CN104356168A - Dicyclopentadienyl iron oxazoline-phosphine ligands containing imidazolium salt group, preparation method of dicyclopentadienyl iron oxazoline-phosphine ligands and application of dicyclopentadienyl iron oxazoline-phosphine ligands in asymmetrical cycloaddition reaction - Google Patents

Dicyclopentadienyl iron oxazoline-phosphine ligands containing imidazolium salt group, preparation method of dicyclopentadienyl iron oxazoline-phosphine ligands and application of dicyclopentadienyl iron oxazoline-phosphine ligands in asymmetrical cycloaddition reaction Download PDF

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CN104356168A
CN104356168A CN201410667517.6A CN201410667517A CN104356168A CN 104356168 A CN104356168 A CN 104356168A CN 201410667517 A CN201410667517 A CN 201410667517A CN 104356168 A CN104356168 A CN 104356168A
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oxazoline
phosphine ligands
reaction
dicyclopentadienyl iron
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周智明
戴力
徐迪
李磊
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Beijing Institute of Technology BIT
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F17/00—Metallocenes
    • C07F17/02—Metallocenes of metals of Groups 8, 9 or 10 of the Periodic System
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/04—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
    • C07D207/10—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D207/16—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/324—Cyclisations via conversion of C-C multiple to single or less multiple bonds, e.g. cycloadditions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0225—Complexes comprising pentahapto-cyclopentadienyl analogues
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Abstract

The invention relates to a synthesis method of novel imidazolium salt-containing planar chiral dicyclopentadienyl iron oxazoline-phosphine ligands and application of the dicyclopentadienyl iron oxazoline-phosphine ligands in asymmetric cycloaddition reaction. According to the synthesis method of the dicyclopentadienyl iron oxazoline-phosphine ligands, (S)-4-methy-2-dicyclopentadienyl iron oxazoline is prepared through six steps to obtain novel ligands containing different negative ions; besides, the novel ligands are applied to cuprous perchlorate tetraacetonitrile-catalyzed asymmetric cycloaddition reaction, so that cycloaddition products with high yield and high enantioselectivity are obtained; meanwhile, a copper complex catalyst can be dissolved in ionic liquid by utilizing imidazolium salt fragments contained in the novel ligands and the asymmetric cycloaddition reaction is carried out; after reaction is finished, the ionic liquid can be utilized for recycling the catalyst.

Description

Containing two luxuriant iron oxazoline-Phosphine ligands of imidazole salts group, its preparation and the application in Asymmetrical annular-addition reaction
Technical field
The present invention relates to the two luxuriant iron oxazoline-Phosphine ligands containing imidazole salts group of a class containing different anions, and Asymmetrical annular-addition reaction, belong to asymmetry catalysis and synthesis field.
Background technology
Asymmetry catalysis is the process preparing a large amount of chipal compounds with a small amount of chiral catalyst.In transition metal-catalyzed asymmetric reaction, its important step is the chiral ligand of design and synthesis high catalytic activity and highly-solid selectively.In numerous chiral ligands, the oxazoline-Phosphine ligands containing face chirality has outstanding performance in many asymmetric catalysis.Face Shou bis-Mao Tie oxazoline-Phosphine ligands all achieves the asymmetric products of high yield and high enantioselectivity in asymmetric allylic substitution, asymmetric conjugated reaction reaction, asymmetric hydrogenation, Asymmetric hydrogen transfer reaction etc.But the efficient metal complex compound catalyst used in reaction is expensive, reaction is made to be difficult to extension, industrialization; In addition, heavy metal catalyst also utilizes further it the pollution of environment and causes huge challenge in reaction process.At present, although there is the recovery method about metal complex catalyst, the luxuriant iron oxazoline-Phosphine ligands part of efficient face hand two be there is no to the report of similar recovery.
For liquid salt is called as ionic liquid under the normal temperature be made up of organic cation and inorganic anion.Regulate the zwitterion in ionic liquid can change himself solvability in inorganics, organism and water by design.Utilize this feature, ionic liquid is being subject to increasing attention as green solvent in recent years in organic synthesis field.Have report to point out, design contains asymmetric catalyst or the part of ion fragment, effectively can be dissolved in ionic liquid, and utilize the solvability difference of ionic liquid and different organic solvents to carry out recovery and the recycling of catalyzer.
Containing two luxuriant iron oxazoline-Phosphine ligands of imidazole salts group as the luxuriant iron oxazoline-Phosphine ligands of the face hand two that a class is novel, in ionic liquid, there is good solubility.Because part has good catalytic activity, transition metal-catalyzed asymmetric reaction can be carried out efficiently.And the solvability in ionic liquid can be utilized, catalyzer is carried out reclaiming and recycling.
Summary of the invention
The object of the invention is to develop a kind of two novel luxuriant iron oxazoline-Phosphine ligands (general formula I), the synthetic method of the two luxuriant iron oxazoline-Phosphine ligands containing imidazole salts group providing a kind of catalytic efficiency high.Its compound formula is as follows:
Wherein, X is OTf, PF 6, BF 4, I, ClO 4
Compou nd synthesis method in general formula (I) is divided into following two steps:
(1) (R, R p) synthesis of-1-[[the luxuriant Tie oxazolin of 2-(2-diphenylphosphine) Er] methyl]-2,3-methylimidazole fluoroform sulphonates.
(2) as required, synthesis has the compound 6 of different anions.
A further object of the present invention is applied in Asymmetrical annular-addition reaction by the luxuriant iron oxazoline-Phosphine ligands 6 of face hand two containing imidazole salts group of synthesis.
Under argon shield, by four acetonitrile perchloric acid cuprous (3.3mg, 0.01mmol) with novelly add contain containing the luxuriant iron oxazoline-Phosphine ligands (0.011mmol) of imidazole salts face hand two after the dry Schlenk bottle of molecular sieve, add 1mL solvent.Room temperature reaction, after 30 minutes, under ice-water bath condition, adds substrate glycine imine ester (0.1mmol) respectively, substrate nitro alkene (0.11mmol) and diisopropyl ethyl amine (1.4 μ L, 0.01 mmol).System was 0 DEG C of reaction 12 hours.After reaction terminates, steam solvent, thick product column chromatography for separation (silica gel 100-200 order, eluent: sherwood oil: ethyl acetate=10:1).The non-corresponding body ratio of product by 1h NMR measures, and exo-configuration cycloaddition product ee value is by chirality Liquid Detection.
Another object of the present invention is applied in the Asymmetrical annular-addition reaction of ionic liquid participation by the luxuriant iron oxazoline-Phosphine ligands 6 of face hand two containing imidazole salts group of synthesis, and catalyst recovery recycled.
Under argon shield, by four acetonitrile perchloric acid cuprous (3.3mg, 0.01mmol) with novelly add contain containing the luxuriant iron oxazoline-Phosphine ligands (0.011mmol) of imidazole salts face hand two after the dry Schlenk bottle of molecular sieve, add 0.9mL methylene dichloride.Room temperature reaction is after 30 minutes, under ice-water bath condition, add ionic liquid (0.1mL) respectively, substrate glycine imine ester (0.1mmol), substrate nitro alkene (0.11mmol) and diisopropyl ethyl amine (1.4 μ L, 0.01mmol).System was 0 DEG C of reaction 10 hours.After reaction terminates, steam organic solvent, ionic liquid uses anhydrous diethyl ether washing until do not have raw material and product to remain.Merge organic phase, steam solvent, thick product column chromatography for separation (silica gel 100-200 order, eluent: sherwood oil: ethyl acetate=10:1).The non-corresponding body ratio of product by 1h NMR measures, and exo-configuration cycloaddition product ee value is by chirality Liquid Detection.Residual ion liquid is at 1mmHg vacuum under pressure after dry 2 hours, rejoin 0.9mL methylene dichloride and substrate glycine imine ester (0.1mmol), substrate nitro alkene (0.11mmol) and diisopropyl ethyl amine (1.4 μ L, 0.01mmol).
Embodiment
Embodiment 1:(R) preparation of the luxuriant Tie oxazolin (2) of-4-methylol-2-Er
By the luxuriant Tie oxazolin of (S)-4-methyl esters-2-Er (2.5g, 8.0mmol) be dissolved in 60 milliliters of untreated anhydrous diethyl ethers, be cooled to 0 DEG C, divide and add lithium aluminum hydride powder (333mg for 5 times, 8.8mmol), reaction solution gradually becomes muddy by clarification.Room temperature reaction 15 minutes, adds large water gaging and extraction into ethyl acetate reaction solution, till water layer clarification.Merge oil phase, anhydrous sodium sulfate drying, steams solvent, thick product column chromatography for separation (silica gel 100-200 order, eluent: sherwood oil: ethyl acetate: ethanol=10:10:1).The luxuriant Tie oxazolin of product (R)-4-methylol-2-Er, orange solids, productive rate 91%.m.p.:119-121℃。[α] D 20＝+84(c0.05,CH 2Cl 2)。IR(cm -1):1640,1479,1379,1306,1261,1125,1101,1030。 1H-NMR(400MHz,CDCl 3):δ3.62(1H,dd,J＝11.2,3.6,CHHOH),3.90(1H,dd,J＝9.6,3.2,CHHOH),4.18(5H,s,Cp-H),4.24-4.34(5H,m,OCH 2+CHN+Cp-H×2),4.70(1H,br s,Cp-H),4.76(1H,br s,Cp-H)。 13C-NMR(400MHz,d 6-DMSO):δ63.0(CH 2OH),67.9(CHN),68.6(Cp×2),69.2(Cp×5),70.0(Cp),70.1(Cp),70.3(Cp),165.2(C＝N)。
Embodiment 2:(S) preparation of the luxuriant Tie oxazolin (3) of-4-(tertiary butyl dimethyl Si base) methyl-2-Er
By the luxuriant Tie oxazolin of (R)-4-methylol-2-Er (1.0g, 3.5mmol) with imidazoles (1.07g, 15.8mmol) be dissolved in 35 milliliters of anhydrous tetrahydro furans, add dimethyl tertiary butyl chlorosilane (1.05g subsequently, 7mmol), reaction solution becomes muddy at once.After room temperature reaction spends the night, add a large amount of ether and saturated aqueous common salt, anhydrous diethyl ether extractive reaction liquid, until water layer is colourless, merge oil phase, anhydrous sodium sulfate drying.Steam solvent, thick product column chromatography for separation (silica gel 100-200 order, eluent: sherwood oil: ethyl acetate=15:1).The luxuriant Tie oxazolin of product (S)-4-(tertiary butyl dimethyl Si base) methyl-2-Er, dark red liquid, productive rate 93%.[α] D 20＝+24.1(c 0.28,CH 2Cl 2)。 1H NMR(400MHz,CDCl 3):δ0.07(s,6H,Si(CH 3) 2),0.90(s,9H,C(CH 3) 3),3.56(dd,J＝7.2,6.4Hz,1H,CHHOTBS),3.88(dd,J＝11.8,3.6Hz,1H,CHHOTBS),4.12(s,5H,Cp-H),4.22-4.33(m,5H,OCH 2+CHN+Cp-H×2),4.73(br s,2H,Cp-H)。 13C NMR(100MHz,d 6-DMSO)δ-5.03,18.05,25.08,64.67,67.66,68.65(d,J＝17Hz),69.44(Cp×5),70.01,70.33,165.36。MS(ESI)m/z(M+H +)400.5。
Embodiment 3:(S, R p)-4-(tertiary butyl dimethyl Si base) methyl-2-[preparation of (2-diphenylphosphine) ferrocenyl] oxazoline (4)
Under nitrogen protection; by the luxuriant Tie oxazolin of (S)-4-(tertiary butyl dimethyl Si base) methyl-2-Er (1.615g; 4.04mmol) He newly steam N; N; N; N-Tetramethyl Ethylene Diamine (610mg, 5.25mmol) is dissolved in 50 milliliters of anhydrous diethyl ethers, obtains orange solution.After system is cooled to-78 DEG C, drips n-Butyl Lithium (3.3mL, 1.6M, 5.28mmol) to system, within 30 minutes, finish.After dropwising, system is slowly returned to 0 DEG C, react 2 hours, the orange intensification of reaction system or become redness.Again system is cooled to-78 DEG C, drips the diethyl ether solution of diphenyl phosphine chloride (1.16g, 5.25mmol) to system, within 20 minutes, finish.After dropwising, system is slowly returned to room temperature, reaction is spent the night.React complete, in solution, have Precipitation; In system, add saturated aqueous ammonium chloride, rear ethyl acetate and saturated aqueous common salt extractive reaction liquid, until water layer is colourless, merge oil phase, anhydrous sodium sulfate drying.Steam solvent, thick product column chromatography for separation (silica gel 100-200 order, eluent: sherwood oil: ethyl acetate=15:1).Product (S, R p)-4-(tertiary butyl dimethyl Si base) methyl-2-[(2-diphenylphosphine) ferrocenyl] oxazoline, yellow solid, productive rate 65%.m.p.:114-116℃。[α] D 20＝+82.4(c 0.24,CH 2Cl 2)。 1H NMR(500MHz,CDCl 3):δ0.03(s,6H,Si(CH 3) 2),0.86(s,9H,C(CH 3) 3),3.24(t,J＝9.0Hz,1H,OCHH),3.66(s,1H,Cp-H),3.84(dd,J＝10.0,4.0Hz,1H,CHHOTBS),3.91(t,J＝8.0Hz,1H,OCHH)4.16(m,1H,CHN),4.24(s,5H,Cp-H),4.35-4.41(m,2H,Cp-H×2),5.02(s,1H,Cp-H),7.19-7.23(2H,Ph-H),7.25-7.28(3H,Ph-H),7.39(3H,Ph-H),7.50-7.53(2H,Ph-H)。 13C NMR(125MHz,CDCl 3):δ-5.31,18.29,25.87(d,J＝6.3Hz),65.41,67.92,70.91(Cp×5),72.43,74.02(d,J＝3.8Hz),78.46(d,J＝15Hz),127.91,128.03(d,J＝6.5Hz),128.20(d,J＝7.3Hz),129.03,132.32(d,J＝19Hz),134.96(d,J＝21Hz),138.14(d,J＝13Hz),139.58(d,J＝12.5Hz),167.24。 31P NMR(242.95MHz,CDCl 3):δ-18.32(s,PPh 2)。MS(ESI)m/z(M+CH 3OH+H +)616.0。
Embodiment 4:(R, R p)-4-methylol-2-[the preparation of (2-diphenylphosphine) ferrocenyl] oxazoline (5)
Under nitrogen protection, by (S, R p)-4-(tertiary butyl dimethyl Si base) methyl-2-[(2-diphenylphosphine) ferrocenyl] oxazoline (550mg, 0.94mmol) be dissolved in 20 milliliters of anhydrous tetrahydro furans, after system is cooled to 0 DEG C, drip tetrabutyl ammonium fluoride (1.24g, anhydrous tetrahydrofuran solution 4.75mmol), finishes for 20 minutes.After room temperature reaction spends the night, add large water gaging, and be extracted with ethyl acetate reaction solution, until water layer is colourless.Merge oil phase, anhydrous sodium sulfate drying, steams solvent, thick product column chromatography for separation (silica gel 100-200 order, eluent: sherwood oil: ethyl acetate: ethanol=10:10:1).Product (R, R p)-4-methylol-2-[(2-diphenylphosphine) ferrocenyl] oxazoline, orange foaming solid, productive rate 85%.m.p.:184-186℃。[α] D 20＝+246.0(c 0.12,CH 2Cl 2)。 1H NMR(500MHz,CDCl 3):δ3.45(dd,J＝11.0,4.0Hz,1H,CHHOTBS),3.75-3.78(m,2H,OCHH+CHN),4.01(t,J＝8.0Hz,1H,OCHH),4.22(s,5H,Cp-H),4.37(t,J＝9.0Hz,1H,Cp-H),4.43(d,J＝6.0Hz,1H,Cp-H),4.97(s,1H,Cp-H),7.22-7.24(2H,Ph-H),7.26-7.29(3H,Ph-H),7.39-7.40(3H,Ph-H),7.51-7.54(2H,Ph-H)。 13C NMR(125MHz,CDCl 3):δ64.19,67.70,69.30,70.94(Cp×5),72.86,74.05(d,J＝4Hz),75.32(d,J＝17.5Hz),78.26(d,J＝13Hz),127.95,128.05(d,J＝6.5Hz),128.22(d,J＝7.3Hz),129.15,132.24(d,J＝18.5Hz),135.08(d,J＝21Hz),137.91(d,J＝11.5Hz),139.70(d,J＝11Hz),167.17。 31P NMR(242.95MHz,CDCl 3):δ-18.80(s,PPh 2)。MS(ESI)m/z(M+CH 3OH+H +)502.0。
Embodiment 6:(R, R p) preparation of-1-[[the luxuriant Tie oxazolin of 2-(2-diphenylphosphine) Er] methyl]-2,3-methylimidazole fluoroform sulphonates (6-OTf)
Under nitrogen protection, by (R, R p) [(2-diphenylphosphine) ferrocenyl] oxazoline (150mg, 0.32mmol), is dissolved in 5 milliliters of anhydrous methylene chlorides-4-methylol-2-.After newly steaming diisopropyl ethyl amine (41.3mg, 0.32mmol) to system dropping, system is cooled to-78 DEG C.Slowly Trifluoromethanesulfonic anhydride (90.1mg, 0.32mmol) is newly steamed in dropping under this condition, within 25 minutes, finishes.After dropwising, system is slowly warming up to-40 DEG C, reacts 2 hours.After completion of the reaction, slowly system is returned to 0 DEG C, the saturated sodium bicarbonate solution of ice is slowly dripped in system, and at such a temperature, rapid use 0 DEG C of extraction into ethyl acetate 1 time, anhydrous sodium sulfate drying, steams solvent, thick product column chromatography for separation (silica gel 100-200 order, eluent: sherwood oil: ethyl acetate=5:1).Product (S, R p)-4-(trifluoromethayl sulfonic acid ester group) methyl-2-[(2-diphenylphosphine) ferrocenyl] oxazoline.
Under nitrogen protection, by (S, R p)-4-(trifluoromethayl sulfonic acid ester group) methyl-2-[(2-diphenylphosphine) ferrocenyl] oxazoline (100mg, 0.17mmol) be dissolved in 20 milliliters of anhydrous diethyl ethers, 1 is added under ice-water bath condition, 2-methylimidazole (100mg, 1.04mmol) diethyl ether solution.After 5 minutes, in solution, significantly separate out yellow mercury oxide.React after 15 minutes, filtering reacting liquid, a large amount of anhydrous diethyl ether of much filtrate washs, filter cake decompressing and extracting.Product (R, R p)-1-[[the luxuriant Tie oxazolin of 2-(2-diphenylphosphine) Er] methyl]-2,3-methylimidazole fluoroform sulphonates, yellow solid, productive rate 65%.m.p.:171-173℃。[α] D 20＝+261.6(c 0.17,CH 2Cl 2)。 1H NMR(600MHz,d 6-DMSO):δ2.78(s,3H,imidazole-2-Me),3.56(s,1H,CHHOTBS),3.86(s,3H,imidazole-3-Me),4.08(t,J＝7.8Hz,1H,OCHH),4.15(s,5H,Cp-H),4.30(s,1H,OCHH),4.42(t,J＝12.6Hz,2H,CHN+Cp-H),4.53(s,1H,Cp-H),4.92(s,1H,Cp-H),7.01(2H,Ph-H),7.25(3H,Ph-H),7.45(5H,Ph-H),7.71(s,1H,imidazole-H),7.83(s,1H,imidazole-H)。 13C NMR(150MHz,d 6-DMSO):δ11.21,35.78(d,J＝23Hz),51.17,66.81,69.61,71.55(Cp×5),72.09,73.81,74.12,74.99(d,J＝19Hz),77.58(d,J＝16Hz),120.53,122.54,123.04(d,J＝14Hz),128.08,129.07,130.05(d,J＝32Hz),132.61(d,J＝35Hz),135.63(d,J＝10Hz),138.75(d,J＝12.6Hz),140.41(d,J＝12.6Hz),146.34,166.80。 31P NMR(242.95MHz,CDCl 3):δ-19.06(s,PPh 2)。MS(MALDI-TOF)m/z＝548.1M +(ESI)148.9M -。
Embodiment 7:(R, R p)-1-[[the luxuriant Tie oxazolin of 2-(2-diphenylphosphine) Er] methyl]-2,3-methylimidazole hexafluorophosphate (6-PF 6) preparation
Under nitrogen protection, by (R, R p)-1-[[the luxuriant Tie oxazolin of 2-(2-diphenylphosphine) Er] methyl]-2,3-methylimidazole fluoroform sulphonate (100mg, 0.14mmol) be dissolved in 50 ml waters, under ice-water bath condition, add Potassium Hexafluorophosphate (200mg, the 1.09mmol) aqueous solution.Faint yellow solid is had to separate out in solution.React 10 minutes under 0 DEG C of condition, filtering reacting liquid, a large amount of anhydrous diethyl ether of much filtrate washs, filter cake decompressing and extracting.Product (R, R p)-1-[[the luxuriant Tie oxazolin of 2-(2-diphenylphosphine) Er] methyl]-2,3-methylimidazole hexafluorophosphates, yellow solid, productive rate 90%.m.p.:181℃(decomp.)。[α] D 20＝+296.1(c 0.10,CH 2Cl 2)。 31P NMR(242.95MHz,d 6-DMSO):δ-19.09(s,PPh 2),-143.56(m,J＝710Hz,PF 6)。MS(MALDI-TOF)m/z＝548.1M +(ESI)145.0M -。
Embodiment 8:(R, R p)-1-[[the luxuriant Tie oxazolin of 2-(2-diphenylphosphine) Er] methyl]-2,3-methylimidazole a tetrafluoro borate (6-BF 4) preparation
Under nitrogen protection, by (R, R p)-1-[[the luxuriant Tie oxazolin of 2-(2-diphenylphosphine) Er] methyl]-2,3-methylimidazole fluoroform sulphonate (100mg, 0.14mmol) be dissolved in 50 ml waters, under ice-water bath condition, add Sodium tetrafluoroborate (200mg, the 1.83mmol) aqueous solution.Faint yellow solid is had to separate out in solution.React 10 minutes under 0 DEG C of condition, filtering reacting liquid, a large amount of anhydrous diethyl ether of much filtrate washs, filter cake decompressing and extracting.Product (R, R p)-1-[[the luxuriant Tie oxazolin of 2-(2-diphenylphosphine) Er] methyl]-2,3-methylimidazole a tetrafluoro borates, yellow solid, productive rate 88%.m.p.:172℃(decomp.)。[α] D 20＝+326.0(c 0.10,CH 2Cl 2)。 31PNMR(242.95MHz,d 6-DMSO):δ-19.08(s,PPh 2)。MS(MALDI-TOF)m/z＝548.1M +(ESI)87.0M -。
Embodiment 9:(R, R p) preparation of-1-[[the luxuriant Tie oxazolin of 2-(2-diphenylphosphine) Er] methyl]-2,3-methylimidazole salt compounded of iodine (6-I)
Under nitrogen protection, by (R, R p)-1-[[the luxuriant Tie oxazolin of 2-(2-diphenylphosphine) Er] methyl]-2,3-methylimidazole fluoroform sulphonate (100mg, 0.14mmol) be dissolved in 50 ml waters, under ice-water bath condition, add sodium iodide (200mg, the 1.33mmol) aqueous solution.Faint yellow solid is had to separate out in solution.React 10 minutes under 0 DEG C of condition, filtering reacting liquid, a large amount of anhydrous diethyl ether of much filtrate washs, filter cake decompressing and extracting.Product (R, R p)-1-[[the luxuriant Tie oxazolin of 2-(2-diphenylphosphine) Er] methyl]-2,3-methylimidazole salt compounded of iodine, yellow solid, productive rate 85%.m.p.:187℃(decomp.)。[α] D 20＝+239.3(c 0.22,CH 2Cl 2)。 31P NMR(242.95MHz,d 6-DMSO):δ-19.08(s,PPh 2)。MS(MALDI-TOF)m/z＝548.1M +(ESI)126.9M -。
Embodiment 10:(R, R p)-1-[[the luxuriant Tie oxazolin of 2-(2-diphenylphosphine) Er] methyl]-2,3-methylimidazole perchlorate (6-ClO 4) preparation
Under nitrogen protection, by (R, R p)-1-[[the luxuriant Tie oxazolin of 2-(2-diphenylphosphine) Er] methyl]-2,3-methylimidazole fluoroform sulphonate (100mg, 0.14mmol) be dissolved in 50 ml waters, under ice-water bath condition, add sodium perchlorate (200mg, the 1.67mmol) aqueous solution.Faint yellow solid is had to separate out in solution.React 10 minutes under 0 DEG C of condition, filtering reacting liquid, a large amount of anhydrous diethyl ether of much filtrate washs, filter cake decompressing and extracting.Product (R, R p)-1-[[the luxuriant Tie oxazolin of 2-(2-diphenylphosphine) Er] methyl]-2,3-methylimidazole perchlorate, yellow solid, productive rate 70%.m.p.:187℃(decomp.)。[α] D 20＝+298.1(c 0.11,CH 2Cl 2)。 31P NMR(242.95MHz,d 6-DMSO):δ-19.08(s,PPh 2)。MS(MALDI-TOF)m/z＝548.1M +(ESI)99.0M -。
Embodiment 11:(R, R p)-1-[[the luxuriant Tie oxazolin of 2-(2-diphenylphosphine) Er] methyl]-2,3-methylimidazole fluoroform sulphonate (6-OTf) catalysis Asymmetrical annular-addition reaction
Under argon shield, by four acetonitrile perchloric acid cuprous (3.3mg, 0.01mmol) and (R, R p)-1-[[the luxuriant Tie oxazolin of 2-(2-diphenylphosphine) Er] methyl]-2,3-methylimidazole fluoroform sulphonates (7.7mg, 0.011mmol) add and contain after the dry Schlenk bottle of molecular sieve, add 1mL methylene dichloride.Room temperature reaction, after 30 minutes, under ice-water bath condition, adds substrate glycine imine ester (0.1mmol) respectively, substrate nitro alkene (0.11mmol) and diisopropyl ethyl amine (1.4 μ L, 0.01mmol).System was 0 DEG C of reaction 12 hours.After reaction terminates, steam solvent, thick product column chromatography for separation (silica gel 100-200 order, eluent: sherwood oil: ethyl acetate=10:1).The non-corresponding body ratio of product by 1h NMR measures, and exo-configuration cycloaddition product ee value is by chirality Liquid Detection.
Product (exo)-3,5-phenylbenzene-2-methoxycarbonyl-4-nitro-pyrrole alkane.White solid.m.p.100-102℃。ee＝98.6％。[α] D 20＝-96.6(c 0.12,CH 2Cl 2)。 1H NMR(400MHz,CDCl 3):δ2.75(s b,1H),3.30(s,3H,COOMe),4.39(t,J＝8.4Hz,1H),4.51(d,J＝8.8Hz,1H),4.77(d,J＝8.0Hz,1H),5.22(t,J＝8.0Hz,1H),7.24-7.59(m,10H,Ph-H)。HPLC(Chiralpak AD-H column,hexane/2-propanol＝85/15,flow rate＝0.7mL/min)t R＝17.42min,18.83min。
Products collection efficiency 93%, product non-corresponding body ratio 92:8, exo-configuration enantiomeric excess value 98.6%.Embodiment 12:(R, R p)-1-[[the luxuriant Tie oxazolin of 2-(2-diphenylphosphine) Er] methyl]-2,3-methylimidazole hexafluorophosphate (6-PF 6) catalysis Asymmetrical annular-addition reaction
Under argon shield, by four acetonitrile perchloric acid cuprous (3.3mg, 0.01mmol) and (R, R p)-1-[[the luxuriant Tie oxazolin of 2-(2-diphenylphosphine) Er] methyl]-2,3-methylimidazole hexafluorophosphates (7.6mg, 0.011mmol) add and contain after the dry Schlenk bottle of molecular sieve, add 1mL methylene dichloride.Room temperature reaction, after 30 minutes, under ice-water bath condition, adds substrate glycine imine ester (0.1mmol) respectively, substrate nitro alkene (0.11mmol) and diisopropyl ethyl amine (1.4 μ L, 0.01mmol).System was 0 DEG C of reaction 12 hours.After reaction terminates, steam solvent, thick product column chromatography for separation (silica gel 100-200 order, eluent: sherwood oil: ethyl acetate=10:1).The non-corresponding body ratio of product by 1h NMR measures, and exo-configuration cycloaddition product ee value is by chirality Liquid Detection.
Products collection efficiency 83%, product non-corresponding body ratio 80:20, exo-configuration enantiomeric excess value 93.8%.Embodiment 13:(R, R p)-1-[[the luxuriant Tie oxazolin of 2-(2-diphenylphosphine) Er] methyl]-2,3-methylimidazole a tetrafluoro borate (6-BF 4) catalysis Asymmetrical annular-addition reaction
Under argon shield, by four acetonitrile perchloric acid cuprous (3.3mg, 0.01mmol) and (R, R p)-1-[[the luxuriant Tie oxazolin of 2-(2-diphenylphosphine) Er] methyl]-2,3-methylimidazole a tetrafluoro borates (7.0mg, 0.011mmol) add and contain after the dry Schlenk bottle of molecular sieve, add 1mL methylene dichloride.Room temperature reaction, after 30 minutes, under ice-water bath condition, adds substrate glycine imine ester (0.1mmol) respectively, substrate nitro alkene (0.11mmol) and diisopropyl ethyl amine (1.4 μ L, 0.01mmol).System was 0 DEG C of reaction 12 hours.After reaction terminates, steam solvent, thick product column chromatography for separation (silica gel 100-200 order, eluent: sherwood oil: ethyl acetate=10:1).The non-corresponding body ratio of product by 1h NMR measures, and exo-configuration cycloaddition product ee value is by chirality Liquid Detection.
Products collection efficiency 88%, product non-corresponding body ratio 85:15, exo-configuration enantiomeric excess value 97.8%.Embodiment 14:(R, R p)-1-[[the luxuriant Tie oxazolin of 2-(2-diphenylphosphine) Er] methyl]-2,3-methylimidazole salt compounded of iodine (6-I) catalysis Asymmetrical annular-addition reaction
Under argon shield, by four acetonitrile perchloric acid cuprous (3.3mg, 0.01mmol) and (R, R p)-1-[[the luxuriant Tie oxazolin of 2-(2-diphenylphosphine) Er] methyl]-2,3-methylimidazole salt compounded of iodine (7.4mg, 0.011mmol) add and contain after the dry Schlenk bottle of molecular sieve, add 1mL methylene dichloride.Room temperature reaction, after 30 minutes, under ice-water bath condition, adds substrate glycine imine ester (0.1mmol) respectively, substrate nitro alkene (0.11mmol) and diisopropyl ethyl amine (1.4 μ L, 0.01mmol).System was 0 DEG C of reaction 12 hours.After reaction terminates, steam solvent, thick product column chromatography for separation (silica gel 100-200 order, eluent: sherwood oil: ethyl acetate=10:1).The non-corresponding body ratio of product by 1h NMR measures, and exo-configuration cycloaddition product ee value is by chirality Liquid Detection.
Products collection efficiency 74%, product non-corresponding body ratio 78:22, exo-configuration enantiomeric excess value 91.6%.Embodiment 15:(R, R p)-1-[[the luxuriant Tie oxazolin of 2-(2-diphenylphosphine) Er] methyl]-2,3-methylimidazole perchlorate (6-ClO 4) catalysis Asymmetrical annular-addition reaction
Under argon shield, by four acetonitrile perchloric acid cuprous (3.3mg, 0.01mmol) and (R, R p)-1-[[the luxuriant Tie oxazolin of 2-(2-diphenylphosphine) Er] methyl]-2,3-methylimidazole perchlorate (7.1mg, 0.011mmol) add and contain after the dry Schlenk bottle of molecular sieve, add 1mL methylene dichloride.Room temperature reaction, after 30 minutes, under ice-water bath condition, adds substrate glycine imine ester (0.1mmol) respectively, substrate nitro alkene (0.11mmol) and diisopropyl ethyl amine (1.4 μ L, 0.01mmol).System was 0 DEG C of reaction 12 hours.After reaction terminates, steam solvent, thick product column chromatography for separation (silica gel 100-200 order, eluent: sherwood oil: ethyl acetate=10:1).The non-corresponding body ratio of product by 1h NMR measures, and exo-configuration cycloaddition product ee value is by chirality Liquid Detection.
Products collection efficiency 65%, product non-corresponding body ratio 85:15, exo-configuration enantiomeric excess value 90.2%.Embodiment 16: the asymmetric catalysis participated in from liquid and the recycling of catalyzer
Under argon shield, by four acetonitrile perchloric acid cuprous (3.3mg, 0.01mmol) and R, R p)-1-[[the luxuriant Tie oxazolin of 2-(2-diphenylphosphine) Er] methyl]-2,3-methylimidazole fluoroform sulphonates (7.7mg, 0.011mmol) add and contain after the dry Schlenk bottle of molecular sieve, add 0.9mL methylene dichloride.Room temperature reaction is after 30 minutes, under ice-water bath condition, add ionic liquid (0.1mL) respectively, substrate glycine imine ester (0.1mmol), substrate nitro alkene (0.11mmol) and diisopropyl ethyl amine (1.4 μ L, 0.01mmol).System was 0 DEG C of reaction 10 hours.After reaction terminates, steam organic solvent, ionic liquid uses anhydrous diethyl ether washing until do not have raw material and product to remain.Merge organic phase, steam solvent, thick product column chromatography for separation (silica gel 100-200 order, eluent: sherwood oil: ethyl acetate=10:1).The non-corresponding body ratio of product by 1h NMR measures, and exo-configuration cycloaddition product ee value is by chirality Liquid Detection.Residual ion liquid is at 1mmHg vacuum under pressure after dry 2 hours, rejoin 0.9mL methylene dichloride and substrate glycine imine ester (0.1mmol), substrate nitro alkene (0.11mmol) and diisopropyl ethyl amine (1.4 μ L, 0.01mmol).

Claims (4)

1., containing two luxuriant iron oxazoline-Phosphine ligands of imidazole salts group, it is characterized in that the compound of following general formula:
Wherein, X is OTf, PF 6, BF 4, I, ClO 4
2. the preparation method of two luxuriant iron oxazoline-Phosphine ligands containing imidazole salts group as claimed in claim 1; it is characterized in that: with the luxuriant iron oxazolin of (S)-4-methyl esters-2-two for starting raw material, obtain two luxuriant iron oxazoline-Phosphine ligands containing imidazole salts group through five steps such as ester group reduction, hydroxyl protection, the introducing of diphenylphosphine group, hydroxyl deprotection, ion fragment introducings.
3. the application of two luxuriant iron oxazoline-Phosphine ligands in Asymmetrical annular-addition reaction containing imidazole salts group as claimed in claim 1.It is characterized in that: under argon shield, by cuprous for four acetonitrile perchloric acid and add contain containing the luxuriant iron oxazoline-Phosphine ligands of imidazole salts two after the dry Schlenk bottle of molecular sieve, add methylene dichloride.Room temperature reaction, after 30 minutes, under ice-water bath condition, adds substrate glycine imine ester, substrate nitro alkene and diisopropyl ethyl amine respectively.System was 0 DEG C of reaction 12 hours.After reaction terminates, steam solvent, thick product column chromatography for separation (silica gel 100-200 order, eluent: sherwood oil: ethyl acetate=10:1).
4. recovery and the recycling containing two luxuriant iron oxazoline-Phosphine ligands of imidazole salts group as claimed in claim 1.It is characterized in that: in reaction, add methylene dichloride and ionic liquid.After reaction terminates, steam organic solvent, ionic liquid uses anhydrous diethyl ether washing until do not have raw material and product to remain.Merge organic phase, steam solvent, thick product column chromatography for separation (silica gel 100-200 order, eluent: sherwood oil: ethyl acetate=10:1).Residual ion liquid after dry 2 hours, rejoins solvent and substrate at 1mmHg vacuum under pressure.
CN201410667517.6A 2014-11-20 2014-11-20 Dicyclopentadienyl iron oxazoline-phosphine ligands containing imidazolium salt group, preparation method of dicyclopentadienyl iron oxazoline-phosphine ligands and application of dicyclopentadienyl iron oxazoline-phosphine ligands in asymmetrical cycloaddition reaction Pending CN104356168A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101486737A (en) * 2009-03-06 2009-07-22 北京理工大学 Ferrocene phosphinimine ligand containing quaternary ammonium salt group, preparation thereof and use for catalyzing asymmetric allyl group substitution reaction
CN101712697A (en) * 2008-10-07 2010-05-26 北京理工大学 Ferrocene phosphinimine ligand containing imidazole salt group, preparation thereof and application in catalyzing asymmetric allyl substitution reaction

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101712697A (en) * 2008-10-07 2010-05-26 北京理工大学 Ferrocene phosphinimine ligand containing imidazole salt group, preparation thereof and application in catalyzing asymmetric allyl substitution reaction
CN101486737A (en) * 2009-03-06 2009-07-22 北京理工大学 Ferrocene phosphinimine ligand containing quaternary ammonium salt group, preparation thereof and use for catalyzing asymmetric allyl group substitution reaction

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
YOSHIAKI NISHIBAYASHI等: "Asymmetric Synthesis and Highly Diastereoselective ortho-Lithiation of Oxazolinylferrocenes", 《SYNLETT》 *
ZHI-MING ZHOU等: "Catalytic effect and recyclability of imidazolium-tagged bis(oxazoline) based catalysts in asymmetric Henry reactions", 《ORG. BIOMOL. CHEM.》 *

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