Development of electroactivated heterogeneous transition metal-based systems to synthesize deuterated compounds and alkylamines
"The work explained here introduces heterogeneous transition-metal catalyzed carbon-hydrogen (C-H) activation performed in an electrochemical environment. This method is mild, inexpensive and regioselective and is conducted in an aqueous environment compared to conventional methods that involve homogeneous catalysis or high-pressure high-temperature batch reactor conditions. The synthesis of carbon-deuterium (C-D) and carbon-nitrogen (C-N) bond is significant as deuterated and nitrogenous compounds have wide arrays of applications in chemical and pharmaceutical industry. The post-synthetic replacement of metabolically labile C-H bond to a relatively stable C-D bond has attracted lot of attention in the pharmaceutical industry as deuterated drugs tend to have altered metabolic profile. Herein, we describe the development and optimization of an aqueous-based electrocatalytic and electrochemical systems with the ability to activate C-H bonds. The ruthenium on activated carbon cloth (Ru/ACC) showed the ability to transform C-H to C-D bonds in amines, alcohols and amino acids regio- and stereoselectively in minutes to hours at 2.2 mA/cm2, 60 °C and ambient pressure. We expanded this electrocatalytic method using palladium on activated carbon cloth (Pd/ACC) to deuterate benzylic and ortho-C-H sites on the substituted benzene. The alkylation of amines is conventionally carried out using alkyl halides as alkylating agents or carbonyl-based compounds in the presence of strong reducing agents. We have developed a 1-compartment (1-C) and 2-compartment (2-C) electrochemical systems to alkylate amines using alcohols as alkylating agents in an aqueous-based environment. The optimized conditions for alkylation of amines with alcohols are 60 °C, 2.2 mA/cm2 and 5% v/v of alcohol."--Pages ii-iii.
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- In Collections
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Electronic Theses & Dissertations
- Copyright Status
- In Copyright
- Material Type
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Theses
- Authors
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Bhatia, Souful
- Thesis Advisors
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Jackson, James E.
- Committee Members
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Swain, Greg M.
Maleczka, Robert E.
Miller, Dennis J.
- Date
- 2016
- Program of Study
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Chemistry - Doctor of Philosophy
- Degree Level
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Doctoral
- Language
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English
- Pages
- xx, 187 pages
- ISBN
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9781369431117
1369431112
- Permalink
- https://doi.org/doi:10.25335/M5BV2J