KR20120043191A - Novel enol phosphate derivatives and their preparation method from alkynes catalyzed by gold - Google Patents

Abstract

PURPOSE: An enol phosphate derivative and a method for preparing the same are provided to enable synthesis of natural products and physiologically active materials. CONSTITUTION: An enol phosphate derivative is denoted by chemical formula 1. A method for preparing enol phosphate derivative comprises: a step of reacting alkane derivative of chemical formula 2 with a phosphate derivative of chemical formula 4 under the presence of a gold catalyst to prepare kinetic enol phosphate derivative of chemical formula A. The gold catalyst includes AuCl, AuCl_3, AuBr_3, PPh_3AuCl, (C_6F_5)_3PAuCl, (IPr)AuCl, or (IMes)AuCl.

Description

Novel enol phosphate derivatives and their preparation method from alkynes catalyzed by gold}

The present invention relates to novel enol phosphate derivatives and methods for their preparation. More specifically, a method of selectively preparing a kinetic enol phosphate derivative and a thermodynamic enol phosphate derivative by respectively adding an alkane derivative to a phosphate derivative using a different gold catalyst system It is about.

Enol phosphate derivatives serve as very useful intermediates in organic chemistry. This is because the enol phosphate can be used to synthesize various organic compounds and further to synthesize natural products. The general enol phosphate synthesis method can be synthesized through the reaction of lithium enolate and dialkylphosphorochlorate. Especially for thermodynamic enol derivatives, they can be made from asymmetric ketones, but it is not easy to produce thermodynamic enol derivatives with high selectivity. Therefore, the method of synthesizing kinetic enol phosphate or thermodynamic enol phosphate with high selectivity is very important. In particular, the existing methods make enol phosphate from carbonyl groups, that is, aldehyde or ketone, and therefore, the development of a synthetic method of making enol phosphate through the addition reaction of phosphate from alkane is very important.

In addition, there have been no reports on the selective synthesis of kinetic enol phosphate derivatives or thermodynamic enol phosphate derivatives using different gold catalyst systems.

It is an object of the present invention to provide novel enol phosphate derivatives.

It is also an object of the present invention to provide a process for the selective preparation of enol phosphate derivatives from alkane which serve as useful intermediates of various organic reactions.

Another object of the present invention is to provide a method for selectively preparing a kinetic enol phosphate derivative and a thermodynamic enol phosphate derivative by addition of an alkane derivative and a phosphate using different gold catalyst systems.

The present invention provides a novel enol phosphate derivative represented by the following formula (1) and a preparation method thereof.

[Formula 1]

In addition, the present invention is a method for preparing a kinetic enol phosphate derivative represented by the following formula (A) and a thermodynamic enol phosphate derivative represented by the following formula B, using a different gold catalyst And a kinetic enol phosphate derivative represented by the following formula (A) and a thermodynamic enol phosphate derivative represented by the following formula (B) by adding an alkane derivative represented by the following formula (3) to a phosphate represented by the following formula (4): It is characterized in that the manufacturing.

[Formula A]

[Formula B]

[Formula 2]

(3)

[Formula 4]

Hereinafter, the present invention will be described in detail.

At this time, if there is no other definition in the technical terms and scientific terms used, it has a meaning commonly understood by those of ordinary skill in the art. Repeated descriptions of the same technical constitution and operation as those of the conventional art will be omitted.

The present invention provides an enol phosphate derivative represented by the following formula (1).

[Formula 1]

이며;[R ¹ is hydrogen, (C1-C7) alkyl, halo (C1-C7) alkyl, (C6-C20) aryl (C1-C7) alkyl, (C6-C20) arylthio, (C6-C20) aryl (C1 -C7) alkylthio, (C1-C7) alkyloxycarbonyl, (C6-C20) aryl, halo (C6-C20) aryl, ferrocenyl or

Is;

R ² is (R ² And R ³ ) hydrogen, (C1-C8) alkyl, halo (C1-C8) alkyl, (C3-C7) cycloalkyl, (C1-C7) alkoxycarbonyl, (C6-C20) arylthio, (C6-C20 ) Aryl or (C6-C20) aryl (C1-C8) alkyl;

R ³ is (C6-C20) aryl, (C1-C7) alkyl or (C6-C20) aryl (C1-C7) alkyl;

Alkyl and aryl of R ¹ and R ² are (C ¹ -C 7) alkyl, halo (C 1 -C 7) alkyl, (C 1 -C 7) alkoxy, (C 1 -C 7) alkylcarbonyloxy, (C 6 -C 20) aryl ( C1-C7) alkyloxy, cyano, (C1-C7) alkyl (C6-C20) aryloxy and (C3-C7) cycloalkyl may be further substituted with one or more selected.]

The 'alkyl' includes both linear or pulverized carbon chains.

이며; R²는 수소, 에틸, 펜틸, 헥실, 사이클로헥실, 페닐에틸, 클로로에틸, 에톡시카보닐, 페닐, 페닐티오, 메틸카보닐옥시메틸 또는 클로로페닐이고; R³ 페닐, 메틸, 에틸, 프로필 또는 벤질이다.Specifically in Formula 1 R ¹ is hydrogen, methyl, ethyl, hexyl, benzyl, phenylpropyl, chloromethyl, bromomethyl, chloroethyl, chloropropyl, cyanopropyl, methylcarbonyloxymethyl, benzyloxypropyl, di Methylphenoxypropyl, cyclohexylmethyl, benzylthio, phenylthio, ethoxycarbonyl, phenyl, pentylphenyl, trifluoromethylphenyl, chlorophenyl, ferrocenyl, methoxyphenyl or

Is; R ² is hydrogen, ethyl, pentyl, hexyl, cyclohexyl, phenylethyl, chloroethyl, ethoxycarbonyl, phenyl, phenylthio, methylcarbonyloxymethyl or chlorophenyl; R ^{3 is} phenyl, methyl, ethyl, propyl or benzyl.

Enol phosphate derivatives of the present invention are selected from, but not limited to, compounds of the structure:

In addition, the present invention includes the preparation method of the kinetic enol phosphate derivative represented by the following general formula (A) and the thermodynamic enol phosphate derivative represented by the following general formula (B) as a scope, and the preparation method according to the present invention will be described in detail below. . To prepare a kinetic enol phosphate represented by the following formula (A) through the addition of the alkane derivative represented by the formula (2) using a phosphate and a gold catalyst represented by the following formula (4) (Scheme 1) and A process of selectively preparing a thermodynamic enol phosphate derivative represented by the following formula (B) from an alkane derivative through addition and isomerization with an phosphate represented by the following formula (4) using another gold catalyst It includes the manufacturing method containing (Scheme 2).

Scheme 1

이며; R²는 수소, (C1~C7)알킬, (C1-C7)알콕시카보닐, (C6-C20)아릴티오 또는 (C6-C20)아릴이고; R³는 (C6-C20)아릴, (C1-C7)알킬 또는 (C6-C20)아릴(C1-C7)알킬이고; 상기 R¹ 및 R²의 알킬 및 아릴은 (C1-C7)알킬, 할로(C1-C7)알킬, (C1-C7)알콕시, (C1-C7)알킬카보닐옥시, (C6-C20)아릴(C1-C7)알킬옥시, 시아노, (C1-C7)알킬(C6-C20)아릴옥시 및 (C3-C7)사이클로알킬로 이루어진 군으로부터 선택되는 하나 이상으로 더 치환될 수 있다.]
[In Scheme 1, R ¹ is hydrogen, (C1-C7) alkyl, halo (C1-C7) alkyl, (C6-C20) aryl (C1-C7) alkyl, (C6-C20) arylthio, (C6- C20) aryl (C1-C7) alkylthio, (C1-C7) alkyloxycarbonyl, (C6-C20) aryl, halo (C6-C20) aryl, ferrocenyl or

Is; R ² is hydrogen, (C1-C7) alkyl, (C1-C7) alkoxycarbonyl, (C6-C20) arylthio or (C6-C20) aryl; R ³ is (C6-C20) aryl, (C1-C7) alkyl or (C6-C20) aryl (C1-C7) alkyl; Alkyl and aryl of R ¹ and R ² are (C ¹ -C 7) alkyl, halo (C 1 -C 7) alkyl, (C 1 -C 7) alkoxy, (C 1 -C 7) alkylcarbonyloxy, (C 6 -C 20) aryl ( C1-C7) alkyloxy, cyano, (C1-C7) alkyl (C6-C20) aryloxy and (C3-C7) cycloalkyl may be further substituted with one or more selected.]

Scheme 2

[In Scheme 2, R ² is (C1-C7) alkyl, halo (C1-C7) alkyl, (C3-C7) cycloalkyl, (C6-C20) aryl or (C6-C20) aryl (C1-C7) Alkyl; R ³ is (C6-C20) aryl, (C1-C7) alkyl or (C6-C20) aryl (C1-C7) alkyl]

The reaction vessel used in the production method of the present invention is preferably selected from the group consisting of a round bottom flask, a test tube and a V-vial, more preferably using a V-vial.

The gold catalyst used in the preparation method of the present invention is at least one selected from the group consisting of AuCl, AuCl ₃ , AuBr ₃ , PPh ₃ AuCl, (C ₆ F ₅ ) ₃ PAuCl, (IPr) AuCl, (IMes) AuCl Preference is given to the use of PPh ₃ AuCl as catalyst in the preparation of the kinetic enol phosphate derivative (Formula A), and to the preparation of the thermodynamic enol phosphate derivative (Formula B) (C ₆ F ₅ ) ₃ PAuCl. More preferably used as a catalyst.

In the production method of the present invention, the silver catalyst is used in addition to the gold catalyst to increase the Lewis acidity of the gold catalyst, which is more preferable in view of selectivity and yield of the reaction. The silver catalyst used in the preparation method of the present invention is preferably selected from the group consisting of AgOTf, AgBF ₄ , AgAsF ₆ , AgNTf ₂ , AgSbF ₆ , AgPF _{6 ,} AgNO ₃ , a kinetic enol phosphate derivative It is more preferable to use AgPF _{6 together} with the gold catalyst in the preparation of A), and more preferably to use AgOTf together with the gold catalyst in the preparation of the thermodynamic enol phosphate derivative (Formula B).

The amount of the gold catalyst used in the production method of the present invention is preferably used 1 to 10 mol%, more preferably 5 mol% based on the phosphate derivative represented by the formula (4).

The amount of the silver catalyst used in the production method of the present invention depends on the gold catalyst used, and when using a monovalent gold catalyst, the silver catalyst preferably uses the same equivalents as the gold catalyst, and more preferably 1 equivalent. In addition, when using a trivalent gold catalyst, it is preferable to use 2-5 equivalents with respect to a gold catalyst, and, as for the said silver catalyst, it is more preferable to use 3 equivalents.

The alkane derivatives (2, 3) used in the preparation method of the present invention preferably use 1 to 2 equivalents, more preferably 1.2 equivalents, relative to the phosphate derivative (4).

The solvent used in the preparation method of the present invention is a conventional organic solvent, dichloromethane (DCM), dichloroethane (DCE), toluene (Toluene), acetonitrile (MeCN), nitromethan (tetraethan), tetrahydro It is preferable that at least one selected from the group consisting of furan (THF), N, N -dimethylformamide (DMF) and N, N -dimethylacetamide (DMA) is used, and toluene is used as a solvent. More preferred.

The reaction temperature is carried out at 20 to 140 ° C and may vary depending on the alkane derivative used.

The reaction time may vary depending on the reactants, the type of solvent, and the amount of the solvent. After confirming that the starting material alkane derivative is consumed through TLC, the reaction is completed. After the reaction is completed, the solvent may be distilled off under reduced pressure after the extraction process, and the desired product may be separated and purified through a conventional method such as column chromatography.

The novel enol phosphate derivatives according to the present invention are very important intermediates in organic synthesis and can be used for the synthesis of medicinal and novel substances, or for the synthesis of fine chemical intermediates including pesticides, and also for the synthesis of natural and bioactive substances. It is also available in the city. Through the selective manufacturing method of the kinetic enol phosphate and thermodynamic enol phosphate according to the invention it is possible to synthesize a variety of organic materials and further development of natural products or pharmaceuticals. In addition, the kinetic enol phosphate and thermodynamic enol phosphate derivatives according to the present invention can be selectively prepared through high yields and simple experiments by addition reaction between various alkane derivatives and phosphate derivatives in the presence of different gold catalysts. Has

Hereinafter, the configuration of the present invention in more detail through examples, the following examples are provided to help the understanding of the present invention, the scope of the present invention is not limited thereto.

Example 1 Preparation of Oct-1-en-2-yl diphenyl phosphate

To a V-vial, add PPh ₃ AuCl (12.4 mg, 0.025 mmol) and AgPF ₆ (6.3 mg, 0.025 mmol), add toluene (2 mL) and stir at room temperature, add diphenyl phosphate (125 mg, 0.5 mmol) and 1-octin (66 mg, 0.6 mmol) was added sequentially and stirred at room temperature for 9 hours before terminating the reaction. The solvent was removed and the residue was separated by column chromatography to obtain the title compound oct-1-en-2-yl diphenyl phosphate (159 mg, 88%).

¹ H NMR (400 MHz, CDCl ₃ ) δ 7.37-7.33 (m, 4H), 7.25-7.19 (m, 6H), 4.93 (t, J = 2.2 Hz, 1H), 4.59 (t, J = 2.0 Hz, 1H), 2.19 (t, J = 7.6 Hz , 2H), 1.44 (quint , J = 7.4 Hz, 2H), 1.31-1.19 (m, 6H), 0.87 (t, J = 6.9 Hz, 3H)

Example 2 Preparation of 3-Phenyl-1-propen-2-yl diphenyl phosphate

To a V-vial, add PPh ₃ AuCl (12.4 mg, 0.025 mmol) and AgPF ₆ (6.3 mg, 0.025 mmol), add toluene (2 mL) and stir at room temperature, add diphenyl phosphate (125 mg, 0.5 mmol) and 3-phenyl-1-propyne (78 mg, 0.6 mmol) was added sequentially and stirred at room temperature for 9 hours before terminating the reaction. After the solvent was removed, the residue was separated by column chromatography to obtain 3-phenyl-1-propen-2-yl diphenyl phosphate (146 mg, 88%) as a title compound.

¹ H NMR (400 MHz, CDCl _{3 ,} 25 ° C., TMS): δ 7.34-7.24 (m, 8H), 7.22-7.13 (m, 7H) 5.05 (t, J = 2.2 Hz, 2H), 4.59 (t, J = 1.8 Hz, 1H), 3.51 (s, 1H)

Example 3 Preparation of Diphenyl 5-phenylpent-1-en-2-yl phosphate

To a V-vial, add PPh ₃ AuCl (12.4 mg, 0.025 mmol) and AgPF ₆ (6.3 mg, 0.025 mmol), add toluene (2 mL) and stir at room temperature, add diphenyl phosphate (125 mg, 0.5 mmol) and 5-phenyl-1-pentin (87 mg, 0.6 mmol) was added sequentially and stirred at room temperature for 9 hours before terminating the reaction. The solvent was removed and the residue was separated by column chromatography to obtain the title compound diphenyl 5-phenylpent-1-en-2yl phosphate (160 mg, 81%).

¹ H NMR (400 MHz, CDCl ₃ ): δ 7.3-7.4 (m, 4H), 7.2-7.3 (m, 9H), 7.11-7.13 (m, 2H), 4.97 (t, J = 2.2 Hz, 1H) , 4.62 (s, 1H), 2.60 (t, J = 7.7 Hz, 2H), 2.24 (t, J = 7.5 Hz, 2H), 1.78 (q, J = 7.6 Hz, 2H)

Example 4 Preparation of 1- (1-cyclohexylmethyl) vinyl diphenyl phosphate (1- (1-Cyclohexylmethyl) vinyl diphenyl phosphate)

To a V-vial, add PPh ₃ AuCl (12.4 mg, 0.025 mmol) and AgPF ₆ (6.3 mg, 0.025 mmol), add toluene (2 mL) and stir at room temperature, add diphenyl phosphate (125 mg, 0.5 mmol) and 3-cyclohexyl-1-propyne (73 mg, 0.6 mmol) was added sequentially and stirred at room temperature for 17 hours before terminating the reaction. The solvent was removed and the residue was separated by column chromatography to obtain 1- (1-cyclohexylmethyl) vinyl diphenyl phosphate (177 mg, 95%) as a title compound.

¹ H NMR (400 MHz, CDCl ₃ ): δ 7.37-7.34 (m, 4H), 7.26-7.24 (m, 4H), 7.22-7.19 (m, 2H), 4.93 (t, J = 2.1 Hz, 1H) , 4.56 (t, J = 2.1 Hz, 1H), 2.06 (d, J = 7.1 Hz, 2H), 1.69-1.60 (m, 5H), 1.46-1.40 (m, 1H), 1.19-1.08 (m, 3H ), 0.88-0.79 (m, 2H)

Example 5 Preparation of 3-chloroprop-1-en-2-yl diphenyl phosphate

To a V-vial, add PPh ₃ AuCl (12.4 mg, 0.025 mmol) and AgPF ₆ (6.3 mg, 0.025 mmol), add toluene (2 mL) and stir at room temperature, add diphenyl phosphate (125 mg, 0.5 mmol) and Propargylchloride (45 mg, 0.6 mmol) was added sequentially and stirred at room temperature for 15 hours before terminating the reaction. After the solvent was removed, the residue was separated by column chromatography to obtain 3-chloroprop-1-en-2-yl diphenyl space (122 mg, 70%) as a title compound.

¹ H NMR (400 MHz, CDCl ₃ ): δ 7.25-7.29 (m, 4H), 7.10-7.17 (m, 6H), 5.09 (t, J = 2.5 Hz, 1H), 4.93 (t, J = 2.4 Hz , 1H), 3.96 (s, 2H)

Example 6 Preparation of 3-Bromo-1-propen-2-yl diphenyl phosphate

To a V-vial, add PPh ₃ AuCl (12.4 mg, 0.025 mmol) and AgPF ₆ (6.3 mg, 0.025 mmol), add toluene (2 mL) and stir at room temperature, add diphenyl phosphate (125 mg, 0.5 mmol) and Propazilbromide (71 mg, 0.6 mmol) was added in sequence and stirred at room temperature for 16 hours before terminating the reaction. After the solvent was removed, the residue was separated by column chromatography to obtain 3-bromo-1-propen-2-yl diphenyl phosphate (170 mg, 92%) as a title compound.

¹ H NMR (400 MHz, CDCl ₃ ) δ 7.26-7.36 (m, 10H), 5.17 (s, 1H), 5.03 (s, 1H), 3.95 (s, 2H)

Example 7 Preparation of 1- (3-Chloropropyl) vinyl diphenyl phosphate (1- (3-Chloropropyl) vinyl diphenyl phosphate)

To a V-vial, add PPh ₃ AuCl (12.4 mg, 0.025 mmol) and AgPF ₆ (6.3 mg, 0.025 mmol), add toluene (2 mL) and stir at room temperature, add diphenyl phosphate (125 mg, 0.5 mmol) and 5-chloro-1-pentin (62 mg, 0.6 mmol) was added sequentially and stirred at room temperature for 7 hours before terminating the reaction. After the solvent was removed, the residue was separated by column chromatography to obtain 1- (3-chloropropyl) vinyl diphenyl phosphate (138 mg, 78%) as a title compound.

¹ H NMR (400 MHz, CDCl ₃ ): δ 7.34-7.38 (m, 4H), 7.20-7.26 (m, 6H), 5.02 (s, 1H), 4.68 (s, 1H), 2.39 (t, J = 7.3 Hz, 2H), 1.91 (q, J = 6.8 Hz, 2H)

Example 8 Preparation of 5- (benzyloxy) pent-1-en-2-yl diphenyl phosphate (5- (Benzyloxy) pent-1-en-2-yl diphenyl phosphate)

To a V-vial, add PPh ₃ AuCl (12.4 mg, 0.025 mmol) and AgPF ₆ (6.3 mg, 0.025 mmol), add toluene (2 mL) and stir at room temperature, add diphenyl phosphate (125 mg, 0.5 mmol) and ((Pent-4-ynilocy) methyl) benzene (104.5 mg, 0.6 mmol) was added sequentially and stirred at 80 ° C. for 4 hours before terminating the reaction. The solvent was removed and the residue was separated by column chromatography to obtain 5- (benzyloxy) pent-1-en-2-yl diphenyl phosphate (169.8 mg, 80%) as a title compound.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.35-7.32 (m, 10H), 7.25-6.91 (m, 5H), 4.96 (t, J = 2.2 Hz, 1H), 4.61 (t, J = 2.2 Hz, 1H), 4.47 (s, 2H), 3.46 (t, J = 15.2 Hz, 2H), 2.33 (t, J = 7.5 Hz, 2H), 1.75 (qunt, J = 6.2 Hz, 2H)

Example 9 Preparation of 5-Cyanopent-1-en-2-yl diphenyl phosphate (5-Cyanopent-1-en-2-yl diphenyl phosphate)

To a V-vial, add PPh ₃ AuCl (12.4 mg, 0.025 mmol) and AgPF ₆ (6.3 mg, 0.025 mmol), add toluene (2 mL) and stir at room temperature, add diphenyl phosphate (125 mg, 0.5 mmol) and 5-hexaninnitrile (55.9 mg, 0.6 mmol) was added sequentially and stirred at room temperature for 8 hours before terminating the reaction. The solvent was removed and the residue was separated by column chromatography to obtain 5-thiophen-1--1-en-2-yl diphenyl phosphate (137 mg, 80%) as a title compound.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.40-7.37 (m, 4H), 7.37-7.20 (m, 6H), 5.05 (t, J = 2.4 Hz, 1H), 4.72 (t, J = 2.4 Hz, 1H), 2.37 (t, J = 7.2 Hz, 2H), 2.31 (t, J = 7.1 Hz, 2H), 1.78 (q, J = 7.1 Hz, 2H)

Example 10 5- (3,5-dimethylphenoxy) pent-1-en-2-yl diphenyl phosphate (5- (3,5-Dimethylphenoxy) pent-1-en-2-yl diphenyl phosphate Manufacturing

To a V-vial, add PPh ₃ AuCl (12.4 mg, 0.025 mmol) and AgPF ₆ (6.3 mg, 0.025 mmol), add toluene (2 mL) and stir at room temperature, add diphenyl phosphate (125 mg, 0.5 mmol) and 1,3-dimethyl-5- (pent-4-ynilocy) benzene (123 mg, 0.6 mmol) was added sequentially and stirred at 80 ° C. for 8 hours before terminating the reaction. After the solvent was removed, the residue was separated by column chromatography to obtain 5- (3,5-dimethylphenoxy) pent-1-en-2-yl diphenyl phosphate (186.3 mg, 85%) as a title compound.

¹ H NMR (400 MHz, CDCl ₃ ): δ 7.35 (t, J = 7.9 Hz, 4H), 7.26-7.18 (m, 6H), 6.59 (s, 1H), 6.49 (s, 2H), 4.99 (t, J = 2.3 Hz, 1H), 4.66 ( t, J = 2.2 Hz, 1H), 3.90 (t, J = 6.4 Hz, 2H), 2.41 (t, J = 7.5 Hz, 2H), 2.27 (s, 6H), 1.92 (qunt, J = 6.7 Hz, 2H)

Example 11 Preparation of 1-Phenylvinyl diphenyl phosphate

To a V-vial, add PPh ₃ AuCl (12.4 mg, 0.025 mmol) and AgPF ₆ (6.3 mg, 0.025 mmol), add toluene (2 mL) and stir at room temperature, add diphenyl phosphate (125 mg, 0.5 mmol) and Phenylacetylene (61 mg, 0.6 mmol) was added sequentially and stirred at 60 ° C. for 12 hours before terminating the reaction. After the solvent was removed, the residue was separated by column chromatography to obtain 1-phenyl-1-ethen-1-yl diphenyl phosphate (155 mg, 88%) as a title compound.

¹ H NMR (400 MHz, CDCl ₃ ) δ 7.49-7.51 (m, 2H), 7.30-7.36 (m, 7H), 7.23-7.26 (m, 4H), 7.18-7.22 (m, 2H), 5.38 (t , J = 2.9 Hz, 1H), 5.34 (t, J = 2.7 Hz, 1H)

Example 12 Preparation of Diphenyl 1- (4-trifluoromethylphenyl) vinyl Diphenyl Phosphate (1- (4-Trifluoromethylphenyl) vinyl diphenyl phosphate)

To a V-vial, add PPh ₃ AuCl (12.4 mg, 0.025 mmol) and AgPF ₆ (6.3 mg, 0.025 mmol), add toluene (2 mL) and stir at room temperature, add diphenyl phosphate (125 mg, 0.5 mmol) and 4-trifluorophenylacetylene (102 mg, 0.6 mmol) was added sequentially and stirred at 60 ° C. for 17 hours before terminating the reaction. After the solvent was removed, the residue was separated by column chromatography to obtain 1- (4-trifluoromethylphenyl) vinyl diphenyl phosphate (168 mg, 80%) as a title compound.

¹ H NMR (300 MHz, CDCl ₃ ) δ 7.57 (s, 4H), 7.39-7.34 (m, 4H), 7.26-7.20 (m, 6H), 5.49 (t, J = 3.0 Hz, 1H), 5.46 ( t, J = 2.3 Hz, 1H)

Example 13 Preparation of 1- (4-pentylphenyl) vinyl diphenyl phosphate (1- (4-Pentylphenyl) vinyl diphenyl phosphate)

To a V-vial, add PPh ₃ AuCl (12.4 mg, 0.025 mmol) and AgPF ₆ (6.3 mg, 0.025 mmol), add toluene (2 mL) and stir at room temperature, add diphenyl phosphate (125 mg, 0.5 mmol) and 4-pentylphenylacetylene (103 mg, 0.6 mmol) was added sequentially and stirred at 60 ° C. for 8 hours before terminating the reaction. After the solvent was removed, the residue was separated by column chromatography to obtain 1- (4-pentylphenyl) vinyl diphenyl phosphate (201 mg, 95%) as a title compound.

¹ H NMR (400 MHz, CDCl ₃ ) δ 7.40 (d, J = 8.3 Hz, 2H), 7.36-7.32 (m, 4H), 7.26-7.18 (m. 6H), 7.12 (d , J = 8.3 Hz, 2H), 5.33 (t, J = 2.9 Hz, 1H), 5.23 (t, J = 2.6 Hz, 1H), 2.59 (t , J = 7.7 Hz, 2H), 1.60 (quint, J = 7.6 Hz, 2H) , 1.34-1.28 (m, 4H), 0.89 (t, J = 6.9, 3H)

Example 14 Preparation of 1- (benzylthio) vinyl diphenyl phosphate (1- (Benzylthio) vinyl diphenyl phosphate)

To a V-vial, add PPh ₃ AuCl (12.4 mg, 0.025 mmol) and AgPF ₆ (6.3 mg, 0.025 mmol), add toluene (2 mL) and stir at room temperature, add diphenyl phosphate (125 mg, 0.5 mmol) and Phenyl propazyl thioser (90 mg, 0.6 mmol) was added sequentially and stirred at room temperature for 2 hours before terminating the reaction. The solvent was removed and the residue was separated by column chromatography to obtain 1- (benzyltao) vinyl diphenyl phosphate (195 mg, 98%) as a title compound.

¹ H NMR (300 MHz, CDCl ₃ ) δ 7.39-7.34 (m, 4H), 7.29-7.19 (m, 11H), 5.26 (t, J = 2.6 Hz, 1H), 4.91 (t, J = 2.4 Hz, 1H), 3.90 (s, 2H)

Example 15 Preparation of ( Z) -(2- (ethoxycarbonyl) vinyl) diphenyl phosphate (( Z) -(2- (Ethoxycarbonyl) vinyl) diphenyl phosphate)

To a V-vial, add PPh ₃ AuCl (12.4 mg, 0.025 mmol) and AgPF ₆ (6.3 mg, 0.025 mmol), add toluene (2 mL) and stir at room temperature, add diphenyl phosphate (125 mg, 0.5 mmol) and Ethyl propiolate (59 mg, 0.6 mmol) was added sequentially and stirred at room temperature for 10 hours before terminating the reaction. After the solvent was removed, the residue was separated by column chromatography to obtain the title compound Z -2- (ethoxycarbonyl) vinyl diphenyl phosphate (146 mg, 84%).

¹ H NMR (400 MHz, CDCl ₃ ) δ 7.24-7.36 (m, 10H), 6.98 (t, J = 6.2 Hz, 1H), 5.31-5.33 (m, 1H), 4.18 (q, J = 7.34 Hz, 2H), 1.25 (t, J = 7.34 Hz, 3H)

Example 16 Preparation of ethyl ( Z ) -3- (diphenoxyphosphoryloxy) -3-phenylacrylate (Ethyl ( Z ) -3- (Diphenoxyphosphoryloxy) -3-phenylacrylate)

To a V-vial, add PPh ₃ AuCl (12.4 mg, 0.025 mmol) and AgPF ₆ (6.3 mg, 0.025 mmol), add toluene (2 mL) and stir at room temperature, add diphenyl phosphate (125 mg, 0.5 mmol) and Phenylpropionic acid ethyl ester (104 mg, 0.6 mmol) was added sequentially and stirred at 60 ° C. for 10 hours before terminating the reaction. After the solvent was removed, the residue was separated by column chromatography to obtain ethyl ( Z ) -3- (diphenoxyphosphoryloxy) -3-phenylacrylate (166 mg, 78%) as a title compound.

¹ H NMR (400 MHz, CDCl ₃ ) δ 7.12-7.65 (m, 15H), 6.11 (s, 1H), 4.18 (q, J = 7.3 Hz, 2H), 1.27 (t, J = 7.1 Hz, 3H)

Preparation of hex-3-en-3-yl-diphenyl phosphate ((Z) -Hex-3- en-3-yl diphenyl phosphate) - [ Example 17] (Z)

To a V-vial, add PPh ₃ AuCl (12.4 mg, 0.025 mmol) and AgPF ₆ (6.3 mg, 0.025 mmol), add toluene (2 mL) and stir at room temperature, add diphenyl phosphate (125 mg, 0.5 mmol) and 3-hexine (49 mg, 0.6 mmol) was added sequentially and stirred at 110 ° C. for 15 hours, after which the reaction was terminated. After the solvent was removed, the residue was separated by column chromatography to obtain ethyl ( Z) -hex-3-en-3-yl diphenyl phosphate (120 mg, 72%) as a title compound.

¹ H NMR (300 MHz, CDCl ₃ ) δ 7.38-7.30 (m, 4H), 7.27-7.17 (m, 6H), 4.87 (t, J = 7.3 Hz, 1H), 2.34 (q, J = 6.0 Hz, 2H), 2.05 (q, J = 7.5 Hz, 2H), 1.05 (t, J = 7.4 Hz, 3H), 0.88 (t, J = 7.5 Hz, 3H)

Preparation of diphenyl-1-phenyl-prop-1-en-2-yl phosphate ((Z) -Diphenyl-1- phenylprop-1-en-2-yl phosphate) - [ Example 18] (Z)

To a V-vial, add PPh ₃ AuCl (12.4 mg, 0.025 mmol) and AgPF ₆ (6.3 mg, 0.025 mmol), add toluene (2 mL) and stir at room temperature, add diphenyl phosphate (125 mg, 0.5 mmol) and 1-phenyl-1-propyne (70 mg, 0.6 mmol) was added sequentially and stirred at 110 ° C. for 10 hours before terminating the reaction. The solvent was removed and the residue was separated by column chromatography to obtain ( Z ) -diphenyl-1-phenylprop-1-en-2-yl phosphate (126 mg, 69%) as a title compound.

¹ H NMR (400 MHz, CDCl ₃ ) δ 7.39-7.37 (m, 2H), 7.32-7.28 (m, 4H), 7.22-7.16 (m, 9H), 5.76 (s, 1H), 2.29 (s, 3H )

Example 19 Preparation of 1- (3- (1-diphenoxyphosphoryloxyvinyl) phenyl) vinyl diphenyl phosphate (1- (3- (1-Diphenoxyphosphoryloxyvinyl) phenyl) vinyl diphenyl phosphate)

To a V-vial, add PPh ₃ AuCl (12.4 mg, 0.025 mmol) and AgPF ₆ (6.3 mg, 0.025 mmol), add toluene (2 mL) and stir at room temperature, add diphenyl phosphate (125 mg, 0.5 mmol) and 1,3-diethynyl benzene (75.7 mg, 0.6 mmol) was added sequentially, stirred at 110 ° C. for 5 hours, and the reaction was terminated. The solvent was removed and the residue was separated by column chromatography to obtain 1- (3- (1-diphenoxyphosphoryloxyvinyl) phenyl) vinyl diphenyl phosphate (303.87 mg, 97%) as a title compound.

¹ H NMR (300 MHz, CDCl ₃ ) δ 7.62-7.36 (m, 10H), 7.25-7.17 (m, 14H), 5.35 (t, J = 1.6 Hz, 2H), 5.29 (t, J = 3.0 Hz, 2H)

Example 20 Preparation of 2- (Diphenoxyphosphoryloxy) allyl Acetate (2- (Diphenoxyphosphoryloxy) allyl acetate)

To a V-vial, add PPh ₃ AuCl (12.4 mg, 0.025 mmol) and AgPF ₆ (6.3 mg, 0.025 mmol), add toluene (2 mL) and stir at room temperature, add diphenyl phosphate (125 mg, 0.5 mmol) and Propargyl acetate (58.9 mg, 0.6 mmol) was added sequentially and stirred at 80 ° C. for 8 hours before terminating the reaction. After the solvent was removed, the residue was separated by column chromatography to obtain 2- (diphenoxyphoryloxy) allyl acetate (88.8 mg, 51%) as a title compound.

¹ H NMR (300 MHz, CDCl ₃ ) δ 7.39-7.34 (m, 4H), 7.26-7.19 (m, 6H), 5.21 (t, J = 2.4 Hz, 1H), 4.93 (t, J = 2.4 Hz, 1H), 4.59 (s, 2H), 2.01 (s, 3H)

Preparation of [Example 21] (E) -3- (di-shi page phosphorylation reel City) allyl acetate ((E) -3- (Diphenoxyphosphoryloxy) allyl acetate)

To a V-vial, add PPh ₃ AuCl (12.4 mg, 0.025 mmol) and AgPF ₆ (6.3 mg, 0.025 mmol), add toluene (2 mL) and stir at room temperature, add diphenyl phosphate (125 mg, 0.5 mmol) and Propargyl acetate (58.9 mg, 0.6 mmol) was added sequentially and stirred at 80 ° C. for 8 hours before terminating the reaction. After the solvent was removed, the residue was separated by column chromatography to obtain 2- (diphenoxyphoryloxy) allyl acetate (41.8 mg, 24%) as a title compound.

¹ H NMR (300 MHz, CDCl ₃ ) δ 7.39-7.34 (m, 4H), 7.26-7.19 (m, 6H), 6.72-6.68 (m, 1H), 5.19-5.16 (m, 1H), 4.65 (d , J = 7.0 Hz, 2H), 2.05 (s, 3H)

[Example 22] (Z) - diphenyl-1- (phenyl thio) oct-1-en-2-yl phosphate ((Z) -Diphenyl-1- ( phenylthio) oct-1-en-2-yl phosphate)

To a V-vial, add PPh ₃ AuCl (12.4 mg, 0.025 mmol) and AgPF ₆ (6.3 mg, 0.025 mmol), add toluene (2 mL) and stir at room temperature, add diphenyl phosphate (125 mg, 0.5 mmol) and Oct-1-ynyl (phenyl) sulfane (139.43 mg, 0.6 mmol) was added sequentially and stirred at 110 ° C. for 7 hours before terminating the reaction. The solvent was removed and the residue was separated by column chromatography to obtain the title compound ( Z ) -diphenyl-1- (phenylthio) oct-1-en-2-yl phosphate (153.4 mg, 80%).

¹ H NMR (300 MHz, CDCl ₃ ) δ 7.37-7.27 (m, 10H), 7.24-7.08 (m, 5H), 5.71 (s, 1H), 1.52-1.43 (m, 2H), 1.33-1.24 (m , 8H), 0.86 (t, J = 6.6 Hz, 3H)

Example 23 Preparation of Diphenyl-1- (phenylthio) oct-1-enyl Phosphate (Diphenyl 1- (phenylthio) oct-1-enyl phosphate)

To a V-vial, add PPh ₃ AuCl (12.4 mg, 0.025 mmol) and AgPF ₆ (6.3 mg, 0.025 mmol), add toluene (2 mL) and stir at room temperature, add diphenyl phosphate (125 mg, 0.5 mmol) and Oct-1-ynyl (phenyl) sulfane (139.43 mg, 0.6 mmol) was added sequentially and stirred at 110 ° C. for 7 hours before terminating the reaction. After the solvent was removed, the residue was separated by column chromatography to obtain the title compound diphenyl-1- (phenylthio) oct-1-enyl phosphate (42.2 mg, 18%).

¹ H NMR (300 MHz, CDCl ₃ ) isomer A δ 7.37-7.27 (m, 10H), 7.24-7.08 (m, 5H), 6.04 (t, J = 9.0 Hz, 1H), 2.31 (t, J = 10.1 Hz, 2H), 1.33-1.24 (m, 8H), 0.86 (t, J = 6.6 Hz, 3H). isomer B δ 7.37-7.27 (m, 10H), 7.24-7.08 (m, 5H), 5.79 (t, J = 7.5 Hz, 1H), 2.11 (t, J = 6.5 Hz, 2H), 1.33-1.24 (m , 8H), 0.86 (t, J = 6.6 Hz, 3H)

Example 24 Preparation of 1- (2-Chlorophenyl) vinyl Diphenyl Phosphate (1- (2-Chlorophenyl) vinyl diphenyl phosphate)

To a V-vial, add PPh ₃ AuCl (12.4 mg, 0.025 mmol) and AgPF ₆ (6.3 mg, 0.025 mmol), add toluene (2 mL) and stir at room temperature, add diphenyl phosphate (125 mg, 0.5 mmol) and 1-chloro-2-ethynyl benzene (81.9 mg, 0.6 mmol) was added sequentially, stirred at 110 ° C. for 9 hours, and the reaction was terminated. After the solvent was removed, the residue was separated by column chromatography to obtain 1- (2-chlorophenyl) vinyl diphenyl phosphate (54.1 mg, 28%) as a title compound.

¹ H NMR (300 MHz, CDCl ₃ ) δ 7.43-7.37 (m, 2H), 7.35-7.27 (m, 5H), 7.23-7.16 (m, 7H), 5.52 (t, J = 2.5 Hz, 1H), 5.20 (t, J = 2.5 Hz, 1H)

Example 25 Preparation of (E) -2-chlorostyryl diphenyl phosphate ((E) -2-Chlorostyryl diphenyl phosphate)

To a V-vial, add PPh ₃ AuCl (12.4 mg, 0.025 mmol) and AgPF ₆ (6.3 mg, 0.025 mmol), add toluene (2 mL) and stir at room temperature, add diphenyl phosphate (125 mg, 0.5 mmol) and 1-chloro-2-ethynyl benzene (81.9 mg, 0.6 mmol) was added sequentially, stirred at 110 ° C. for 9 hours, and the reaction was terminated. After the solvent was removed, the residue was separated by column chromatography to obtain (E) -2-chlorostyryl diphenyl phosphate (131.5 mg, 68%) as a title compound.

¹ H NMR (300 MHz, CDCl ₃ ) δ 7.67 (d, J = 7.4 Hz, 1H), 7.40-7.32 (m, 5H), 7.24-7.09 (m, 8H), 6.87 (dd, J = 6.7 Hz, 1H), 6.17 (dd, J = 6.8 Hz, 1H)

Example 26 Preparation of 1- (4-methoxyphenyl) vinyl diphenyl phosphate (1- (4-Methoxyphenyl) vinyl diphenyl phosphate)

To a V-vial, add PPh ₃ AuCl (12.4 mg, 0.025 mmol) and AgPF ₆ (6.3 mg, 0.025 mmol), add toluene (2 mL) and stir at room temperature, add diphenyl phosphate (125 mg, 0.5 mmol) and 4-ethynylanisole (79.3 mg, 0.6 mmol) was added sequentially and stirred at room temperature for 15 hours before terminating the reaction. After the solvent was removed, the residue was separated by column chromatography to obtain 1- (4-methoxyphenyl) vinyl diphenyl phosphate (47.8 mg, 25%) as a title compound.

¹ H NMR (300 MHz, CDCl ₃ ) δ 7.43 (d, J = 11.9 Hz, 2H), 7.38-7.32 (m, 4H), 7.27-7.18 (m, 6H), 6.83 (d, J = 8.9 Hz, 2H), 5.26 (t, J = 2.9 Hz, 1H), 5.22 (t, J = 2.7 Hz, 1H), 3.81 (s, 3H)

Example 27 Preparation of 1- (Diphenoxyphosphoroxyoxy) vinyl Ferrocene (1- (Diphenoxyphosphoryloxy) vinyl ferrocene)

To a V-vial, add PPh ₃ AuCl (12.4 mg, 0.025 mmol) and AgPF ₆ (6.3 mg, 0.025 mmol), add toluene (2 mL) and stir at room temperature, add diphenyl phosphate (125 mg, 0.5 mmol) and Ethynyl ferrocene (126 mg, 0.6 mmol) was added sequentially and stirred at room temperature for 9 hours, after which the reaction was terminated. The solvent was removed and the residue was separated by column chromatography to obtain 1- (diphenoxyphosphoroxyoxy) vinyl ferrocene (140.6 mg, 55%) as a title compound.

¹ H NMR (300 MHz, CDCl ₃ ) δ 7.43-7.31 (m, 8H), 7.24-7.22 (m, 2H), 5.12 (t, J = 2.4 Hz, 1H), 4.96 (t, J = 2.7 Hz, 1H), 4.35 (t, J = 1.9 Hz, 2H), 4.21 (t, J = 1.9 Hz, 2H), 4.08 (s, 5H)

Example 28 Preparation of Oct-2-en-2-yl Diphenyl Phosphate

To a V-vial, add (C ₆ F ₅ ) ₃ PAuCl (19.1 mg, 0.025 mmol) and AgOTf (6.4 mg, 0.025 mmol), add toluene (2 mL) at room temperature, and diphenyl phosphate (125 mg, 0.5 mmol) and 1-octin (66 mg, 0.6 mmol) were added sequentially and stirred at room temperature for 24 hours before terminating the reaction. After the solvent was removed, the residue was separated by column chromatography to obtain the title compound oct-2-en-2-yl diphenyl phosphate (155 mg, 86%).

¹ H NMR (300 MHz, CDCl ₃ ) δ 7.38-7.32 (m, 4H), 7.27-7.17 (m, 6H), 4.85 (t, J = 7.2 Hz, 1H), 2.02 (s, 3H), 1.97 ( t, J = 7.2 Hz, 2H), 1.47-1.11 (m, 6H), 0.90-0.82 (m, 3H)

Example 29 Preparation of 1-Cyclohexylprop-1-en-2-yl (1-Cyclohexylprop-1-en-2-yl diphenyl phosphate)

To a V-vial, add (C ₆ F ₅ ) ₃ PAuCl (19.1 mg, 0.025 mmol) and AgOTf (6.4 mg, 0.025 mmol), add toluene (2 mL) at room temperature, and diphenyl phosphate (125 mg, 0.5 mmol) and 3-cyclohexyl-1-propyne (74 mg, 0.6 mmol) were added sequentially and stirred at room temperature for 24 hours before terminating the reaction. After the solvent was removed, the residue was separated by column chromatography to obtain 1-cyclohexylprop-1-en-2-yl (173 mg, 93%) as a title compound.

¹ H NMR (300 MHz, CDCl ₃ ) δ 7.39-7.33 (m, 4H), 7.29-7.17 (m, 6H), 4.68 (d, J = 10.6 Hz, 1H), 2.01 (s, 3H), 1.72- 1.56 (m, 6H), 1.29-0.88 (m, 5H)

Example 30 Preparation of 1-phenylprop-1-en-2-yl diphenyl phosphate (1-Phenylprop-1-en-2-yl diphenyl phosphate)

To a V-vial, add (C ₆ F ₅ ) ₃ PAuCl (19.1 mg, 0.025 mmol) and AgOTf (6.4 mg, 0.025 mmol), add toluene (2 mL) at room temperature, and diphenyl phosphate (125 mg, 0.5 mmol) and 3-phenyl-1-propyne (70 mg, 0.6 mmol) were added sequentially and stirred at room temperature for 24 hours before terminating the reaction. After the solvent was removed, the residue was separated by column chromatography to obtain 1-phenylprop-1-en-2-yl diphenyl phosphate (159 mg, 87%) as a title compound.

¹ H NMR (300 MHz, CDCl ₃ ) δ 7.35-7.39 (m, 3H), 7.27-7.33 (m, 5H), 7.16-7.24 (m, 7H), 5.76 (s, 1H), 2.29 (s, 3H )

Example 31 Preparation of Diphenyl 5-phenylpent-2-en-2-yl phosphate

To a V-vial, add (C ₆ F ₅ ) ₃ PAuCl (19.1 mg, 0.025 mmol) and AgOTf (6.4 mg, 0.025 mmol), add toluene (2 mL) at room temperature, and diphenyl phosphate (125 mg, 0.5 mmol) and 5-phenyl-1-pentin (87 mg, 0.6 mmol) were added sequentially, stirred at room temperature for 24 hours, and the reaction was terminated. After the solvent was removed, the residue was separated by column chromatography to obtain the title compound diphenyl 5-phenylpent-2-en-2-yl phosphate (168 mg, 85%).

¹ H NMR (300 MHz, CDCl ₃ ) δ 7.37-7.28 (m, 4H), 7.26-7.10 (m, 10H), 7.09-7.07 (m, 1H), 4.88 (t, J = 7.2 Hz, 1H), 2.98 (t, J = 8.9 Hz, 2H), 2.37-2.24 (m, 2H), 2.02 (s, 3H)

Example 32 Preparation of 5-Chloropent-2-en-2-yl diphenyl phosphate

To a V-vial, add (C ₆ F ₅ ) ₃ PAuCl (19.1 mg, 0.025 mmol) and AgOTf (6.4 mg, 0.025 mmol), add toluene (2 mL) at room temperature, and diphenyl phosphate (125 mg, 0.5 mmol) and 5-chloro-1-pentin (62 mg, 0.6 mmol) were added sequentially and stirred at room temperature for 24 hours before terminating the reaction. After the solvent was removed, the residue was separated by column chromatography to obtain 5-chloropent-2-en-2-yl diphenyl phosphate (155 mg, 86%) as a title compound.

¹ H NMR (300 MHz, CDCl ₃ ) δ 7.34-7.40 (m, 4H), 7.19-7.27 (m, 6H), 4.97 (t, J = 7.3 Hz, 1H), 3.42 (t, J = 6.9 Hz, 2H), 2.39-2.47 (m, 2H), 2.05 (s, 3H)

Claims (17)

Enol phosphate derivative represented by the following formula (1):
[Formula 1]

[R ¹ is hydrogen, (C1-C7) alkyl, halo (C1-C7) alkyl, (C6-C20) aryl (C1-C7) alkyl, (C6-C20) arylthio, (C6-C20) aryl (C1 -C7) alkylthio, (C1-C7) alkyloxycarbonyl, (C6-C20) aryl, halo (C6-C20) aryl, ferrocenyl or

Is;
R ² is (R ² And R ³ ) hydrogen, (C1-C8) alkyl, halo (C1-C8) alkyl, (C3-C7) cycloalkyl, (C1-C7) alkoxycarbonyl, (C6-C20) arylthio, (C6-C20 ) Aryl or (C6-C20) aryl (C1-C8) alkyl;
R ³ is (C6-C20) aryl, (C1-C7) alkyl or (C6-C20) aryl (C1-C7) alkyl;
Alkyl and aryl of R ¹ and R ² are (C ¹ -C 7) alkyl, halo (C 1 -C 7) alkyl, (C 1 -C 7) alkoxy, (C 1 -C 7) alkylcarbonyloxy, (C 6 -C 20) aryl ( C1-C7) alkyloxy, cyano, (C1-C7) alkyl (C6-C20) aryloxy and (C3-C7) cycloalkyl may be further substituted with one or more selected.]
The method of claim 1,
R ¹ is hydrogen, methyl, ethyl, hexyl, benzyl, phenylpropyl, chloromethyl, bromomethyl, chloroethyl, chloropropyl, cyanopropyl, methylcarbonyloxymethyl, benzyloxypropyl, dimethylphenoxypropyl, cyclo Hexylmethyl, benzylthio, phenylthio, ethoxycarbonyl, phenyl, pentylphenyl, trifluoromethylphenyl, chlorophenyl, ferrocenyl, methoxyphenyl or

Is;
R ² is hydrogen, ethyl, pentyl, hexyl, cyclohexyl, phenylethyl, chloroethyl, ethoxycarbonyl, phenyl, phenylthio, methylcarbonyloxymethyl or chlorophenyl;
R ³ is enol phosphate derivative, characterized in that phenyl, methyl, ethyl, propyl or benzyl.
The method of claim 2,
The enol phosphate derivative is selected from the following structures:

In the presence of a gold catalyst,
A method for preparing an enol phosphate derivative, which comprises producing a kinetic enol phosphate derivative of Formula A by reacting an alkane derivative represented by Formula 2 with a phosphate derivative represented by Formula 4.
[Formula A]

(2)

[Chemical Formula 4]

[Wherein, R ¹ is hydrogen, (C1-C7) alkyl, halo (C1-C7) alkyl, (C6-C20) aryl (C1-C7) alkyl, (C6-C20) arylthio, (C6-C20) Aryl (C1-C7) alkylthio, (C1-C7) alkyloxycarbonyl, (C6-C20) aryl, halo (C6-C20) aryl, ferrocenyl or

Is;
R ² is hydrogen, (C1-C7) alkyl, (C1-C7) alkoxycarbonyl, (C6-C20) arylthio or (C6-C20) aryl;
R ³ is (C6-C20) aryl, (C1-C7) alkyl or (C6-C20) aryl (C1-C7) alkyl;
Alkyl and aryl of R ¹ and R ² are (C ¹ -C 7) alkyl, halo (C 1 -C 7) alkyl, (C 1 -C 7) alkoxy, (C 1 -C 7) alkylcarbonyloxy, (C 6 -C 20) aryl ( C1-C7) alkyloxy, cyano, (C1-C7) alkyl (C6-C20) aryloxy and (C3-C7) cycloalkyl may be further substituted with one or more selected.]
In the presence of a gold catalyst,
A method for preparing an enol phosphate derivative, which comprises preparing a thermodynamic enol phosphate derivative of Formula B by reacting an alkane derivative represented by Formula 3 with a phosphate derivative represented by Formula 4.
[Formula B]

(3)

[Chemical Formula 4]

[Wherein R ² is (C 1 -C 7) alkyl, halo (C 1 -C 7) alkyl, (C 3 -C 7) cycloalkyl, (C 6 -C 20) aryl or (C 6 -C 20) aryl (C 1 -C 7) alkyl ;
R ³ is (C6-C20) aryl, (C1-C7) alkyl or (C6-C20) aryl (C1-C7) alkyl]
The method according to claim 4 or 5,
The gold catalyst is AuCl, AuCl ₃ , AuBr ₃ , PPh ₃ AuCl, (C ₆ F ₅ ) ₃ PAuCl, (IPr) AuCl, (IMes) A production method characterized in that at least one selected from the group consisting of.
The method of claim 4, wherein
The gold catalyst is characterized in that the PPh ₃ AuCl.
6. The method of claim 5,
The gold catalyst is characterized in that (C ₆ F ₅ ) ₃ PAuCl.
The method of claim 7, wherein
The PPh ₃ AuCl catalyst is characterized in that 1 to 10 mol% is used for the phosphate derivative represented by the formula (4).
The method of claim 8,
The (C ₆ F ₅ ) ₃ PAuCl catalyst is characterized in that 1 to 10 mol% is used for the phosphate derivative represented by the formula (4).
The method according to claim 4 or 5,
AgOTf, AgBF ₄ , AgPF ₆ , AgAsF ₆ , AgNTf ₂ , AgSbF _{6 in} addition to the gold catalyst And AgNO ₃ , wherein the silver catalyst is selected from the group consisting of AgNO ₃ .
12. The method of claim 11,
The use amount of the silver catalyst is 2 to 4 equivalents to the gold catalyst when using a trivalent gold catalyst, the production method characterized in that the same equivalent when using a monovalent gold catalyst.
The method of claim 4, wherein
A method for producing a kinetic enol phosphate represented by Formula A, wherein AgPF ₆ is used together with a gold catalyst.
6. The method of claim 5,
In the preparation of the thermodynamic enol phosphate represented by the formula (B), AgOTf is used in combination with a gold catalyst.
The method according to claim 13 and 14,
The silver catalyst is a production method, characterized in that used in 1 to 5 equivalents to the gold catalyst.
The method according to claim 4 or 5,
The reaction is dichloromethane (DCM), dichloroethane (DCE), toluene (Toluene), acetonitrile (MeCN), nitromethane (Nitromethan), tetrahydrofuran (THF), N, N -dimethylform A process characterized in that it is carried out under a solvent selected from amide (DMF), N, N -dimethylacetamide (DMA) and mixtures thereof.
The method according to claim 4 or 5,
The reaction is a manufacturing method characterized in that the reaction is carried out using toluene (Toluene) as a solvent at 20 to 140 ℃.