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2,4,6- Or 2,6-Alkoxyphenyl Dialkylphosphine, Tetrafluoroborate, Preparation Method and Use Thereof

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2,4,6- Or 2,6-Alkoxyphenyl Dialkylphosphine, Tetrafluoroborate, Preparation Method and Use Thereof (19) & (11) EP 2 492 274 A1 (12) EUROPEAN PATENT APPLICATION published in accordance with Art. 153(4) EPC (43) Date of publication: (51) Int Cl.: 29.08.2012 Bulletin 2012/35 C07F 9/50 (2006.01) B01J 31/24 (2006.01) C07C 43/215 (2006.01) C07C 41/30 (2006.01) (2006.01) (21) Application number: 09850497.0 C07D 307/58 (22) Date of filing: 21.12.2009 (86) International application number: PCT/CN2009/001527 (87) International publication number: WO 2011/047501 (28.04.2011 Gazette 2011/17) (84) Designated Contracting States: •LV,Bo AT BE BG CH CY CZ DE DK EE ES FI FR GB GR Zhejiang 310027 (CN) HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL • FU, Chunling PT RO SE SI SK SM TR Zhejiang 310027 (CN) (30) Priority: 22.10.2009 CN 200910154029 (74) Representative: Meyer-Dulheuer, Karl-Hermann Dr. Meyer- Dulheuer & Partner (71) Applicant: Zhejiang University Patentanwaltskanzlei Hangzhou, Zhejiang 310027 (CN) Mainzer-Landstrasse 69-71 60329 Frankfurt am Main (DE) (72) Inventors: • MA, Shengming Zhejiang 310027 (CN) (54) 2,4,6- OR 2,6-ALKOXYPHENYL DIALKYLPHOSPHINE, TETRAFLUOROBORATE, PREPARATION METHOD AND USE THEREOF (57) The current invention relates to the structure, current invention uses only one step to synthesize dialkyl synthesis of dialkyl(2,4,6- or 2,6-alkoxyphenyl)phos- (2,4,6- or 2,6-alkoxyphenyl)phosphine and its tetrafluor- phine or its tetrafluoroborate, as well as its applications oborate is stable in the air. Compared with known syn- in the palladium catalyzed carbon-chlorine bond activa- thetic routes of ligands used in activating carbon- chlorine tion for Suzuki coupling reactions and carbon-nitrogen bonds, the method of current invention is short, easy to bond formation reactions. The dialkyl (2,4,6- or 2,6- alkox- operate. Moreover, with this type of ligands, the Suzuki yphenyl)phosphine or its tetrafluoroborate could coordi- coupling products of optically active chlorolactones and nate with the palladium catalyst to activate the inert car- arylboronic acids would maintain their configuration and bon-chlorine bond highly selectively and catalyze Suzuki optical purity. coupling reaction with arylboronic acid or carbon-nitro- gen bond formation reaction with organic amines. The EP 2 492 274 A1 Printed by Jouve, 75001 PARIS (FR) EP 2 492 274 A1 Description Technical Field: 5 [0001] The current invention relates to the structure, a simple one step synthesis of dialkyl(2,4,6- or 2,6- alkoxyphenyl) phosphine or its tetrafluoroborate, as well as its applications in the Suzuki coupling reactions and the carbon-nitrogen bond formation reactions after palladium catalyzed carbon- chlorine bond activation reactions. To be more specific, during the synthesis of stable dialkyl(2,4,6- or 2,6-alkoxyphenyl)phosphine or its tetrafluoroborate, the highly active organic phosphine is used to coordinate with the palladium catalyst in order to activate the inert carbon-chlorine bond highly 10 selectively. Background technology: [0002] Organic halides are very important building blocks in organic synthesis. However, in their application in the 15 past, expensive but relatively active organic bromides and iodides were used in coupling reactions to synthesize target molecules (Chem. Rev. 1994, 94, 1047). If inert carbon-chlorine bonds can be selectively activated and to use cheap chlorides in these types of reactions, it would be much better not only in respect of atom economy but also in respect of industrial cost. So far, some organic phosphine ligands can be used to activate inert carbon-chlorine bonds (Angew. Chem. Int. Ed. 2002, 41, 4176 ; Acc. Chem. Res. 2007, 40, 275 ; Acc. Chem. Res. 2007, 40, 676 ; Acc. Chem. Res. 20 2008, 41, 1461 ; Eur. J. Org. Chem. 2008, 2013 ; Angew. Chem. Int. Ed. 2008, 47, 6338). However, during the study on the carbon- chlorine bond coupling reactions of the optically active β-chloro-α,β-unsaturated five-membered lactones, the inventor of the current invention has discovered that some ligands commonly used in the activation of carbon- chlorine bonds (such as: tricyclohexylphosphonium tetrafluoroborate or 2-dicyclohexylphosphino-2’,6’-dimethoxybiphenyl etc.) cannot yield the corresponding optically active coupling products highly selectively (please see embodiments for specific 25 examples). Content of the invention: [0003] The object of the current invention is to provide a new type of organic phosphine ligand --- dialkyl (2,4,6- or 2,6- 30 alkoxyphenyl)phosphine and its tetrafluoroborate as well as the method of their preparation. [0004] Another goal of the current invention is to provide a method and application for the inert sp2 carbon-chlorine bonds activations highly selectively in the presence of the palladium catalyst and the above mentioned organic phosphine or its tetrafluoroborate. [0005] The coordination of dialkyl (2,4,6- or 2,6- alkoxyphenyl)phosphine or its tetrafluoroborate with palladium catalyst 35 can activate inert carbon-chlorine bonds highly selectively, and can catalyze Suzuki coupling reaction with arylboronic acid, or carbon-nitrogen bond formation reaction with organic amines. Compared with known synthetic routes of ligands used in activating carbon- chlorine bonds, the method of current invention is short, easy to operate, which has undoubtedly high research and application value. [0006] The structures of the dialkyl(2,4,6- or 2,6-alkoxyphenyl)phosphine and its tetrafluoroborate of the current in- 40 vention are as follows: 45 50 wherein, R1, R2 is isopropyl, tertbutyl, cyclopropyl, cyclopentyl, cyclohexyl or admantyl group and R3 is alkyl group. [0007] In the method to synthesize dialkyl (2,4,6- or 2,6-alkoxyphenyl)phosphine or its tetrafluoroborate of the current invention, trichlorophosphine, alkylmagnesium chloride, alkoxybenzene and n-butyl lithium are used as starting materials. 1,3- or 1,3,5-alkoxybenzene is reacted with n-butyl lithium in tetrahydrofuran to produce the corresponding lithium reagent. Alkylmagnesium chloride is reacted with trichlorophosphine to produce chlorodialkyl phosphine. The above 55 mentioned lithium reagent is reacted with chlorodialkyl phosphine to produce dialkyl(2,4,6- or 2,6-alkoxyphenyl)phos- phine. Tetrafluoroboric acid aqueous solution can be used to quench the reaction to produce the corresponding pure dialkyl(2,4,6- or 2,6-alkoxyphenyl)phosphine tetrafluoroborate after re-crystallization. [0008] More detailed reaction steps are described as follows: 2 EP 2 492 274 A1 3 1) use tetrahydrofuran as an organic solvent, and at room temperature, alkoxybenzene (RO)nC6H(6-n) is reacted 3 with n-butyl lithium for 2-15 hours to produce the corresponding lithium reagent (R O)nC6H(5-n)Li; 3 1 2 2) react the lithium reagent above (R O)nC6H(5-n)Li with chlorodialkyl phosphine R R PCl under -78-30 °C for 2 to 3 1 2 10 hours to produce a dialkyl(2,4,6- or 2,6-alkoxyphenyl)phosphine (R O)nC6H(5-n)P R R , tetrafluoroboric acid 5 aqueous solution is used to quench the reaction and to produce the corresponding dialkyl (2,4,6- or 2,6- alkoxyphenyl) 3 1 2 + - phosphine tetrafluoroborate ((R O)nC6H(5-n)P R R )(H BF4 ); the molar ratio of said chlorodialkyl phosphine and (2,4,6- or 2,6-alkoxyphenyl) lithium is 0.8-1.2 : 1; said R1, R2 and R3 are as described before. The reaction products can be purified by re-crystallization. 10 [0009] A typical reaction formula is as follows: 15 20 25 30 [0010] In the reaction, R1, R2 is isopropyl, tertbutyl, cyclopropyl, cyclopentyl, cyclohexyl or admantyl group and R 3 is alkyl group. [0011] Dialkyl(2,4,6- or 2,6-alkoxyphenyl)phosphine and its tetrafluoroborate of the current invention can be used in 35 the selective activation of inert carbon-chlorine bond for Suzuki coupling reaction to produce biphenyl compounds. [0012] The more detailed description of the above mentioned application is as follows: The synthesis of the coupling compounds are carried out under the protection of inert gases, at 80-120 °C, in an organic solvent, with the dialkyl (2,4,6- or 2,6-alkoxyphenyl)phosphine or its tetrafluoroborate and palladium as catalysts, arylboronic acid, base, water and arylchloride are reacted for 0.6-28 hours to produce the corresponding biphenyl compounds; said organic solvent is 1,4- 40 dioxane or toluene; the equivalent molar ratio of base, palladium catalyst, dialkyl(2,4,6- or 2,6-alkoxyphenyl)phosphine or its tetrafluoroborate, arylboronic acid, water and arylchloride is 2.0~4.0 : 0.03~0.05 : 0.06~0.10 : 1.5~2.5 : 0~5.0 : 1.0; said organic solvent is 1,4-dioxane or toluene; said base is potassium carbonate, potassium phosphate, cesium car- bonate, or cesium fluoride; dialkyl (2,4,6- or 2,6-alkoxyphenyl)phosphine or its tetrafluoroborate is as claimed in claim 1; said arylchloride is R4 substituted chlorobenzene; said arylboronic acid is R5 substituted aryl boronic acid; R4 is ortho-, 45 meta-, para- substituted alkyl, alkoxy or hydrogen; R 5 is ortho-, meta-, para- substituted alkyl, alkoxy, aryl or hydrogen. [0013] Alternatively, the synthesis of the coupling compounds is carried out under the protection of inert gases, the reaction temperature is 80-120°C, toluene is the solvent, palladium acetate, dialkyl (2,4,6- or 2,6- alkoxyphenyl)phosphine or its tetrafluoroborate, potassium carbonate, arylboronic acid and optically active chlorolactone undergo reaction for 5-60 minutes and the corresponding coupling optically active lactone compounds are obtained; the equivalent molar 50 ratio of said palladium acetate, dialkyl (2,4,6- or 2,6- alkoxyphenyl)phosphine or its tetrafluoroborate, potassium carbonate, arylboronic acid and optically active chlorolactone is 0.05 : 0.05~0.10 : 3.0~4.5 : 1.2~2.0 : 1.0; the organic phosphine or its salt is the dialkyl(2,4,6- or 2,6-alkoxyphenyl)phosphine or its tetrafluoroborate of claim 1; the arylboronic acid is 5 R C6H4B(OH)2; the chemical structure of the optically active chlorolactone is 55 3 EP 2 492 274 A1 the chemical structure of the product coupled by optically active chlorolactone and aryl boronic acid is 5 R5 is ortho-, meta-, para- substituted alkyl, alkoxy, aryl or hydrogen; R 6 is alkyl, phenyl or heterocyclic group; R 7 is alkyl group; said heterocyclic group is thiophene, furan or pyridine; * is optically active carbon.
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