CN105801415A - Fluorine-containing chiral allylic compound and preparation method thereof - Google Patents

Fluorine-containing chiral allylic compound and preparation method thereof Download PDF

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CN105801415A
CN105801415A CN201610164307.4A CN201610164307A CN105801415A CN 105801415 A CN105801415 A CN 105801415A CN 201610164307 A CN201610164307 A CN 201610164307A CN 105801415 A CN105801415 A CN 105801415A
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fluorine
allylic compound
chirality
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赵晓明
张红波
陈骥腾
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Tongji University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/62—Halogen-containing esters
    • C07C69/65—Halogen-containing esters of unsaturated acids
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2282—Unsaturated compounds used as ligands
    • B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
    • C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/73—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids
    • C07C69/734—Ethers
    • 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
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/44—Allylic alkylation, amination, alkoxylation or analogues
    • 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
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/827—Iridium

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  • Inorganic Chemistry (AREA)
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention provides a fluorine-containing chiral allylic compound and a preparation method thereof and mainly provides a synthesis method of the fluorine-containing chiral allylic compound. The preparation method includes the steps that firstly, [Ir(COD)Cl] 2 and a Feringa ligand are subjected to complexing, and a catalyst is generated; then, under the action of the catalyst, the reaction temperature is controlled, proper solvent is screened, an allyl substrate and 2-dimethyl fluoromalonate are added into a reaction tube through a one-pot method, the reaction time is controlled within 36 hours, and a final product, namely the fluorine-containing chiral allylic compound is generated. Compared with the prior art, the fluorine-containing chiral allylic compound is high in catalytic activity, mild in condition, high in regioselectivity, wide in substrate application scope and the like.

Description

A kind of fluorine-containing chirality allylic compound and preparation method thereof
Technical field
Synthetic organic chemical art belonging to the present invention.
Background technology
Fluorine-containing chipal compounds is important medicine fragment, and it plays important role in life chemistry.Meanwhile, contain Fluorine chipal compounds is the compound of a class high bioactivity, has a wide range of applications, at pesticide in agricultural and biomedicine In chemistry, it is also a kind of well insecticide.(a)E.J.Corey,K.A.Cimprich,Tetrahedron Lett.1992, 33,4099–4102.(b)C.A.Kiener,C.T.Shu,C.Incarvito,J.F.Hartwig, J.Am.Chem.Soc.2003,125,14272–14273.(c)A.W.van Zijl,L.A.Arnold,A.J.Minnaard, B.L.Feringa,Adv.Synth.Catal.2004,346,413–420.(d)M.Yan,L.W.Yang,K.Y.Wong, A.S.C.Chan,Chem.Commun.1999,11–12.
Fluorine-Containing Active Methylene derivant has stronger reactivity, has bigger answering in asymmetric catalysis Use prospect.In the asymmetric allylation of iridium catalysis, use Fluorine-Containing Active Methylene derivant as nucleopilic reagent mesh Front rarely found document report.(e)P.H.Carlsen,T.Katsuki,V.S.Martin and K.B.Sharpless, J.Org.Chem.,1981,46,3936.(f)B.S.Bal,W.E.Childers,Jr and H.W.Pinnick, Tetrahedron,1981,37,2091.(g)W-B Liu,L.-X.Dai and S.-L.You,Chem.Commun.2009, 6604–6606.
Summary of the invention
The purpose of the present invention is contemplated to synthesize a kind of fluorine-containing chirality allylic compound.
The fluorine-containing chirality allylic structural formula of compound of the present invention is:
Wherein R1Can be aryl or alkyl, R2Being methyl or ethyl, * represents chiral atom
The purpose of the present invention can be achieved through the following technical solutions:
First with [Ir (COD) Cl]2Catalyst is generated with Feringa ligand complex, then under the effect of additive, Control reaction temperature, screen suitable solvent, pi-allyl substrate and 2-fluorine dimethyl malenate one kettle way are added in reaction tube, time Between control at 36h, ultimately generate required fluorine-containing chirality allylic compound.
Reaction equation is as follows:
Wherein L is Feringa part, and Sol. is organic solvent, and Add. is various additive mentioned above, and T is reaction Temperature, OCO2Me is leaving group.
Wherein 3 and 4 is that the present invention synthesizes the target product obtained, and by the screening of condition, finds optimal conditions height region Optionally synthesize target product.Ligand structure is as it has been described above, be Feringa part.
Described additive be for 1,8-diazabicylo [5.4.0] 11 carbon-7-alkene (DBU), potassium phosphate, cesium carbonate, Cesium fluoride, potassium tert-butoxide, lithium chloride or combination therein.
Described pi-allyl substrate, 2-fluorine dimethyl malenate, [Ir (COD) Cl]2, Feringa part, the rubbing of additive That ratio is 1:2-4:0.03-0.04:0.06-0.08:2-4.The mol ratio of recommendation response is 1:2:0.03:0.06:2.
Reaction temperature is at-35 DEG C-30 DEG C, it is recommended that temperature is-10 DEG C.Response time is 24 hours-36 hours.
In the inventive method, garbled described garbled organic solvent be toluene, dimethyl sulfoxide, dichloromethane, Methanol, oxolane, N,N-dimethylformamide, dioxane or acetonitrile.
Use the inventive method products therefrom fluorine-containing chirality allylic compound can through thin layer chromatography, column chromatography or The method of decompression distillation separates.As by thin layer chromatography, the method for column chromatography, developing solvent used is that non-polar solven is molten with polarity The mixed solvent of agent.Recommendation developing solvent is petrol ether/ethyl acetate=10/1.
Fluorine-containing chipal compounds is important medicine fragment, and it plays important role in life chemistry.Meanwhile, exist In chemistry of pesticide, fluorine-containing chipal compounds is also a kind of well insecticide.In studying this course of reaction, the present invention is with iridium The lower Fluorine-Containing Active Methylene of catalysis is the allyl substitution reaction of nucleopilic reagent, makes reaction can realize the conjunction of high enantioselectivity Become fluorine-containing chirality allylic compound.The synthetic route of the present invention has reaction condition gentleness, wide application range of substrates, with Time also achieve good yield and enantioselectivity.
The fluorine-containing chipal compounds of present invention synthesis is important synthesis fragment, is widely used in organic chemistry, medicine The fields such as and chemistry of pesticide.
Compared with prior art, the present invention is first with [Ir (COD) Cl]2Catalyst is generated with Feringa ligand complex, Then under the effect of additive, control reaction temperature, screen suitable solvent, by pi-allyl substrate and 2-fluorine dimethyl malenate One kettle way adds in reaction tube, and the time controls at 36h, generates final required fluorine-containing chirality allylic compound.The party Method is applicable to different types of 2-fluoromalonic acid ester type compound and allyl carbonate methyl ester compounds, reaction condition temperature With.The additionally productivity of this reaction very well (yield is generally 75%-99%), regioselectivity the highest (generally >=99:1) is right Reflect selectivity higher (generally ee >=90%).
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in detail.
Embodiment 1
Metal iridium reacts interpolation with 2-fluorine dimethyl malenate with the allyl carbonate methyl ester of Feringa ligand catalysis The research of agent, temperature and solvent, and the impact that different ligands is on reaction.
Wherein add. refers to that additive, sol. refer to that solvent, T refer to temperature.
Wherein DCM is dichloromethane, and Toluene is toluene, and THF is oxolane, CH3CN is acetonitrile, and DMSO is diformazan Base sulfoxide, Dioxane is dioxane, CH3OH is methanol.L is Feringa part.
Embodiment 2
Metal iridium reacts with 2-fluorine dimethyl malenate with the allyl carbonate methyl ester of Feringa ligand catalysis
In the reaction tube of an argon shield being dried, it is sequentially added into [Ir (COD) Cl]2(0.003mmol), part (0.006mmol) with DCM (2.0mL), complexation 30 minutes at room temperature 30 DEG C.In reaction tube, pi-allyl is added with microsyringe Methyl carbonate substrate (0.1mmol), complexation 15min, with microsyringe, 2-fluorine dimethyl malenate (0.2mmol) is added subsequently Enter in reaction tube, under argon shield, add Cs2CO3(0.2mmol), reaction 36 hours.After reaction terminates, after removal of solvent under reduced pressure Residue thin layer chromatography obtains target product 3 (petrol ether/ethyl acetate=10:1, v/v).
Target product 1:(S)-fluoro-the 2-of dimethyl-2-(1-phenyl allyl) malonate
White solid, 93% yield, 94%ee [chiral column AD-H (0.46cm x 25cm)；Normal hexane/isopropanol=98/ 2；Flow velocity=1.0mL/min；Detection wavelength=214nm；tR=9.782 (major), 10.273 (minor) min].
[α]D 20=+25.5 ° of (c 0.6, CHCl3).
1H NMR(400MHz,CDCl3) δ=7.46 7.25 (m, 5H), 6.17 (dt, J=17.2,9.6Hz, 1H), 5.39 5.13 (m, 2H), 4.41 (dd, J=31.8,8.9Hz, 1H), 3.91 (d, J=6.6Hz, 3H), 3.63 (s, 3H) ppm.
19F NMR(376MHz,CDCl3) δ=-176.04 (s) ppm.
13C NMR(101MHz,CDCl3) δ=165.69 (d, J=25.7Hz), 165.22 (d, J=25.9Hz), 136.43,133.69 (d, J=4.7Hz), 129.13 (d, J=2.2Hz), 128.63,127.84,119.54,98.51, 96.43,54.52 (d, J=18.4Hz), 53.59,53.26ppm.
HRMS(ESI+)calcd for C14H15NaO4[M+Na]+:289.0846,Found:289.0847.
Target product 2:(S)-fluoro-the 2-of dimethyl-2-(1-(3-methoxyphenyl) pi-allyl) malonate
White solid, 93% yield, 94%ee [chiral column AD-H (0.46cm x 25cm)；Normal hexane/isopropanol= 98/2；Flow velocity=1.0mL/min；Detection wavelength=214nm；tR=9.655 (major), 10.284 (minor) min].
[α]D 20=+25.4 ° of (c 0.5, CHCl3).
1H NMR(400MHz,CDCl3) δ=7.34 7.25 (m, 1H), 7.13 6.64 (m, 3H), 6.15 (dt, J= 17.2,9.6Hz, 1H), 5.27 (dd, J=13.6,8.0Hz, 2H), 4.38 (dd, J=31.5,8.9Hz, 1H), 3.99 3.85 (m, 3H), 3.83 (s, 3H), 3.68 (d, J=21.4Hz, 3H) .ppm.
19F NMR(376MHz,CDCl3) δ=-175.63 (s) ppm.
13C NMR(101MHz,CDCl3) δ=165.68 (d, J=25.9Hz), 165.19 (d, J=25.9Hz), (159.58,137.94,133.61 d, J=4.9Hz), 129.55,121.41 (d, J=2.3Hz), 119.50,114.84 (d, J =2.5Hz), 113.23,99.16 97.82 (m), 97.12 95.97 (m), and 55.20,54.45 (d, J=18.4Hz), 53.54, 53.25ppm.
HRMS(ESI+)calcd for C15H17FNaO5[M+Na]+:319.0952,Found:319.0966.
Target product 3:(S)-dimethyl-2-fluorine 2-(1-(2-naphthyl) pi-allyl) malonate
White solid, 93% yield, 95%ee [chiral column IC (0.46cm x 25cm)；Normal hexane/isopropanol=98/2； Flow velocity=1.0mL/min；Detection wavelength=214nm；tR=19.007 (major), 21.006 (minor) min].
[α]D 20=+35.3 ° of (c 0.5, CHCl3).
1H NMR(400MHz,CDCl3) δ=7.84 (d, J=6.0Hz, 4H), 7.62 7.36 (m, 3H), 6.28 (dt, J= 17.3,9.5Hz, 1H), 5.48 5.12 (m, 2H), 4.61 (dd, J=31.7,8.7Hz, 1H), 3.92 (d, J=12.8Hz, 3H),3.59(s,3H)ppm.
19F NMR(376MHz,CDCl3) δ=-175.59 (s) ppm.
13C NMR(101MHz,CDCl3) δ=165.73 (d, J=25.8Hz), 165.25 (d, J=25.9Hz), (134.05,133.74 d, J=4.6Hz), 133.36,132.83,128.28,128.04,127.62,126.97 (d, J= 2.5Hz), 126.17,119.68,98.62,96.53,54.54 (d, J=18.4Hz), 53.60,53.26 ppm.
HRMS(ESI+)calcd for C18H17FNaO4[M+Na]+:339.1003,Found:339.0979.
Target product 4:(S)-dimethyl-2-fluorine 2-(1-(4-fluorophenyl) pi-allyl) malonate
White solid, 96% yield, 93%ee [chiral column IC (0.46cm x 25cm)；Normal hexane/isopropanol=98/2； Flow velocity=1.0mL/min；Detection wavelength=214nm；tR=14.038 (major), 15.075 (minor) min].
1H NMR(400MHz,CDCl3) δ=7.34 (dd, J=7.5,5.6Hz, 2H), 7.04 (t, J=8.6Hz, 2H), 6.27 6.00 (m, 1H), 5.42 5.11 (m, 2H), 4.41 (dd, J=31.6,8.8Hz, 1H), 3.90 (s, 3H), 3.65 (s, 3H)ppm.
19F NMR(376MHz,CDCl3) δ=-114.37 (s) ,-176.51 (s) ppm
13C NMR(101MHz,CDCl3) δ=165.52 (d, J=25.8Hz), 165.13 (d, J=25.8Hz), 163.54,161.09,133.49 (d, J=4.6Hz), 132.19 (d, J=3.3Hz), 130.83 (dd, J=8.1,2.4Hz), (d, J=21.3Hz), 119.71,115.54 98.40,96.31,53.70 (d, J=9.0Hz), 53.56,53.35ppm.
HRMS(ESI+)calcd for C14H14F2NaO4[M+Na]+:307.0752,Found:307.0754.
Target product 5:(S)-dimethyl-2-fluorine 2-(1-(4-bromophenyl) pi-allyl) malonate
White solid, 90% yield, 94%ee [chiral column AD-H (0.46cm x 25cm)；Normal hexane/isopropanol=98/ 2；Flow velocity=1.0mL/min；Detection wavelength=214nm；tR=13.035 (major), 14.065 (minor) min].
1H NMR(400MHz,CDCl3) δ=7.50 (dd, J=18.6,8.4Hz, 2H), 7.27 (dd, J=22.6, 8.0Hz, 2H), 6.42 5.85 (m, 1H), 5.58 4.80 (m, 2H), 4.43 (ddd, J=40.3,23.2,5.6Hz, 1H), 4.04 3.75 (m, 3H), 3.68 (d, J=21.2Hz, 3H).
19F NMR(376MHz,CDCl3) δ=-176.19 (s).
13C NMR(101MHz,CDCl3) δ=165.43 (d, J=25.8Hz), 165.05 (d, J=25.8Hz), 135.54,133.23 (d, J=4.6Hz), 131.76,130.88 (d, J=2.4Hz), 121.99,119.90,98.16, 96.08,53.78 (d, J=18.5Hz), 53.61,53.35ppm.
HRMS(ESI+)calcd for C14H14BrFNaO4[M+Na]+:366.9952,Found:366.9926.
Target product 6:(S)-dimethyl-2-fluorine 2-(1-(4-chlorphenyl) pi-allyl) malonate
White solid, 97% yield, 99%ee [chiral column AD-H (0.46cm x 25cm)；Normal hexane/isopropanol=98/ 2；Flow velocity=1.0mL/min；Detection wavelength=214nm；tR=14.048 (major), 15.077 (minor) min].
1H NMR(400MHz,CDCl3) δ=7.48 7.22 (m, 4H), 6.31 5.87 (m, 1H), 5.50 5.05 (m, 2H), 4.40 (dd, J=31.5,8.8Hz, 1H), 3.89 (d, J=6.8Hz, 3H), 3.66 (s, 3H).
19F NMR(376MHz,CDCl3) δ=-176.27 (s).
13C NMR(101MHz,CDCl3) δ=165.46 (d, J=25.8Hz), 165.07 (d, J=25.8Hz), (134.96,133.81,133.24 d, J=4.6Hz), 130.54 (d, J=2.4Hz), 128.82,119.94,98.26, 96.18,53.84,53.67 (d, J=3.2Hz), 53.41ppm.
HRMS(ESI+)calcd for C14H14ClFNaO4[M+Na]+:323.0457,Found:323.0439.
Target product 7:(S)-dimethyl-2-fluorine 2-(1-(4-tolyl) pi-allyl) malonate
White solid, 90% yield, 95%ee [chiral column IC (0.46cm x 25cm)；Normal hexane/isopropanol=98/2； Flow velocity=1.0mL/min；Detection wavelength=214nm；tR=10.041 (major), 11.103 (minor) min].
1H NMR(400MHz,CDCl3) δ=7.30 7.05 (m, 4H), 6.33 5.97 (m, 1H), 5.25 (dd, J= 13.6,7.2Hz, 2H), 4.38 (dd, J=31.8,8.9Hz, 1H), 3.88 (d, J=7.5Hz, 3H), 3.64 (s, 3H), 2.36 (d, J=7.2Hz, 3H).
19F NMR(376MHz,CDCl3) δ=-176.06 (s).
13C NMR(101MHz,CDCl3) δ=165.75 (d, J=25.8Hz), 165.27 (d, J=26.0Hz), 137.47,133.91 (d, J=4.7Hz), 133.40,129.31,128.96 (d, J=2.2Hz), 119.22,98.5,96.47, 54.14 (d, J=18.5Hz), 53.50,53.19,21.10ppm.
HRMS(ESI+)calcd for C15H17FNaO4[M+Na]+:303.1003,Found:303.1001。

Claims (8)

1. a fluorine-containing chirality allylic compound, it is characterised in that the molecular formula of this compound is as follows:
Wherein R1Can be aryl or alkyl, R2Being methyl or ethyl, * represents chiral atom.
2. one kind synthesizes the preparation method of fluorine-containing chirality allylic compound described in claim 1, it is characterised in that first profit With [Ir (COD) Cl]2Generate catalyst with Feringa ligand complex, then under the effect of additive, control reaction temperature, Screening suitable solvent, adds in reaction tube by pi-allyl substrate and 2-fluorine dimethyl malenate one kettle way, and the control response time exists 36h, generates end-product fluorine-containing chirality allylic compound.
A kind of method synthesizing fluorine-containing chirality allylic compound the most according to claim 2, it is characterised in that described Side chain pi-allyl substrate, 2-fluorine dimethyl malenate, [Ir (COD) Cl]2, Feringa part, the mol ratio of additive be 1: 2-4:0.03-0.04:0.06-0.08:2-4。
A kind of method synthesizing fluorine-containing chirality allylic compound the most according to claim 2, it is characterised in that described Expansion the structural formula of 2-fluorine dimethyl malenate be:
Described allyl carbonate methyl ester compounds structural formula:
Described part is optical voidness part, and structural formula is as follows:
Wherein * is chiral atom, R3Selected from C1-C16Alkyl, C4-C10Containing N, O or the heterocyclic radical of sulfur or C4-C10Containing N, O or The heteroaryl of sulfur, aryl, R4Selected from C4-C10Containing N, O or the heterocyclic radical of sulfur or C4-C10Containing N, O or the heteroaryl of sulfur, virtue Base.
A kind of method synthesizing fluorine-containing chirality allylic compound the most according to claim 2, it is characterised in that described Garbled additive is 1,8-diazabicylo [5.4.0] 11 carbon-7-alkene (DBU), potassium phosphate, cesium carbonate, cesium fluoride, uncle Butanol potassium, lithium chloride.
A kind of method synthesizing fluorine-containing chirality allylic compound the most according to claim 2, it is characterised in that described Garbled organic solvent be toluene, dimethyl sulfoxide, dichloromethane, methanol, oxolane, N,N-dimethylformamide, two Oxygen six ring or acetonitrile.
A kind of method synthesizing fluorine-containing chirality allylic compound the most according to claim 2, it is characterised in that described Garbled reaction temperature-35 DEG C～30 DEG C.
A kind of method synthesizing fluorine-containing chirality allylic compound the most according to claim 2, it is characterised in that synthesis The product obtained is through thin layer chromatography, column chromatography or decompression separated.
CN201610164307.4A 2016-03-22 2016-03-22 Fluorine-containing chiral allylic compound and preparation method thereof Pending CN105801415A (en)

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CN108373431A (en) * 2018-02-08 2018-08-07 同济大学 Fluorine-containing chirality allyl compound and its synthetic method
CN114736108A (en) * 2022-04-12 2022-07-12 同济大学 Allyl carbonyl enol compound and synthetic method thereof
CN114736108B (en) * 2022-04-12 2023-10-27 同济大学 Allyl carbonyl enol compound and synthesis method thereof

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