CN103788133A - Phosphorus-containing five-membered heterocycle compound and synthesis method thereof - Google Patents
Phosphorus-containing five-membered heterocycle compound and synthesis method thereof Download PDFInfo
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- CN103788133A CN103788133A CN201410029708.XA CN201410029708A CN103788133A CN 103788133 A CN103788133 A CN 103788133A CN 201410029708 A CN201410029708 A CN 201410029708A CN 103788133 A CN103788133 A CN 103788133A
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- ZATIJXWTXXUICY-UHFFFAOYSA-N OCC(CCC1)P1c1ccccc1 Chemical compound OCC(CCC1)P1c1ccccc1 ZATIJXWTXXUICY-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention relates to a phosphorus-containing five-membered heterocycle compound and a synthesis method thereof, belonging to the technical field of synthesis of organic compounds. The phosphorus-containing five-membered heterocycle compound has the general formula described in the specification, wherein R<1> is phenyl, a substituted phenyl group or a alkyl group; R<2> is a hydrogen atom, methyl sulfonyl, p-tolylsulfonyl group, or trimethylsilyl; R<3> is a hydrogen atom, a phenyl group, a substituted phenyl group or an alkyl group; R<4> is a hydrogen atom, a phenyl group, a substituted phenyl group or an alkyl group. The invention further provides the synthesis method of the phosphorus-containing five-membered heterocycle compound. Compared with an existing phosphorus organic micromolecule catalyst, a novel phosphorus-containing five-membered heterocycle compound is provided.
Description
Technical field
The invention belongs to organic compound synthesis technical field, be specifically related to a kind of phosphorous five-membered heterocycles and synthetic method thereof.
Background technology
Phosphorous five-membered heterocycles is an organic micromolecule catalyst of similar proline(Pro) structure.Proline(Pro) and derivative thereof, due to the special five-ring molecular skeleton having, are used as chiral organic micromolecule catalyst and are widely used.On basis in view of forefathers, we have developed a kind of chiral phosphine organic micromolecule catalyst of similar proline(Pro) structure.
L-PROLINE is the asymmetric organic micromolecule catalyst of finding the earliest, and it is simple in structure, and natural content is very abundant, and cheap, so people are comparatively deep to its research.At present be found can the many reactions of catalysis for proline(Pro), and most of reaction can obtain more satisfactory yield and stereoselectivity.So the organic phosphine micromolecule catalyst of developing a kind of novel praline-type becomes very valuable.Compared with chiral transition metal, that chiral organic micromolecule catalyst has is nontoxic, cheap and easy to get, reaction system is without metal residual and be easy to modify and the feature such as load, meets the requirement of Green Chemistry.
At present, there are some organic phosphine micromolecule catalysts successfully for asymmetry catalysis, representative reactions has: isomerization reaction, Rauhut-Currier reaction, MBH reaction, the electron deficiency connection cyclization of alkene and the nucleophilic addition of alkynes etc. of alkynes, aspect these reactions, obtaining good asymmetry catalysis effect.Be exemplified below:
This achievement in research on the one hand proves to people: the appropriate design of catalyzer is for the significance of the chiral phosphine organic micromolecule catalyst aspect of acquisition high catalytic activity and high enantioselectivity.
Summary of the invention
Content of the present invention is to provide a kind of phosphorous five-membered heterocycles;
Content of the present invention is also to provide a kind of synthetic method of phosphorous five-membered heterocycles.
The phosphorous five-membered heterocycles of this class has following general formula:
Wherein, R
1for phenyl, substituted-phenyl, alkyl; R
2for hydrogen atom, methyl sulphonyl, to Methyl benzenesulfonyl base, trimethyl silicon based; R
3for hydrogen atom, phenyl, substituted-phenyl, alkyl; R
4for hydrogen atom, phenyl, substituted-phenyl, alkyl.
Content of the present invention is specific as follows:
A kind of preparation method of phosphorous five-membered heterocycles, carry out according to following step: compound (II) 1-phenyl phospholane borane complex is dissolved in organic solvent,-40 ℃ with s-BuLi(s-butyl lithium) and DPE(1,2-dipiperidino ethane) do under the condition of alkali and pass into CO
2, obtain compound (III) 1-phenyl phospholane-2-formic acid borane complex.Again this product is reacted in anhydrous organic solvent with methyl esterification reagent and obtain compound (IV) 1-phenyl phospholane-2-methyl-formiate borane complex, the product of resulting separation, get wherein a kind of configuration and take off compound (V) the 1-phenyl phospholane-2-methyl-formiate obtaining after borine, react with reductive agent, obtain reduzate (VI) 1-phenyl phospholane-2-methyl alcohol, then this product is reacted to the derivative that obtains replacement with SULPHURYL CHLORIDE; Or get wherein a kind of and halogenated aromatic compound and siliceous reagent react, obtain another kind of derivative.
Above-described reaction organic solvent used is tetrahydrofuran (THF), methylene dichloride, trichloromethane, methyl alcohol, benzene, pyridine, triethylamine etc.
At the temperature of above-described-40 ℃, s-BuLi do highly basic be with tetrahydrofuran (THF) as solvent, add DPE and s-butyl lithium first to form an alkaline system, then drip compound (II) 1-phenyl phospholane borane complex, after pass into CO
2just replace the hydrogen atom on the carbon of phosphorus atom ortho position, carboxylic five member ring heterocyclic compound (III) the 1-phenyl phospholane-2-formic acid borane complex obtaining.
The ingredient proportion of above-described s-BuLi and DPE and reactant (II) 1-phenyl phospholane borane complex is 0.5-2.0:0.5-2.0:1.
Above-described compound (III) 1-phenyl phospholane-2-formic acid borane complex reacts with methyl esterification reagent, methyl esterification reagent herein refers to trimethyl silicane diazomethane, solvent for use is benzene and methyl alcohol, and compound (III) is 1:0.5-2.0 with the feed ratio of methyl esterification reagent.
After the above compound (III) 1-phenyl phospholane-2-formic acid borane complex reacts with methyl esterification reagent, obtained two kinds of isomerized product cis and trans, and the ratio of two kinds of products is cis:trans=5:1.
Above-described compound (V) 1-phenyl phospholane-2-methyl-formiate reacts with reductive agent, refer to and under the reduction of lithium aluminium hydride, obtain compound (VI) 1-phenyl phospholane-2-methyl alcohol, the molar weight of lithium aluminium hydride is 3 times of compound (V).
Above-described compound (VI) 1-phenyl phospholane-2-methyl alcohol reagent used with reacting of SULPHURYL CHLORIDE is Methanesulfonyl chloride and Tosyl chloride, and the feed ratio of the two and compound (VI) is 1.1:1.
Above-described aryl or alkyl Grignard reagent are 3,5-, bis-trifluoromethyl magnesium bromides etc., and silica reagent is trifluoromethanesulfonic acid trimethylsilyl group etc., and the mol ratio of the two and reactant (V) 1-phenyl phospholane-2-methyl-formiate is 1-4:1-4:1.
Compared with existing chiral phosphine organic micromolecule catalyst, the present invention is said is a kind of novel phosphorous five member ring heterocyclic compound.
Embodiment
By the following examples phosphorous five member ring heterocyclic compound of the present invention and synthetic method thereof are described further.
DPE(1 used in following examples, 2-dipiperidino ethane) be reference (a) Macromolecules, 2012,45,1190-1197; (b) Nankai University's journal, prepared by the method for 2003,36,60-67. report, and concrete reaction formula is as follows:
Compound (II) 1-phenyl phospholane borane complex used in following examples is reference Chem.Eur.J, prepared by the method for 2005,11,361-368 report, and concrete reaction formula is as follows:
Synthesizing of embodiment 1, compound (III) 1-phenyl phospholane-2-formic acid borane complex, (IV) 1-phenyl phospholane-2-methyl-formiate borane complex and (V) 1-phenyl phospholane-2-methyl-formiate
The 25mL of nitrogen protection execute Rec pipe in add 0.294g(1.5mmol) DPE; add the anhydrous THF of 2mL as solvent; at the temperature of-40 ℃, slowly drip 2mL(1.3M) the hexane solution of s-BuLi; after being added dropwise to complete; reaction 1h; drip again (II) 1-phenyl phospholane borane complex 1.78g(1mmol and be dissolved in anhydrous THF), then pass into CO after reacting 2h
2, aeration time is 1h, TLC detection reaction completes.Add the dilute hydrochloric acid of 1.0M to process to the aobvious slightly acidic of water, ethyl acetate aqueous phase extracted, merge organic phase anhydrous sodium sulfate drying, concentrated by rotary evaporation, first sherwood oil: ethyl acetate=6:1 crosses post, use again the sherwood oil of the Glacial acetic acid that contains 5%: ethyl acetate=2:1 crosses post can obtain product (III) 1-phenyl phospholane-2-formic acid borane complex, and productive rate is 72%.
The 25mL of nitrogen protection execute Rec pipe in add 0.222g(1mmol) compound (III) 1-phenyl phospholane-2-formic acid borane complex, add benzene that 4.5mL is dry and methyl alcohol as solvent, the ratio of two kinds of solvents is 8:1.Under condition of ice bath, slowly drip Me
3siCHN
2(trimethyl silicane diazomethane) 0.75mL(2.0M, 1.5mmol), after being added dropwise to complete, 0 ℃ of reaction adds 10mL methyl alcohol after 10min, moves to room temperature reaction and transfers to colourlessly to the color of solution by faint yellow, and TLC detection reaction completes.Rotary evaporation falls solvent, sherwood oil: ethyl acetate=5:1 crosses post and obtains product, this product has two kinds of configurations, cis-(IV) 1-phenyl phospholane-2-methyl-formiate borane complex and trans-(IV) 1-phenyl phospholane-2-methyl-formiate borane complex, productive rate is respectively 77%, the ratio cis-:trans-of 15%, two kind of configuration is about 5:1.Products therefrom is reacted with tetramethyleneimine take off and protect the borine of phosphorus atom to obtain compound (V) 1-phenyl phospholane-2-methyl-formiate, productive rate is 80%.cis-：
1H?NMR(300MHz,CDCl
3)δ2.07-2.44（m，6H），3.11（s，3H），3.32-3.40（q，1H），7.43-7.56（m，3H），7.68-7.71（m，2H）；
13C?NMR(75MHz,CDCl
3)δ25.6，26.1，30.2，46.1，51.6，126.7，128.5，132.0，132.6，170.2；trans-：
1H?NMR(300MHz,CDCl
3)δ0.77（q，3H），1.90-2.02（m，1H），2.14-2.39（m，5H），3.26-3.33（m，1H），7.46-7.55（m，3H），7.74-7.79（m，2H）；
13C?NMR(75MHz,CDCl
3)δ26.24，26.38，29.96，46.45，129.13，129.82，131.38，131.73，175.39。
Synthesizing of embodiment 2, compound (VI) 1-phenyl phospholane-2-methyl alcohol
The 25mL of nitrogen protection execute Rec pipe in add 0.1137g(3mmol) lithium aluminium hydride; add the anhydrous THF of 2mL as solvent; by 0.222g(1mmol) the cis-configuration of compound (V) 1-phenyl phospholane-2-methyl-formiate and the anhydrous tetrahydro furan wiring solution-forming of 2mL; at 0 ℃, be slowly added drop-wise in reaction solution; after being added dropwise to complete, move to room temperature reaction 15h, TLC detection reaction completes.Equally, under ice bath, slowly drip the dilute hydrochloric acid solution of 1.0M, ethyl acetate extraction, anhydrous sodium sulfate drying, concentrated by rotary evaporation, sherwood oil: ethyl acetate=2:1 crosses post and obtains product (VI) 1-phenyl phospholane-2-methyl alcohol, and productive rate is 57%.
1H?NMR(300MHz,CDCl
3)δ2.19-2.33（m，4H），2.37-2.43（m，1H），1.61-1.69（m，2H），3.27-3.46（m，2H），7.44-7.52（m，3H），7.69-7.76（m，4H）；
13CNMR(75MHz,CDCl
3)δ23.9，24.2，30.0，42.3，60.9，125.6，127.7，130.6，131.7。
Synthesizing of embodiment 3, compound (VII) tosic acid (1-phenyl phospholane-2-first) ester
The 25mL of nitrogen protection execute Rec pipe in add 0.101g(1.1mmol) Tosyl chloride (TsCl); toward the anhydrous pyridine dissolved solids that adds 2mL in pipe; by compound (VI) 1-phenyl phospholane-2-methyl alcohol 0.194g(1mmol) be made into the pyridine solution of 1mL; at 0 ℃, be slowly added drop-wise in reaction solution; wait to be added dropwise to complete; move to room temperature reaction 24h, TLC detection reaction completes.Under ice bath, slowly drip the dilute hydrochloric acid solution of 1.0M, ethyl acetate extraction, saturated common salt water washing, anhydrous sodium sulfate drying, concentrated by rotary evaporation, sherwood oil: ethyl acetate=2:1 crosses post and obtains product (VII) tosic acid (1-phenyl phospholane-2-first) ester, and productive rate is 75%.
1H?NMR(300MHz,CDCl
3)δ1.58-1.68（m，1H），1.83-1.93（m，1H），2.22-2.25（m，4H），2.30-2.45（m，4H），3.57-3.66（q，1H），3.80-3.87（q，1H），7.26-7.30（d，2H），7.43-7.48（t，2H），7.52-7.68（m，5H）；
13C?NMR(75MHz,CDCl
3)δ21.7，24.9，25.1，31.2，39.6，68.9，125.6，127.7，129.0，132.0，132.6，132.7。
Synthesizing of embodiment 4, compound (VIII) methylsulfonic acid (1-phenyl phospholane-2-first) ester
The 25mL of nitrogen protection execute Rec pipe in add anhydrous methylene chloride to dissolve compound (VI) 1-phenyl phospholane-2-methyl alcohol 0.194g(1mmol); at 0 ℃, add again the anhydrous triethylamine of 0.28mL; stir; extract 0.116mL(1.1mmol) Methanesulfonyl chloride slowly splash in pipe; reaction 2h, TLC detection reaction.Add appropriate water to process, ethyl acetate extraction, anhydrous sodium sulfate drying, concentrated by rotary evaporation, sherwood oil: ethyl acetate=2:1 crosses post and obtains product (VIII) methylsulfonic acid (1-phenyl phospholane-2-first) ester, and productive rate is 88%.
1H?NMR(300MHz,CDCl
3)δ1.66-1.76（m，1H），1.89-1.98（m，1H），2.25-2.36（m，4H），2.51-2.60（m，1H），2.80（s，3H），3.89-3.95（m，2H），7.46-7.55（m，3H），7.68-7.75（m，2H）；
13C?NMR(75MHz,CDCl
3)δ25.0，25.2，31.3，37.4，40.0，68.0，125.7，129.1，132.2，132.8。
Synthesizing of embodiment 5, compound (IX) (two (3,5 two trifluoromethyl)) (1-phenyl phospholane-2-) methyl alcohol
The 25mL of nitrogen protection execute Rec pipe in add 0.52mL(3mmol) 3; 5-bis-methyl bromobenzene trifluorides; add the anhydrous tetrahydro furan of 2mL to make solvent; 0 ℃ slowly drips 1.5mL(3mmol; 2.0M) isopropylmagnesium chloride; react 1h under ice bath after, drip compound (V) 1-phenyl phospholane-2-methyl-formiate 0.222g(1mmol) THF solution, be added dropwise to complete at 65 ℃ of rear oil baths and react 6h, TLC detection reaction.Add ammonium chloride solution to process, ethyl acetate processing, saturated nacl aqueous solution washing organic phase, anhydrous sodium sulfate drying, concentrated by rotary evaporation, sherwood oil: ethyl acetate=6:1 crosses post and obtains product (IX) (two (3,5 two trifluoromethyl)) (1-phenyl phospholane-2-) methyl alcohol, and productive rate is 70%.
1H?NMR(300MHz,CDCl
3)δ1.77-1.91（m，1H），1.99-2.13（m，3H），2.29-2.54（m，3H），3.58-3.65（m，1H），7.27-7.38（m，4H），7.49-7.54（m，1H），7.72（s，1H），7.77-7.79（d，2H），7.84（s，2H）；
13C?NMR(75MHz,CDCl
3)δ24.1，25.2，25.7，30.1，50.7，115.8，117.5，121.1，122.3，124.8，125.2，125.7，129.5，132.0，132.4，132.9，146.5，147.0。
Synthesizing of embodiment 6, compound (X) (two (3,5 two trifluoromethyl)) (1-phenyl phospholane-2-) trimethylammonium silica methane
The 25mL of nitrogen protection execute Rec pipe in add compound (IX) (two (3; 5 two trifluoromethyls)) (1-phenyl phospholane-2-) methyl alcohol 0.618g(1mmol); extract anhydrous triethylamine and the methylene dichloride of 3mL; 0 ℃ slowly drips 0.55mL(3mmol) TMSOTf(trifluoromethanesulfonic acid trimethylammonium silicone grease); under ice bath, react 1h; after move to normal-temperature reaction 8h, TLC detection reaction.Add appropriate water to process, ethyl acetate processing, saturated nacl aqueous solution washing organic phase, anhydrous sodium sulfate drying, concentrated by rotary evaporation, sherwood oil: ethyl acetate=5:1 crosses post and obtains product (X) (two (3,5 two trifluoromethyl)) (1-phenyl phospholane-2-) trimethylammonium silica methane, and productive rate is 62%.
1H?NMR(300MHz,CDCl
3)δ0（s，9H），2.23-2.55（m，6H），3.65-3.70（m，1H），7.29-7.39（m，4H），7.49（s，3H），7.57（s，2H），7.83-7.86（d，2H）；
13C?NMR(75MHz,CDCl
3)δ1.8，24.4，27.0，27.6，32.0，52.0，81.6，121.0，122.2，122.3，124.6，126.6，127.1，127.8，128.1，131.3，131.7，133.5，145.9，146.3。
Claims (9)
1. phosphorous five-membered heterocycles, is characterized in that having following general formula:
Formula I
Wherein, R
1for phenyl, substituted-phenyl, alkyl; R
2for hydrogen atom, methyl sulphonyl, to Methyl benzenesulfonyl base, trimethyl silicon based; R
3for hydrogen atom, phenyl, substituted-phenyl, alkyl; R
4for hydrogen atom, phenyl, substituted-phenyl, alkyl.
2. the preparation method of phosphorous five-membered heterocycles, it is characterized in that carrying out according to following step: compound (II) 1-phenyl phospholane borane complex is dissolved in organic solvent,-40 ℃ with s-BuLi(s-butyl lithium) and DPE(1,2-dipiperidino ethane) do under the condition of alkali and pass into CO
2, obtain compound (III) 1-phenyl phospholane-2-formic acid borane complex;
Again this product is reacted in anhydrous organic solvent with methyl esterification reagent and obtain compound (IV) 1-phenyl phospholane-2-methyl-formiate borane complex, the product of resulting separation, get wherein a kind of configuration and take off compound (V) the 1-phenyl phospholane-2-methyl-formiate obtaining after borine, react with reductive agent, obtain reduzate (VI) 1-phenyl phospholane-2-methyl alcohol, then this product is reacted to the derivative that obtains replacement with SULPHURYL CHLORIDE; Or get wherein a kind of and aryl or alkyl Grignard reagent and siliceous reagent react, obtain another kind of derivative.
3. the preparation method of phosphorous five-membered heterocycles according to claim 2, is characterized in that described organic solvent is tetrahydrofuran (THF), methylene dichloride, trichloromethane, methyl alcohol, benzene, pyridine, triethylamine.
4. the preparation method of phosphorous five-membered heterocycles according to claim 2, is characterized in that described s-BuLi and the ingredient proportion of DPE and reactant (II) 1-phenyl phospholane borane complex are 0.5-2.0:0.5-2.0:1.
5. the preparation method of phosphorous five-membered heterocycles according to claim 2, it is characterized in that described methyl esterification reagent refers to trimethyl silicane diazomethane, solvent for use is benzene or methyl alcohol, and compound (III) is 1:0.5-2.0 with the feed ratio of methyl esterification reagent.
6. the preparation method of phosphorous five-membered heterocycles according to claim 2, is characterized in that having obtained two kinds of isomerized products after described compound (III) 1-phenyl phospholane-2-formic acid borane complex reacts with methyl esterification reagent
ciswith
trans, and the ratio of two kinds of products is
cis:
trans=5: 1.
7. the preparation method of phosphorous five-membered heterocycles according to claim 2, it is characterized in that described compound (V) 1-phenyl phospholane-2-methyl-formiate reacts with reductive agent, refer to and under the reduction of lithium aluminium hydride, obtain compound (VI) 1-phenyl phospholane-2-methyl alcohol, the molar weight of lithium aluminium hydride is 3 times of compound (V).
8. the preparation method of phosphorous five-membered heterocycles according to claim 2, it is characterized in that above-described compound (VI) 1-phenyl phospholane-2-methyl alcohol reagent used with reacting of SULPHURYL CHLORIDE is Methanesulfonyl chloride and Tosyl chloride, the feed ratio of the two and compound (VI) is 1.1:1.
9. the preparation method of phosphorous five-membered heterocycles according to claim 2, it is characterized in that described aryl or alkyl Grignard reagent are 3,5-bis-trifluoromethyl magnesium bromides etc., silica reagent is trifluoromethanesulfonic acid trimethylsilyl group etc., and the mol ratio of the two and reactant (V) 1-phenyl phospholane-2-methyl-formiate is 1-4:1-4:1.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002069086A (en) * | 2000-08-25 | 2002-03-08 | Japan Science & Technology Corp | Optically active phosphorus compound |
| WO2005095424A1 (en) * | 2004-04-01 | 2005-10-13 | Warner-Lambert Company Llc | Preparation of p-chirogenic phospholanes and their use in asymetric synthesis |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002069086A (en) * | 2000-08-25 | 2002-03-08 | Japan Science & Technology Corp | Optically active phosphorus compound |
| WO2005095424A1 (en) * | 2004-04-01 | 2005-10-13 | Warner-Lambert Company Llc | Preparation of p-chirogenic phospholanes and their use in asymetric synthesis |
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Application publication date: 20140514 |