CN108947754B - Use of bidentate phosphite ligands in C-F bond building reactions - Google Patents
Use of bidentate phosphite ligands in C-F bond building reactions Download PDFInfo
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- CN108947754B CN108947754B CN201811005586.5A CN201811005586A CN108947754B CN 108947754 B CN108947754 B CN 108947754B CN 201811005586 A CN201811005586 A CN 201811005586A CN 108947754 B CN108947754 B CN 108947754B
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/16—Preparation of halogenated hydrocarbons by replacement by halogens of hydroxyl groups
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/22—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of halogens; by substitution of halogen atoms by other halogen atoms
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- C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
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Abstract
The invention discloses an application of bidentate phosphite ligand in C-F bond construction reaction, the bidentate phosphite ligand with different connection structures can be applied to C-F bond construction reaction catalyzed by iron, the ligand and ferric salt are co-catalyzed to generate allyl alcohol compound fluorination reaction in an organic solvent, and the bidentate phosphite ligand has the following general formula:
Description
Technical Field
The invention relates to an application of a bidentate phosphite ligand with a biphenyl diphenol skeleton in a C-F bond construction reaction. The catalyst can be used for catalyzing the fluorination reaction of allyl alcohol compounds to synthesize fluorine-containing organic compounds.
Background
Since fluorine has a high electronegativity and a property different from that of other elements, if it is introduced into an organic molecule, the physical, chemical and biophysical properties of a parent compound can be changed, thereby imparting unique properties to the fluorine-containing organic compound, and the fluorine-containing organic compound is widely applied to the fields of medicines, pesticides, materials and the like. The design and synthesis of ligand capable of forming complex catalyst with metal is key for high-efficiency C-F bond construction reaction, the catalyst used in the C-F bond construction reaction mainly is palladium, silver, copper and other compounds, and the ligand is mainly concentrated in monophosphine ligand PPh3(Angew. chem. int. Ed.2011,50,2613-2617), bisphosphine ligands (J.Am. chem. Soc.2011,133, 15902-15905) (J.Am. chem. Soc.2010,132, 17402-17404) and the like, while bidentate phosphite ligands having the advantages of simple synthesis, insensitivity to air and water, close chelation with metals and the like are less applied in the reaction. Bidentate phosphite ligands are widely used in asymmetric hydroformylation, asymmetric hydrogenation reactions (inorg. chem.,1990,29,5006), (org. lett.,2004,69, 4031-. On the basis, the patent applies for the application of a bidentate phosphite ligand taking biphenyl diphenol as a framework in C-F bond construction reaction.
Disclosure of Invention
The invention aims to provide the application of bidentate phosphite ester ligands taking biphenol as a framework in C-F bond construction reaction based on the thought, the catalyst has mild synthesis condition and short reaction time, the ligands are stable and easy to prepare in large quantity, and the ligands and iron co-catalyze allyl fluorination reaction to construct a novel carbon-fluorine bond to synthesize different fluorine-containing compounds.
In order to achieve the purpose, the invention adopts the following technical scheme:
a bidentate phosphite ligand with a different linkage structure and capable of reacting with iron catalyzed allylic fluorination to create a carbon-fluorine bond. The bidentate phosphite ligand has the general formula:
linker in the general formula is different connecting structures, wherein the Linker is connected with P after H on a hydroxyl group of a corresponding diol is removed. The following compounds are selected as examples:
the invention aims to provide the application of the series of ligands, namely the ligands are used for preparing a catalyst for C-F bond construction reaction and catalyzing allyl fluorination reaction. The ligand and iron co-catalyze the reaction in which hydroxyl groups using allyl alcohol as a substrate are substituted by fluorine to build a carbon-fluorine bond. The method comprises the following steps: under the protection of inert gas, adding a ligand/Fe catalyst, an allyl alcohol compound and a fluorination reagent into an organic solvent by a one-pot method, reacting at the temperature of 20-150 ℃ for 1-36h, quenching after the reaction is completed, and carrying out column chromatography separation to obtain the product.
The organic solvent used in the above method of the present invention is toluene, dichloromethane, tetrahydrofuran, dioxane, N-dimethylformamide, or dimethylsulfoxide.
The iron catalyst is FeCl2、FeSO4、Fe(OTf)2、Fe(OTf)3Or Fe2O3Wherein OTf represents trifluoromethanesulfonate; the molar ratio of the ferric salt to the ligand is 1: 0.5-10.
In the above-mentioned method of the present invention, the allyl alcohol is cinnamyl alcohol, 4-methylcinnamyl alcohol, 3-methylcinnamyl alcohol, 2-methylcinnamyl alcohol, 4-methoxycinnamyl alcohol, 4-tert-butylcinnamyl alcohol, 4-bromocinnamyl alcohol, 4-nitrocinnamyl alcohol, 4-trifluoromethylcinnamyl alcohol, 4-phenylcinnamyl alcohol, 3-naphthyl-2-allyl alcohol, 3-methyl-2-butenol, 2-cyclohexenol, or geraniol. The fluorinating agent is KF, CsF, AgF, or NEt3·3HF。
The molar ratio of the ligand to the allyl alcohol compound is 0.1: 1.
The invention has the beneficial effects that: the invention provides a new application of bidentate phosphite ester ligand using biphenol as a framework for catalyzing allyl fluorination reaction, and a catalytic system has high reaction activity and wide substrate universality. The catalyst system constructs carbon-fluorine bonds to synthesize different fluorine-containing organic compounds, and the consumption of the reaction catalyst is small.
Detailed Description
The present invention will be further described with reference to the following examples, which are provided to assist in further understanding of the invention, but are not intended to limit the scope of the invention.
Application of bidentate phosphite ligand/iron-catalyzed C-F bond construction reaction
Screening the optimal reaction conditions:
cinnamyl alcohol and silver fluoride are used as templates for reaction, and conditions such as ligand, solvent, temperature and the like are screened.
The chemical formula is allyl fluoridized template reaction
TABLE 1 screening of conditions for L/Fe catalyzed reaction of cinnamyl alcohol with silver fluoride[a]
[a]Reaction conditions are as follows: cinnamyl alcohol (0.5mmol), silver fluoride (1.5mmol), solvent (2.0mL), Fe (OTf)2(5 mol%), ligand (10 mol%), reaction time 12h in N2Reaction under atmosphere [ b]The yield is the isolation yield [ c ]]The ligand dosage is 20 mol%.
Firstly, cinnamyl alcohol and silver fluoride are selected as templates for reaction,with Fe (OTf)2The ligand was selected for the metal catalyst using toluene as solvent (examples 1-7), and comparison revealed that ligand L2Yields of up to 80% were obtained (example 7) and the yield of the same type of bidentate phosphite ligand was higher than the other types of phosphine ligand. Illustrating the superiority of bidentate phosphite ligands in catalyzing the fluorination of allyl alcohol. When with L2When the solvent was examined as a ligand (examples 7 to 11), toluene was found to be the most preferable solvent. The reaction was greatly affected by temperature (examples 7, 12-15), the reaction was not substantially reacted at normal temperature, the yield was improved when the temperature was increased, the yield reached 80% when the temperature reached 110 ℃ and was not substantially changed when the temperature was increased to 120 ℃, so that the optimum temperature was determined to be 110 ℃.
By screening the reaction conditions of cinnamyl alcohol and silver fluoride, the optimal reaction conditions are selected: 110 ℃ in Fe (OTf)2/L2As a catalyst, allyl alcohol was catalyzed in toluene solvent, and aromatic allyl alcohol and aliphatic allyl alcohol were studied and searched, respectively (Table 2)
Chemical formula Fe (OTf)2/L2Catalysis of allylic fluorination of different substrates
TABLE 2 Fe (OTf)2/L2Catalytic reaction results of allylic fluorination of different substrates
Reaction conditions are as follows: cinnamyl alcohol (0.5mmol), silver fluoride (1.5mmol), toluene (2.0mL), Fe (OTf)2(5mol％)/L2(10 mol%) as catalyst in N2Counter reaction in atmosphereThe reaction time is 12h, and the yield is the isolation yield.
From the reaction result, when the selected catalytic system is used for the fluorination reaction of allyl alcohol compounds, the overall catalytic effect is good, and the yield is mostly greater than 80%. When an aromatic allyl alcohol compound is used as a substrate, the target product can be obtained in a high yield (80 to 88%) without greatly affecting the reaction when the aromatic allyl alcohol compound has a structure having different steric hindrance (examples 17 to 20). The yield was slightly affected when there was a different electronic effect in the 4 position (examples 21-27), as shown by: the yield is improved when the 4-position is electron donating, and the yield is reduced when the 4-position is electron withdrawing. To further verify the catalytic activity of the catalytic system, we tried the reaction of fatty allyl alcohol derivatives (examples 28-30) and silver fluoride as substrates, and found that the catalyst used has high catalytic activity on the fatty allyl alcohol derivatives as well.
Fe(OTf)2/L2The catalytic system has high activity for fluorination reaction of aromatic allyl alcohol derivatives and reaction of aliphatic allyl alcohol derivatives; using AgF as fluorine source in Fe (OTf)2/L2The carbon-fluorine bond is constructed under the catalysis system to synthesize fluorine-containing organic compounds with different structures, the reaction area selectivity is good, the yield is high, and the substrate universality is strong.
The foregoing shows and describes the general principles and features of the present invention, together with the advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (3)
1. Use of a bidentate phosphite ligand in a C-F bond formation reaction, wherein: bidentate phosphite ligands with different connection structures can be applied to the construction reaction with iron-catalyzed C-F bonds, the ligand and ferric salt are co-catalyzed to generate the fluorination reaction of allyl alcohol compounds in an organic solvent, and the bidentate phosphite ligand has the following structural formula:
the iron salt is Fe (OTf)2；
The organic solvent is toluene, tetrahydrofuran or dioxane;
the molar ratio of the ligand to the ferric salt is 1 (0.5-10), the reaction temperature is 60-150 ℃, and the reaction time is 1-36 h;
the fluorination reagent adopted in the fluorination reaction of the allyl alcohol compound is AgF.
2. Use of a bidentate phosphite ligand according to claim 1 in a C-F bond building reaction, wherein: the allyl alcohol compound is cinnamyl alcohol, 4-methyl cinnamyl alcohol, 3-methyl cinnamyl alcohol, 2-methyl cinnamyl alcohol, 4-methoxy cinnamyl alcohol, 4-tert-butyl cinnamyl alcohol, 4-bromo cinnamyl alcohol, 4-nitro cinnamyl alcohol, 4-trifluoromethyl cinnamyl alcohol, 4-phenyl cinnamyl alcohol, 3-naphthyl-2-allyl alcohol, 3-methyl-2-butenol or geraniol.
3. Use of a bidentate phosphite ligand according to claim 1 in a C-F bond building reaction, wherein: the molar ratio of the ligand to the allyl alcohol compound is 0.1: 1.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102516300A (en) * | 2011-11-09 | 2012-06-27 | 中山大学 | Phosphine ligands, enantiomers or racemates thereof, and preparation methods of above |
| CN105801625A (en) * | 2016-05-30 | 2016-07-27 | 郑州大学 | Preparation method of novel bidentate phosphite ligand and application thereof in Buchwald-Hartwig reaction |
| CN107827931A (en) * | 2017-11-21 | 2018-03-23 | 郑州大学 | Using '-biphenyl diphenol as bidentate phosphite ester ligand of construction unit and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102516300A (en) * | 2011-11-09 | 2012-06-27 | 中山大学 | Phosphine ligands, enantiomers or racemates thereof, and preparation methods of above |
| CN105801625A (en) * | 2016-05-30 | 2016-07-27 | 郑州大学 | Preparation method of novel bidentate phosphite ligand and application thereof in Buchwald-Hartwig reaction |
| CN107827931A (en) * | 2017-11-21 | 2018-03-23 | 郑州大学 | Using '-biphenyl diphenol as bidentate phosphite ester ligand of construction unit and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| Iron-Catalyzed Synthesis of Amines and Thioethers Directly from Allylic Alcohols;Panke Zhang等;《Asian J. Org. Chem 》;20180516;第7卷;第875-878页 * |
| Iron-Catalyzed, Fluoroamide-Directed C−H Fluorination;Brian J.等;《J. Am. Chem. Soc》;20160927;第138卷;第12771-12774页 * |
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