Use of Suzuki Coupling Reaction for Synthesis of Functionalized Materials

Authors' Affiliations

Anastasia Kuvayskaya, Department of Chemistry, College of Arts and Sciences, East Tennessee State University, Johnson City, TN. Aleksey Vasiliev, Department of Chemistry, College of Arts and Sciences, East Tennessee State University, Johnson City, TN.

Location

Ballroom

Start Date

4-12-2019 9:00 AM

End Date

4-12-2019 2:30 PM

Poster Number

45

Faculty Sponsor’s Department

Chemistry

Name of Project's Faculty Sponsor

Dr. Aleksey Vasiliev

Classification of First Author

Graduate Student-Master’s

Type

Poster: Competitive

Project's Category

Organic Chemistry

Abstract or Artist's Statement

Hybrid materials synthesized by grafting of organic molecules onto silica surface have found numerous applications in chemistry, biochemistry, and chemical engineering. In particular, the functionalization of silica gel can be accomplished by various surface reactions of immobilized boronic acids. Suzuki coupling has been chosen due to several advantages, such as mild reaction conditions, tolerance to the aqueous environment, and high yields of the products. The objective of this work was to determine the most effective reaction conditions for modifying porous hybrid materials with large specific surface areas and high density of surface organoboron reactive sites by various functional groups. Prior to modification by Suzuki coupling, the surface of silica gel was functionalized by phenylboronic acid. Two methods were tested for immobilization of phenylboronic acid: hydrosilylation and thiol-ene coupling. The later radical reaction between surface alkylthiol groups and 4-vinylphenylboronic acid was found more effective. Obtained boronated silica gel was used for further functionalization by various aryl halides. Surface Suzuki coupling reaction was catalyzed by palladium acetate in the presence of cesium carbonate as a base, while dimethylformamide was chosen as a solvent. The coupling reactions proceeded at mild heating under constant sonication. Such ultrasonic irradiation was reported earlier to have an activating effect on Suzuki coupling. The analysis of the obtained products indicated formation of surface biaryl compounds, the highest yields have been obtained in reactions with iodobenzene and bromobenzene. Thus, novel functionalized organic/inorganic hybrid materials were successfully synthesized by surface modification of mesoporous silica gel.

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Apr 12th, 9:00 AM Apr 12th, 2:30 PM

Use of Suzuki Coupling Reaction for Synthesis of Functionalized Materials

Ballroom

Hybrid materials synthesized by grafting of organic molecules onto silica surface have found numerous applications in chemistry, biochemistry, and chemical engineering. In particular, the functionalization of silica gel can be accomplished by various surface reactions of immobilized boronic acids. Suzuki coupling has been chosen due to several advantages, such as mild reaction conditions, tolerance to the aqueous environment, and high yields of the products. The objective of this work was to determine the most effective reaction conditions for modifying porous hybrid materials with large specific surface areas and high density of surface organoboron reactive sites by various functional groups. Prior to modification by Suzuki coupling, the surface of silica gel was functionalized by phenylboronic acid. Two methods were tested for immobilization of phenylboronic acid: hydrosilylation and thiol-ene coupling. The later radical reaction between surface alkylthiol groups and 4-vinylphenylboronic acid was found more effective. Obtained boronated silica gel was used for further functionalization by various aryl halides. Surface Suzuki coupling reaction was catalyzed by palladium acetate in the presence of cesium carbonate as a base, while dimethylformamide was chosen as a solvent. The coupling reactions proceeded at mild heating under constant sonication. Such ultrasonic irradiation was reported earlier to have an activating effect on Suzuki coupling. The analysis of the obtained products indicated formation of surface biaryl compounds, the highest yields have been obtained in reactions with iodobenzene and bromobenzene. Thus, novel functionalized organic/inorganic hybrid materials were successfully synthesized by surface modification of mesoporous silica gel.