CN113429286A - Method for synthesizing polysubstituted biaryl derivative by using aryl diazonium salt - Google Patents

Method for synthesizing polysubstituted biaryl derivative by using aryl diazonium salt Download PDF

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CN113429286A
CN113429286A CN202110892930.2A CN202110892930A CN113429286A CN 113429286 A CN113429286 A CN 113429286A CN 202110892930 A CN202110892930 A CN 202110892930A CN 113429286 A CN113429286 A CN 113429286A
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norbornene
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傅颖
张玉霞
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Northwest Normal University
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    • 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
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    • C07C231/00—Preparation of carboxylic acid amides
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    • C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
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    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms

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Abstract

The invention provides a method for synthesizing a polysubstituted biaryl derivative by utilizing aryl diazonium salt, which comprises the steps of taking palladium salt and norbornene or norbornene derivative as catalysts, taking triaryl phosphine as a ligand, taking iodide as an activating agent, and reacting the aryl diazonium salt, o-iodoarene and olefin in an organic solvent at 75-105 ℃ for 6-12 hours under an alkaline condition to obtain the polysubstituted biaryl derivative. The polysubstituted biaryl derivative is obtained by coupling reaction of o-iodoarene, aryl diazonium salt and olefin under the Pd/NBE concerted catalysis, and has the advantages of simple and convenient synthesis operation, low raw material cost, mild reaction conditions, environmental protection and the like.

Description

Method for synthesizing polysubstituted biaryl derivative by using aryl diazonium salt
Technical Field
The invention belongs to the technical field of organic synthesis, relates to a synthesis method of a polysubstituted biaryl hydrocarbon derivative, and particularly relates to a method for synthesizing the polysubstituted biaryl hydrocarbon derivative by using aryl diazonium salt.
Background
The polysubstituted biaryl derivative plays an important role in the fields of medicine preparation, natural product synthesis, photoelectric material development and the like, and particularly plays a role in constructing polynuclear arene (hydrocarbons containing two or more benzene rings). With the increasing demand for fused aromatic derivatives, particularly in the fields of agricultural chemicals and medicines, the efficient and convenient synthesis method has gradually shown advantages.
The Pd/NBE co-catalysis, first reported by Catellari et al in 1997, a one-pot approach to the synthesis strategy of ortho-and in situ bifunctional aryl halides is very attractive. The reaction carries out ordered ortho C-H functionalization and in-situ coupling reaction on the aryl iodide through the concerted catalysis of palladium and norbornene, thereby efficiently and selectively completing the bi-functionalization or multi-functionalization of the aryl iodide and synthesizing the multi-substituted and complex aromatic hydrocarbon compound by one stepAngew. Chem. 1997, 109,142 - 145.]。
Pd/NBE is used for constructing Ar-Ar bond in a concerted catalysis manner, and the currently developed aromatic source is limited to aryl halideOrg. Lett. 2001, 3, 3611-3614.]And sulfonic acid phenyl ester [ alpha ], [ alpha ] and [ alpha ], [ alpha ] andOrg. Lett. 2011, 13, 1486-1489.]. Aryl halides are more expensive to produce than aryl diazonium salts and the large amount of halide salt present during the reaction is not environmentally friendly. The use of benzene sulfonate electrophiles is limited by their low reactivity (C — O bond is difficult to break) compared to aryl diazonium salts. In recent years, methods for constructing compounds by initiating metal catalytic cycles via C-N bond activation rather than C-X bond or C-O bond cleavage have become new approaches and new ideas for organometallic chemistry research. In such studies, aryl diazonium salts, due to their unique properties, have become very valuable electrophiles for coupling reactions and new heats of researchAnd (4) point.
Aryl diazonium salts can be synthesized from aromatic amines with simple preparation and high yields. The aryl diazonium salt participates in the palladium-catalyzed coupling reaction, and the activity is higher than that of corresponding aryl halide and aromatic ester. The diazo group in the diazonium salt can be removed in the form of nitrogen molecules, and is very environment-friendly. Diazo groups are also advantageous over halogens in the chemical selectivity of the coupling reaction. The invention aims to combine aryl diazonium salt with a Catellani reaction mode through the characteristics of the aryl diazonium salt, and develop the aryl diazonium salt into a new aromatic source of Catellan reaction to construct polysubstituted aromatic hydrocarbon.
Disclosure of Invention
The invention aims to provide a method for synthesizing a polysubstituted biaryl derivative by utilizing aryl diazonium salt, which obtains the polysubstituted biaryl derivative by utilizing the coupling reaction of o-iodoarene, aryl diazonium salt and olefin under the Pd/NBE concerted catalysis.
The invention relates to a method for synthesizing polysubstituted biaryl derivative by utilizing aryl diazonium salt, which comprises the steps of taking palladium salt and norbornene or norbornene derivative as catalysts, taking triaryl phosphine as a ligand, taking iodide as an activating agent, and reacting the aryl diazonium salt, o-iodoarene and olefin in an organic solvent for 6-12 hours at 75-105 ℃ under an alkaline condition to obtain polysubstituted biaryl derivative;
the structure of the polysubstituted biaryl derivative is shown as the formula (I):
Figure 232205DEST_PATH_IMAGE001
the structure of the o-iodoarene is shown as a formula (II):
Figure 352607DEST_PATH_IMAGE002
the aryl diazonium salt has a structure shown in a formula (III):
Figure 210973DEST_PATH_IMAGE003
the structure of the olefin is shown as the following formula (IV):
Figure 668499DEST_PATH_IMAGE004
；
the synthetic route is as follows:
Figure 794456DEST_PATH_IMAGE005
in the formulae (I) to (IV) and the synthetic routes, R1Is any one of alkyl, alkoxy, ester group, aryl, trifluoromethyl and trifluoromethoxy; r2Is any one of alkyl, aryl, alkoxy, ester group, trifluoromethyl, cyano, carbonyl and aldehyde group; x-Is tetrafluoroborate (BF)4 -) Hexafluorophosphate (PF)6 -) Methane sulfonate (CH)3SO3 -) Or p-toluenesulfonate salt (Ts)-）；R3Is any one of hydrogen, alkyl, aryl, aldehyde group, ester group and amide group; r4Is any one of hydrogen, alkyl, aryl, aldehyde group, ester group and amide group.
The molar ratio of the o-iodoarene to the aryl diazonium salt to the olefin is 1:1: 1-1.5: 2: 1.
The palladium salt is one of palladium acetate, bis (triphenylphosphine) palladium dichloride and tetrakis (triphenylphosphine) palladium, and is preferably palladium acetate; the dosage of the palladium salt is 5-10% of the molar weight of the o-iodoarene.
The norbornene derivative is 5-norbornene-2-carboxylic acid methyl ester, cis-5-norbornene-endo-2, 3-dicarboxylic acid or N-hydroxy-5-norbornene-2, 3-dicarboximide; the molar ratio of the norbornene or norbornene derivative to the o-iodoarene is 1: 0.5-1: 1.5.
The triarylphosphine is one of triphenylphosphine, tri (4-methoxyphenyl) phosphine, tri (4-tolyl) phosphine and tri (2-methylphenyl) phosphine, preferably tri (4-methoxyphenyl) phosphine (P (P-MeOPh)3) (ii) a The dosage of the triarylphosphine is 10-20% of the molar weight of the o-iodoarene.
The iodide is one of potassium iodide, sodium iodide and tetrabutylammonium iodide, and potassium iodide is preferred; the molar ratio of the o-iodoarene to the iodide is 1: 1-1: 2.
The organic solvent is one of N, N-Dimethylformamide (DMF), N-Dimethylacetamide (DMA) and N-methylpyrrolidone (NMP), and is preferably N, N-dimethylformamide.
The aryl diazonium salt is synthesized by the following method:
in a 25mL round-bottom flask, aromatic amine (5 mmol) was dissolved in ethanol (1.5 mL) and HBF4(48% aqueous solution, 1.25 mL). Tert-butyl nitrite (1.35 mL) was then added dropwise to the solution at 0 ℃. The mixture was stirred at room temperature for 1h, then diethyl ether (5 mL) was added to precipitate the aromatic diazonium tetrafluoroborate. (Note: if no solid is formed after addition of ether, the flask is placed in a refrigerator for 8-12 h). The solid is filtered off and washed with diethyl ether ((3X 5 mL)
And (6) washing. The aromatic diazonium tetrafluoroborate salt was dried under vacuum for 25 minutes and then used directly without further purification.
Figure DEST_PATH_IMAGE006
Wherein R is2Is any one of alkyl, aryl, alkoxy, ester group, trifluoromethyl, cyano, carbonyl and aldehyde group.
Compared with the prior art, the invention has the following advantages:
1. the aryl diazonium salt provides a new aromatic source for ortho-position arylation reaction under the Catellari mode, and has the advantages of wide source and low price;
2. compared with aryl halide and phenyl sulfonate reactants, the method has the advantages of mild reaction conditions, environmental friendliness and high yield in a Catellari reaction mode.
Detailed Description
The synthesis of the compounds of the present invention is further illustrated by the following specific examples.
Example 1: (E) -2 ' - (3-methoxy-3-oxoprop-1-en-1-yl) -3 ' -methyl- [1,1' -biphenyl ] -4-carboxylic acid methyl ester
Figure 413656DEST_PATH_IMAGE007
To a dry 25mL Schlenk's tube was added o-methyliodobenzene (71.9 mg, 0.33 mmol), 4-methoxycarbonyldiazobenzenetetrafluoroborate (150 mg, 0.6 mmol), methyl acrylate (25.8 mg, 0.3 mmol), NBE (norbornene) (56.4 mg, 0.6 mmol), palladium acetate (6.7 mg, 0.033 mmol), potassium carbonate (207.3 mg, 1.5 mmol), KI (99.6 mg, 0.6 mmol), P (P-MeOPh)3(21.1 mg, 0.066 mmol), N, N-dimethylformamide (3 mL). The reaction mixture was reacted for 8 hours in a constant temperature oil bath magnetic stirrer at 85 ℃. After completion, the reaction mixture was dissolved in ethyl acetate (10 mL) and washed with water (3X 10 mL) and brine (10 mL) in that order. The aqueous phase was further extracted with ethyl acetate (10 mL) and washed again with water (3X 10 mL) and brine (10 mL). The organic phases were combined and washed with anhydrous Na2SO4Dried and concentrated. Purification by silica gel column chromatography gave the desired target product 69.8 mg, 75% yield.
1 (400 MHz, CDCl3) δ 8.05 (d, J = 8.0 Hz, 2H), 7.67 (d, J = 16.3 Hz, 1H), 7.38 - 7.27 (m, 4H), 7.18 (d, J = 7.4 Hz, 1H), 5.76 (d, J = 16.4 Hz, 1H), 3.94 (s, 3H), 3.70 (s, 3H), 2.45 (s, 3H).
13C NMR (151 MHz, CDCl3) δ 166.9, 146.0, 143.1, 141.2, 137.3, 132.6, 130.4, 129.7, 129.4, 128.8, 128.5, 128.1, 124.4, 52.1, 51.6, 21.3 .
Example 2: (E) -methyl 3- (4 '-methoxy-3, 4-dimethyl- [1,1' -biphenyl ] -2-yl) acrylate
Figure 759318DEST_PATH_IMAGE008
To a dry 25mL Schlenk's tube was added 2, 3-dimethyliodobenzene (76.5 mg, 0.33 mmol), 4-methoxyphenyldiazotetrafluoroborate (133.2 mg, 0.6 mmol), methyl acrylate (25.8 mg, 0.3 mmol), NBE (norbornene) (56.4 mg, 0.6 mmol), palladium acetate (6.7 mg, 0.033 mmol), potassium carbonate (207.3 mg, 1.5 mmol), KI (99.6 mg, 0.6 mmol), P (P-MeOPh)3(21.1 mg, 0.066 mmol), N, N-dimethylformamide (3 mL). The reaction mixture was reacted for 8 hours in a constant temperature oil bath magnetic stirrer at 85 ℃. After completion, the reaction mixture was dissolved in ethyl acetate (10 mL) and washed with water (3X 10 mL) and brine (10 mL) in that order. The aqueous phase was further extracted with ethyl acetate (10 mL) and washed again with water (3X 10 mL) and brine (10 mL). The organic phases were combined and washed with anhydrous Na2SO4Dried and concentrated. Purification by silica gel column chromatography gave the desired title product 74.6 mg, 84% yield.
1 (400 MHz, CDCl3) δ 7.73 (d, J = 16.4 Hz, 1H), 7.17 (d, J = 8.6 Hz, 3H), 7.08 (d, J = 7.7 Hz, 1H), 6.89 (d, J = 8.2 Hz, 2H), 5.77 (d, J = 16.3 Hz, 1H), 3.83 (s, 3H), 3.72 (s, 3H), 2.34 (d, J = 8.8 Hz, 6H).
13C NMR (151 MHz, CDCl3) δ 144.8, 139.5, 136.0, 135.1, 133.7, 133.2, 130.8, 129.9, 127.7, 124.2, 113.5, 55.2, 51.5, 20.6, 17.1 .
HRMS (ESI) m/z: Calcd for C19H20KO3 + [M+K]+335.1044; Found 335.1035.
Example 3: (E) -3- (4 '-cyano-3-methoxy- [1,1' -biphenyl ] -2-yl) acrylic acid methyl ester
Figure 286114DEST_PATH_IMAGE009
To a dry 25mL Schlenk tube was added o-methoxyiodobenzene (77.2 mg, 0.33 mmol), 4-cyanobenzodiazobenzene tetrafluoroborate (130.2 mg, 0.6 mmol),methyl acrylate (25.8 mg, 0.3 mmol), NBE (norbornene) (56.4 mg, 0.6 mmol), palladium acetate (6.7 mg, 0.033 mmol), potassium carbonate (207.3 mg, 1.5 mmol), KI (99.6 mg, 0.6 mmol), P (P-MeOPh)3(21.1 mg, 0.066 mmol), N, N-dimethylformamide (3 mL). The reaction mixture was reacted for 8 hours in a constant temperature oil bath magnetic stirrer at 85 ℃. After completion, the reaction mixture was dissolved in ethyl acetate (10 mL) and washed with water (3X 10 mL) and brine (10 mL) in that order. The aqueous phase was further extracted with ethyl acetate (10 mL) and washed again with water (3X 10 mL) and brine (10 mL). The organic phases were combined and washed with anhydrous Na2SO4Dried and concentrated. Purification by silica gel column chromatography gave 68.6mg of the desired title product in 78% yield.
1 (400 MHz, CDCl3) δ 7.69 -7.63 (m, 3H), 7.39 (d, J = 7.9 Hz, 2H), 7.35 -7.27 (m, 2H), 7.15 (d, J = 7.0 Hz, 1H), 5.74 (d, J = 16.3 Hz, 1H), 3.72 (s, 3H), 2.45 (s, 3H).
13C NMR (151 MHz, CDCl3) δ 167.9, 159.2, 145.4, 138.8, 132.0, 130.5, 130.2, 123.0, 122.5, 121.3, 111.4, 111.0, 55.7, 51.5 .
HRMS (ESI) m/z: Calcd for C18H15KNO3 + [M+K]+332.0684; Found 332.0680.
Example 4: (E) -2- (3-methoxy-3-oxoprop-1-en-1-yl) - [1,1 'biphenyl ] -3,4' -dicarboxylic acid methyl ester
Figure 523368DEST_PATH_IMAGE010
To a dry 25mL Schlenk's tube was added methyl orthoformate iodobenzene (86.4 mg, 0.33 mmol), 4-methoxycarbonyldiazobenzenetetrafluoroborate (150 mg, 0.6 mmol), methyl acrylate (25.8 mg, 0.3 mmol), NBE (norbornene) (56.4 mg, 0.6 mmol), palladium acetate (6.7 mg, 0.033 mmol), potassium carbonate (207.3 mg, 1.5 mmol), KI (99.6 mg, 0.6 mmol), P (P-MeOPh)3（21.1 mg，0.066mmol), N, N-dimethylformamide (3 mL). The reaction mixture was reacted for 8 hours in a constant temperature oil bath magnetic stirrer at 85 ℃. After completion, the reaction mixture was dissolved in ethyl acetate (10 mL) and washed with water (3X 10 mL) and brine (10 mL) in that order. The aqueous phase was further extracted with ethyl acetate (10 mL) and washed again with water (3X 10 mL) and brine (10 mL). The organic phases were combined and washed with anhydrous Na2SO4Dried and concentrated. Purification by silica gel column chromatography gave the desired title product 74.4 mg, 70% yield.
1 (400 MHz, CDCl3) δ 7.96 (d, J = 7.8 Hz, 1H), 7.93 -7.85 (m, 2H), 7.53 (t, J = 7.6 Hz, 1H), 7.42 (t, J = 7.7 Hz, 2H), 7.36 -7.32 (m, 1H), 7.19 (d, J = 7.6 Hz, 1H), 5.52 (d, J = 16.2 Hz, 1H), 3.90 (s, 3H), 3.65 (s, 6H).
13C NMR (151 MHz, CDCl3) δ 167.2, 166.4, 143.4, 142.0, 141.4, 134.8, 133.0, 131.7, 131.3, 130.3, 130.2, 130.1, 129.2, 127.7, 127.7, 123.5, 52.3, 51.9, 51.5 .
HRMS (ESI) m/z: Calcd for C20H18KO6+ [M+K]+393.0735; Found 393.0730.
Example 5: (E) -methyl 3- (2- (4- (4-methoxyphenyl) 1-naphthyl) acrylate
Figure 985573DEST_PATH_IMAGE011
To a dry 25mL Schlenk tube was added iodonaphthalene (83.4 mg, 0.33 mmol), 4-methoxyphenyldiazotetrafluoroborate (133.2 mg, 0.6 mmol), methyl acrylate (25.8 mg, 0.33 mmol), NBE (norbornene) (56.4 mg, 0.6 mmol), palladium acetate (6.7 mg, 0.033 mmol), potassium carbonate (207.3 mg, 1.5 mmol), KI (99.6 mg, 0.6 mmol), P (P-MeOPh)3(21.1 mg, 0.066 mmol), N, N-dimethylformamide (3 mL). The reaction mixture was reacted for 8 hours in a constant temperature oil bath magnetic stirrer at 85 ℃. After completion, the reaction mixture was dissolved in ethyl acetate (10 mL), followed by water (3X 10 mL) and brine (R) ((R))10 mL) was washed. The aqueous phase was further extracted with ethyl acetate (10 mL) and washed again with water (3X 10 mL) and brine (10 mL). The organic phases were combined and washed with anhydrous Na2SO4Dried and concentrated. Purification by silica gel column chromatography gave 84.9 mg of the objective product in 89% yield.
1 (400 MHz, CDCl3) δ 8.23 (d, J = 7.9 Hz, 1H), 8.02 (d, J = 16.4 Hz, 1H), 7.86 (t, J = 8.2 Hz, 2H), 7.57 -7.40 (m, 3H), 7.29 (d, J = 8.6 Hz, 2H), 6.96 (d, J = 8.7 Hz, 2H), 6.17 (d, J = 16.4 Hz, 1H), 3.86 (s, 3H), 3.78 (s, 3H).
13C NMR (151 MHz, CDCl3) δ 166.9, 158.9, 143.3, 139.1, 133.3, 132.7, 131.2, 128.9, 128.4, 128.3, 126.9, 125.8, 125.1, 125.1, 113.6, 55.2, 51.6 .
HRMS (ESI) m/z: Calcd for C21H18KO3+ [M+K]+ 357.0888; Found 357.0876.
Example 6: (E) -3- (4 '-methoxy-3- (trifluoromethyl) - [1,1' -biphenyl ] -2-yl) acrylic acid methyl ester
Figure 67798DEST_PATH_IMAGE012
To a dry 25mL Schlenk's tube was added ortho-trifluoromethyliodobenzene (89.7 mg, 0.33 mmol), 4-methoxybenzene diazo tetrafluoroborate (133.2 mg, 0.6 mmol), methyl acrylate (25.8 mg, 0.3 mmol), NBE (norbornene) (56.4 mg, 0.6 mmol), palladium acetate (6.7 mg, 0.033 mmol), potassium carbonate (207.3 mg, 1.5 mmol), KI (99.6 mg, 0.6 mmol), P (P-MeOPh)3(21.1 mg, 0.066 mmol), N, N-dimethylformamide (3 mL). The reaction mixture was reacted for 8 hours in a constant temperature oil bath magnetic stirrer at 85 ℃. After completion, the reaction mixture was dissolved in ethyl acetate (10 mL) and washed with water (3X 10 mL) and brine (10 mL) in that order. The aqueous phase was further extracted with ethyl acetate (10 mL) and washed again with water (3X 10 mL) and brine (10 mL). The organic phases were combined and washed with anhydrous Na2SO4Is dried andand (5) concentrating. Purification by silica gel column chromatography gave 57.5 mg of the objective product, yield 57%.
1 (400 MHz, CDCl3) δ 7.82 (d, J = 16.3 Hz, 1H), 7.70 (d, J = 7.8 Hz, 1H), 7.48 (dt, J = 15.3, 7.7 Hz, 2H), 7.18 (d, J = 8.9 Hz, 2H), 6.92 (d, J = 8.8 Hz, 2H), 5.73 (d, J = 16.3 Hz, 1H), 3.85 (s, 3H), 3.72 (s, 3H).
13C NMR (151 MHz, CDCl3) δ 166.2 , 142.8 , 140.8 , 134.1 , 132.1 , 130.8 , 128.1 , 126.5 , 113.8 , 55.2 , 51.7 .
19F NMR (376 MHz, CDCl3) δ -58.50 .
HRMS (ESI) m/z: Calcd for C18H15F3KO3 + [M+K]+375.0605; Found 375.0603.
Example 7: (E) -3- (4 '-methoxy-3- (trifluoromethoxy) - [1,1' -biphenyl ] -2-yl) acrylic acid methyl ester
Figure 273652DEST_PATH_IMAGE013
To a dry 25mL Schlenk's tube was added ortho-trifluoromethoxyiodobenzene (95.0 mg, 0.33 mmol), 4-methoxybenzene diazo tetrafluoroborate (133.2 mg, 0.6 mmol), methyl acrylate (25.8 mg, 0.3 mmol), NBE (norbornene) (56.4 mg, 0.6 mmol), palladium acetate (6.7 mg, 0.033 mmol), potassium carbonate (207.3 mg, 1.5 mmol), KI (99.6 mg, 0.6 mmol), P (P-MeOPh)3(21.1 mg, 0.066 mmol), N, N-dimethylformamide (3 mL). The reaction mixture was reacted for 8 hours in a constant temperature oil bath magnetic stirrer at 85 ℃. After completion, the reaction mixture was dissolved in ethyl acetate (10 mL) and washed with water (3X 10 mL) and brine (10 mL) in that order. The aqueous phase was further extracted with ethyl acetate (10 mL) and washed again with water (3X 10 mL) and brine (10 mL). The organic phases were combined and washed with anhydrous Na2SO4Dried and concentrated. Purification by silica gel column chromatography gave 67.6 mg of the desired product,the yield was 64%.
1 (400 MHz, CDCl3) δ 7.53 (d, J = 16.6 Hz, 1H), 7.43 -7.37 (m, 1H), 7.32 -7.27 (m, 2H), 7.22 (d, J = 8.9 Hz, 2H), 6.96 (d, J = 8.8 Hz, 2H), 6.34 (d, J = 16.5 Hz, 1H), 3.86 (s, 3H), 3.75 (s, 3H).
13C NMR (151 MHz, CDCl3) δ 167.1 , 159.4 , 144.7 , 138.3 , 131.5 , 130.8 , 129.6 , 128.9 ( d , J=275.7Hz), 124.3 , 119.5 , 113.9 , 110.0 , 55.3 , 51.6 .
19F NMR (376 MHz, CDCl3) δ -57.21 .
HRMS (ESI) m/z: Calcd for C18H15F3KO4 + [M+K]+391.0554; Found 391.0547.
Example 8: (E) -3- (4 '-acetyl-3-methoxy- [1,1' -biphenyl ] -2-yl) acrylic acid methyl ester
Figure 875666DEST_PATH_IMAGE014
To a dry 25mL Schlenk's tube was added o-methoxyiodobenzene (77.2 mg, 0.33 mmol), 4-acetyldiazobenzene tetrafluoroborate (140.4 mg, 0.6 mmol), methyl acrylate (25.8 mg, 0.3 mmol), NBE (norbornene) (56.4 mg, 0.6 mmol), palladium acetate (6.7 mg, 0.033 mmol), potassium carbonate (207.3 mg, 1.5 mmol), KI (99.6 mg, 0.6 mmol), P (P-MeOPh)3(21.1 mg, 0.066 mmol), N, N-dimethylformamide (3 mL). The reaction mixture was reacted for 8 hours in a constant temperature oil bath magnetic stirrer at 85 ℃. After completion, the reaction mixture was dissolved in ethyl acetate (10 mL) and washed with water (3X 10 mL) and brine (10 mL) in that order. The aqueous phase was further extracted with ethyl acetate (10 mL) and washed again with water (3X 10 mL) and brine (10 mL). The organic phases were combined and washed with anhydrous Na2SO4Dried and concentrated. Purification by silica gel column chromatography gave 56.8 mg of the desired title product in 61% yield.
1(400 MHz, CDCl3) δ 8.05 -7.97 (m, 2H), 7.59 (d, J = 16.2 Hz, 1H), 7.45 -7.34 (m, 3H), 7.03 -6.90 (m, 2H), 6.59 (d, J = 16.2 Hz, 1H), 3.95 (s, 3H), 3.71 (s, 3H), 2.65 (s, 3H).
13C NMR (151 MHz, CDCl3) δ 197.7 , 159.2 , 143.9 , 139.2 , 136.0 , 130.1 , 130.0 , 128.2 , 128.2 , 122.6 , 122.5 , 121.3 , 110.6 , 55.6 , 51.4 , 26.6 .
HRMS (ESI) m/z: Calcd for C19H18KO4 + [M+K]+349.0837; Found 349.0835.
Example 9: (E) -3- (2- (4- (trifluoromethyl) phenyl) naphthalen-1-yl) acrylic acid methyl ester
Figure 898985DEST_PATH_IMAGE015
Iodonaphthalene (83.4 mg, 0.33 mmol), 4-trifluoromethyldiazobenzenetetrafluoroborate (156.0 mg, 0.6 mmol), methyl acrylate (25.8 mg, 0.3 mmol), NBE (norbornene) (56.4 mg, 0.6 mmol), palladium acetate (6.7 mg, 0.033 mmol), potassium carbonate (207.3 mg, 1.5 mmol), KI (99.6 mg, 0.6 mmol), P (P-MeOPh) were added to a dry 25mL Schlenk tube3(21.1 mg, 0.066 mmol), N, N-dimethylformamide (3 mL). The reaction mixture was reacted for 8 hours in a constant temperature oil bath magnetic stirrer at 85 ℃. After completion, the reaction mixture was dissolved in ethyl acetate (10 mL) and washed with water (3X 10 mL) and brine (10 mL) in that order. The aqueous phase was further extracted with ethyl acetate (10 mL) and washed again with water (3X 10 mL) and brine (10 mL). The organic phases were combined and washed with anhydrous Na2SO4Dried and concentrated. Purification by silica gel column chromatography gave 82.3 mg of the desired target product in 77% yield.
1 (400 MHz,CDCl3) δ 8.20 (d, J = 7.3 Hz, 1H), 8.01 (d, J = 16.4 Hz, 1H), 7.89 (d, J = 8.2 Hz, 2H), 7.67 (d, J = 8.0 Hz, 2H), 7.59 - 7.51 (m, 2H), 7.47 (d, J = 7.8 Hz, 2H), 7.42 (d, J = 8.5 Hz, 1H), 6.10 (d, J = 16.4 Hz, 1H), 3.77 (s, 3H).
13C NMR (151 MHz, CDCl3) δ 166.5 , 144.7 (d, J = 1.2Hz), 142.3 , 137.6 , 133.0 , 131.1, 130.5 , 130.3 , 129.4(d, J = 32.5 Hz), 129.1 , 128.4 , 127.6 , 127.2 , 126.4 , 126.2 , 125.2 , 125.1(q, J = 3.9 Hz), 124.1(d, J = 272.2 Hz), 51.74 .
19F NMR (376 MHz, CDCl3) δ -62.79 .
HRMS (ESI) m/z: Calcd for C21H16F3O2 + [M+H]+ 357.1097; Found 357.1096.
Example 10: (E) -3- (2- (4-formylphenyl) naphthalen-1-yl) acrylic acid methyl ester
Figure 343873DEST_PATH_IMAGE016
To a dry 25mL Schlenk tube was added iodonaphthalene (83.4 mg, 0.33 mmol), 4-formyldiazobenzenetetrafluoroborate (132.0 mg, 0.6 mmol), methyl acrylate (25.8 mg, 0.3 mmol), NBE (norbornene) (56.4 mg, 0.6 mmol), palladium acetate (6.7 mg, 0.033 mmol), potassium carbonate (207.3 mg, 1.5 mmol), KI (99.6 mg, 0.6 mmol), P (P-MeOPh)3(21.1 mg, 0.066 mmol), N, N-dimethylformamide (3 mL). The reaction mixture was reacted for 8 hours in a constant temperature oil bath magnetic stirrer at 85 ℃. After completion, the reaction mixture was dissolved in ethyl acetate (10 mL) and washed with water (3X 10 mL) and brine (10 mL) in that order. The aqueous phase was further extracted with ethyl acetate (10 mL) and washed again with water (3X 10 mL) and brine (10 mL). The organic phases were combined and washed with anhydrous Na2SO4Dried and concentrated. Purification by silica gel column chromatography gave the desired title product 51.2 mg, 54% yield.
1 (400 MHz, CDCl3) δ 10.08 (s, 1H), 8.20 (d, J = 7.1 Hz, 1H), 8.05 (d, J = 16.3 Hz, 1H), 7.94 (t, J = 8.3 Hz, 4H), 7.61 -7.53 (m, 4H), 7.47 (d, J = 8.5 Hz, 1H), 6.07 (d, J = 16.3 Hz, 1H), 3.77 (s, 3H).
13C NMR (151 MHz, CDCl3) δ 191.9 , 166.5 , 147.5 , 142.3 , 135.1 , 133.1 , 131.1 , 130.7 , 130.6 , 129.6 , 129.2 , 128.5 , 127.5 , 127.3 , 126.6 , 126.3 , 125.2 , 51.7 .
HRMS (ESI) m/z: Calcd for C21H16KO3 + [M+K]+ 355.0731; Found 355.0728.
Example 11: (E) -methyl 3- (3-methoxy- [1,1':4',1'' -terphenyl ] -2-yl) acrylate
Figure 461740DEST_PATH_IMAGE017
To a dry 25mL Schlenk's tube was added o-methoxyiodobenzene (77.2 mg, 0.33 mmol), 4-phenyldiazobenzene tetrafluoroborate (160.8 mg, 0.6 mmol), methyl acrylate (25.8 mg, 0.3 mmol), NBE (norbornene) (56.4 mg, 0.6 mmol), palladium acetate (6.7 mg, 0.033 mmol), potassium carbonate (207.3 mg, 1.5 mmol), KI (99.6 mg, 0.6 mmol), P (P-MeOPh)3(21.1 mg, 0.066 mmol), N, N-dimethylformamide (3 mL). The reaction mixture was reacted for 8 hours in a constant temperature oil bath magnetic stirrer at 85 ℃. After completion, the reaction mixture was dissolved in ethyl acetate (10 mL) and washed with water (3X 10 mL) and brine (10 mL) in that order. The aqueous phase was further extracted with ethyl acetate (10 mL) and washed again with water (3X 10 mL) and brine (10 mL). The organic phases were combined and washed with anhydrous Na2SO4Dried and concentrated. Purification by silica gel column chromatography gave 68.1 mg of the desired title product in 66% yield.
1 (400 MHz, CDCl3) δ 7.70 (d, J = 16.2 Hz, 1H), 7.68 – 7.61 (m, 4H), 7.46 (t, J = 7.6 Hz, 2H), 7.37 (t, J = 7.8 Hz, 4H), 6.98 (dd, J = 11.0, 7.9 Hz, 2H), 6.67 (d, J = 16.2 Hz, 1H), 3.94 (s, 3H), 3.71 (s, 3H).
13C NMR (151 MHz, CDCl3) δ 166.3 , 142.4 , 142.0 , 134.5 , 133.2 , 133.1 , 131.1 , 130.9 , 130.7 , 129.4 , 129.1 , 128.5 , 127.4 , 127.4 , 126.6 , 126.5 , 125.2 , 112.6 , 51.8 .
HRMS (ESI) m/z: Calcd for C23H20KO3 + [M+K]+383.1044; Found 383.1043.
Example 12: (E) -3- (2- (4-methoxyphenyl) naphthalen-1-yl) -2-methacrylic acid methyl ester
Figure 433107DEST_PATH_IMAGE018
To a dry 25mL Schlenk tube was added iodonaphthalene (83.4 mg, 0.33 mmol), 4-methoxyphenyldiazotetrafluoroborate (133.2 mg, 0.6 mmol), methyl 2-methacrylate (30 mg, 0.3 mmol), NBE (norbornene) (56.4 mg, 0.6 mmol), palladium acetate (6.7 mg, 0.033 mmol), potassium carbonate (207.3 mg, 1.5 mmol), KI (99.6 mg, 0.6 mmol), P (P-MeOPh)3(21.1 mg, 0.066 mmol), N, N-dimethylformamide (3 mL). The reaction mixture was reacted for 8 hours in a constant temperature oil bath magnetic stirrer at 85 ℃. After completion, the reaction mixture was dissolved in ethyl acetate (10 mL) and washed with water (3X 10 mL) and brine (10 mL) in that order. The aqueous phase was further extracted with ethyl acetate (10 mL) and washed again with water (3X 10 mL) and brine (10 mL). The organic phases were combined and washed with anhydrous Na2SO4Dried and concentrated. Purification by silica gel column chromatography gave the desired target product 21 mg, 21% yield.
1 (400 MHz, CDCl3) δ 7.99 (s, 1H), 7.91 -7.83 (m, 3H), 7.54 -7.50 (m, 2H), 7.50 (s, 1H), 7.33 -7.28 (m, 2H), 6.92 (d, J = 8.2 Hz, 2H), 3.85 (s, 3H), 3.80 (s, 3H), 1.46 (s, 3H).
13C NMR (151 MHz, CDCl3) δ 168.2, 138.1, 133.8, 132.2, 131.3, 131.1, 130.6, 130.6, 128.2, 128.2, 128.1, 126.5, 125.7, 125.6, 113.5, 55.2, 51.9, 14.3 .
HRMS (ESI) m/z: Calcd for C22H20KO3 + [M+K]+371.1044; Found 371.1042.
Example 13: (E) -3- (2- (4-methoxyphenyl) naphthalen-1-yl) -N, N-dimethylacrylamide
Figure 237115DEST_PATH_IMAGE019
Iodonaphthalene (83.4 mg, 0.33 mmol), 4-methoxyphenyldiazotetrafluoroborate (133.2 mg, 0.6 mmol), N, N-dimethylacrylamide (29.7 mg, 0.3 mmol), NBE (norbornene) (56.4 mg, 0.6 mmol), palladium acetate (6.7 mg, 0.033 mmol), potassium carbonate (207.3 mg, 1.5 mmol), KI (99.6 mg, 0.6 mmol), P (P-MeOPh) were added to a dry 25mL Schlenk tube3(21.1 mg, 0.066 mmol), N, N-dimethylformamide (3 mL). The reaction mixture was reacted for 8 hours in a constant temperature oil bath magnetic stirrer at 85 ℃. After completion, the reaction mixture was dissolved in ethyl acetate (10 mL) and washed with water (3X 10 mL) and brine (10 mL) in that order. The aqueous phase was further extracted with ethyl acetate (10 mL) and washed again with water (3X 10 mL) and brine (10 mL). The organic phases were combined and washed with anhydrous Na2SO4Dried and concentrated. Purification by silica gel column chromatography gave 78.5 mg of the desired title product in 79% yield.
1 (400 MHz, CDCl3) δ 8.22 (d, J = 7.5 Hz, 1H), 8.08 (d, J = 15.7 Hz, 1H), 7.90 -7.82 (m, 2H), 7.57 -7.48 (m, 2H), 7.46 (d, J = 8.4 Hz, 1H), 7.31 (d, J = 8.6 Hz, 2H), 6.95 (d, J = 8.7 Hz, 2H), 6.38 (d, J = 15.7 Hz, 1H), 3.84 (s, 3H), 3.01 (s, 3H), 2.79 (s, 3H).
13C NMR (151 MHz, CDCl3) δ 158.7, 139.5, 134.1, 131.7, 131.3, 131.1, 128.5, 128.2, 128.2, 126.6, 126.0, 125.8, 125.2, 113.7, 55.3, 36.9, 35.6 .
HRMS (ESI) m/z: Calcd for C22H21KNO2 + [M+K]+370.1204; Found 370.1200.
Example 14: (E) -3- (2- (4-methoxyphenyl) naphthalen-1-yl) acrylonitrile
Figure 44665DEST_PATH_IMAGE020
To a dry 25mL Schlenk tube was added iodonaphthalene (83.4 mg, 0.33 mmol), 4-methoxyphenyldiazotetrafluoroborate (133.2 mg, 0.6 mmol), acrylonitrile (15.9 mg, 0.3 mmol), NBE (norbornene) (56.4 mg, 0.6 mmol), palladium acetate (6.7 mg, 0.033 mmol), potassium carbonate (207.3 mg, 1.5 mmol), KI (99.6 mg, 0.6 mmol), P (P-MeOPh)3(21.1 mg, 0.066 mmol), N, N-dimethylformamide (3 mL). The reaction mixture was reacted for 8 hours in a constant temperature oil bath magnetic stirrer at 85 ℃. After completion, the reaction mixture was dissolved in ethyl acetate (10 mL) and washed with water (3X 10 mL) and brine (10 mL) in that order. The aqueous phase was further extracted with ethyl acetate (10 mL) and washed again with water (3X 10 mL) and brine (10 mL). The organic phases were combined and washed with anhydrous Na2SO4Dried and concentrated. Purification by silica gel column chromatography gave the desired title product 62.4 mg, 73% yield.
1 (400 MHz, CDCl3) δ 8.13 (d, J = 8.5 Hz, 1H), 7.92 -7.88 (m, 2H), 7.75 (d, J = 17.0 Hz, 1H), 7.63 -7.51 (m, 3H), 7.46 (d, J = 8.5 Hz, 1H), 7.27 (s, 1H), 6.99 (d, J = 8.7 Hz, 2H), 5.62 (d, J = 17.0 Hz, 1H), 3.88 (s, 3H).
13C NMR (151 MHz, CDCl3) δ 149.2 , 139.4 , 132.7 , 132.6 , 131.0 , 130.7 , 129.7 , 128.8 , 128.6 , 128.3 , 127.4 , 126.1 , 124.2 , 117.8 , 113.9 , 103.7 , 55.3 .
HRMS (ESI) m/z: Calcd for C20H15KNO+ [M+K]+ 324.0785; Found 324.0781.
Example 15: (E) -3- (2- (4-methoxyphenyl) naphthalen-1-yl) -2-methylacrolein
Figure 592321DEST_PATH_IMAGE021
Iodonaphthalene (83.4 mg, 0.33 mmol), 4-methoxyphenyldiazotetrafluoroborate (133.2 mg, 0.6 mmol), 2-methacrolein (21.0 mg, 0.3 mmol), NBE (norbornene) (56.4 mg, 0.6 mmol), palladium acetate (6.7 mg, 0.033 mmol), potassium carbonate (207.3 mg, 1.5 mmol), KI (99.6 mg, 0.6 mmol), P (P-MeOPh) were added to a dry 25mL Schlenk tube3(21.1 mg, 0.066 mmol), N, N-dimethylformamide (3 mL). The reaction mixture was reacted for 8 hours in a constant temperature oil bath magnetic stirrer at 85 ℃. After completion, the reaction mixture was dissolved in ethyl acetate (10 mL) and washed with water (3X 10 mL) and brine (10 mL) in that order. The aqueous phase was further extracted with ethyl acetate (10 mL) and washed again with water (3X 10 mL) and brine (10 mL). The organic phases were combined and washed with anhydrous Na2SO4Dried and concentrated. Purification by silica gel column chromatography gave the desired target product 31.7 mg, 35% yield.
1 (400 MHz, CDCl3) δ 9.70 (s, 1H), 7.93 (d, J = 8.4 Hz, 2H), 7.79 -7.74 (m, 1H), 7.70 (s, 1H), 7.56 -7.53 (m, 2H), 7.52 (d, J = 1.5 Hz, 1H), 7.27 (d, J = 8.8 Hz, 2H), 6.92 (d, J = 8.7 Hz, 2H), 3.85 (s, 3H), 1.44 (s, 3H).
13C NMR (151 MHz, CDCl3) δ 194.9 , 159.0 , 149.0 , 138.3 , 133.3 , 132.3 , 130.7 , 130.4 , 129.5 , 128.9 , 128.4 , 128.1 , 126.8 , 125.9 , 125.2 , 113.6 , 55.2 , 11.2 .
HRMS (ESI) m/z: Calcd for C21H18KO2 + [M+K]+ 341.0938; Found 341.0935.

Claims (7)

1. A method for synthesizing polysubstituted biaryl derivatives by using aryl diazonium salts is characterized in that: palladium salt and norbornene or norbornene derivatives are used as catalysts, triarylphosphine is used as a ligand, iodide is used as an activator, aryl diazonium salt, o-iodoarene and olefin react for 6-12 hours in an organic solvent at 75-105 ℃ under an alkaline condition to obtain polysubstituted biaryl derivatives;
the structure of the polysubstituted biaryl derivative is shown as the formula (I):
Figure 1536DEST_PATH_IMAGE001
the structure of the o-iodoarene is shown as a formula (II):
Figure 997174DEST_PATH_IMAGE002
the aryl diazonium salt has a structure shown in a formula (III):
Figure 134894DEST_PATH_IMAGE003
the structure of the olefin is shown as the following formula (IV):
Figure 738045DEST_PATH_IMAGE004
in the formulae (I) to (IV), R1Is any one of alkyl, alkoxy, ester group, aryl, trifluoromethyl and trifluoromethoxy; r2Is any one of alkyl, aryl, alkoxy, ester group, trifluoromethyl, cyano, carbonyl and aldehyde group; x-Is BF4 -、PF6 -、CH3SO3 -Or Ts-；R3Is any one of hydrogen, alkyl, aryl, aldehyde group, ester group and amide group; r4Is any one of hydrogen, alkyl, aryl, aldehyde group, ester group and amide group.
2. The method for synthesizing polysubstituted biaryl derivatives according to claim 1, wherein: the molar ratio of the o-iodoarene to the aryl diazonium salt to the olefin is 1:1: 1-1.5: 2: 1.
3. The method for synthesizing polysubstituted biaryl derivatives according to claim 1, wherein: the palladium salt is one of palladium acetate, bis (triphenylphosphine) palladium dichloride and tetrakis (triphenylphosphine) palladium; the dosage of the palladium salt is 5-10% of the molar weight of the o-iodoarene.
4. The method for synthesizing polysubstituted biaryl derivatives according to claim 1, wherein: the norbornene derivative is 5-norbornene-2-carboxylic acid methyl ester, cis-5-norbornene-endo-2, 3-dicarboxylic acid or N-hydroxy-5-norbornene-2, 3-dicarboximide; the molar ratio of the norbornene or norbornene derivative to the o-iodoarene is 1: 0.5-1: 1.5.
5. The method for synthesizing polysubstituted biaryl derivatives according to claim 1, wherein: the triarylphosphine is one of triphenylphosphine, tri (4-methoxyphenyl) phosphine, tri (4-tolyl) phosphine and tri (2-methylphenyl) phosphine; the dosage of the triarylphosphine is 10-20% of the molar weight of the o-iodoarene.
6. The method for synthesizing polysubstituted biaryl derivatives according to claim 1, wherein: the iodide is one of potassium iodide, sodium iodide and tetrabutylammonium iodide; the molar ratio of the o-iodoarene to the iodide is 1: 1-1: 2.
7. The method for synthesizing polysubstituted biaryl derivatives according to claim 1, wherein: the organic solvent is one of N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.
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Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
FIORENZA FACCINI等: "A New Reaction Sequence Involving Palladium-Catalyzed Unsymmetrical Aryl Coupling", J. AM. CHEM. SOC. *
HAN, MING-LIANG等: "Palladium-catalyzed decarbonylative Catellani reactio", CHEMRXIV *
MARTA CATELLANI等: "A new catalytic method for the synthesis of selectively substituted biphenyls containing an oxoalkyl chain", JOURNAL OF ORGANOMETALLIC CHEMISTRY *
RASINA, DACE等: "Heterogeneous palladium-catalysed Catellani reaction in biomass-derived γ-valerolactone", ROYAL SOCIETY OF CHEMISTRY *

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