
Selecting mol ratio is 1:0.03-1:0.08.
Synthetic method the most according to claim 1, it is characterised in that: described alkalescence condition is
The conditions that in potassium carbonate, sodium carbonate or potassium phosphate, any one or two kinds or three kinds exist, preferably phosphoric acid
Potassium, β-trifluoromethyl-alpha, the mole of alpha, beta-unsaturated ketone with the ratio of the integral molar quantity of above-mentioned three kinds of materials is
1:0.04-1:0.20, it is preferably in a proportion of 1:0.05-1:0.15.
Synthetic method the most according to claim 1, it is characterised in that: described asymmetric boronation
The solvent of reaction be the one in 1,4-dioxane, oxolane, the tert-butyl alcohol or tertriary amylo alcohol or two kinds with
On, preferably tertriary amylo alcohol, β-trifluoromethyl-alpha, alpha, beta-unsaturated ketone molar concentration in a solvent is 0.01-1.0
M, preferably molar concentration are 0.05-0.5M.
Synthetic method the most according to claim 1, it is characterised in that: described asymmetric boronation is anti-
The response time answered is 10-30 hour, and the preferably response time is 12-24 hour, and reaction temperature is 30-120
DEG C, preferable reaction temperature is 40-100 DEG C.
7. the chirality boron containing trifluoromethyl according to the synthesis of claim 1-6 arbitrary described synthetic method
Compound, it is characterised in that: structural formula is as follows:
It is abbreviated as
Wherein R is on phenyl, phenyl ring in aryl, naphthyl or heterocyclic aryl with substituent group
Plant or more than two kinds；On phenyl ring, institute's band substituent group is a length of C of chain1-C4Alkyl, methoxyl group, bromine,
One or two or more kinds in chlorine, fluorine, acetyl group, trifluoromethyl or hydroxyl, benzene ring substituents
Number is 1-3.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111153819A (en) * | 2020-01-15 | 2020-05-15 | 湖南科技大学 | Method for splitting 3-chloro-phenylglycine enantiomer by liquid-liquid extraction |
-
2015
- 2015-07-01 CN CN201510378131.8A patent/CN106317094B/en not_active Expired - Fee Related
Non-Patent Citations (3)
| Title |
|---|
| J A. SCHIFFNER. ET AL: ""Enantioselective Conjugate Borylation"", 《ANGEW. CHEM. INT. ED》 * |
| S KOBAYASHI. ET AL: ""Chiral Copper(II)-Catalyzed Enantioselective Boron Conjugate Additions toa,b-Unsaturated Carbonyl Compounds in Water"", 《ANGEW. CHEM. INT. ED》 * |
| S RADOMKIT. ET AL: ""Enantioselective Synthesis of Boron-Substituted Quaternary Carbon Stereogenic Centers through NHC-Catalyzed Conjugate Additions of (Pinacolato)boron Units to Enones"", 《ANGEW. CHEM. INT. ED》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111153819A (en) * | 2020-01-15 | 2020-05-15 | 湖南科技大学 | Method for splitting 3-chloro-phenylglycine enantiomer by liquid-liquid extraction |
| CN111153819B (en) * | 2020-01-15 | 2022-09-02 | 湖南科技大学 | Method for splitting 3-chloro-phenylglycine enantiomer by liquid-liquid extraction |
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