2017 November 08 | Ming Yan, Yu Kawamata, and Phil S. Baran
Synthetic organic electrochemistry has seen significant advancements since 2000, with electrochemical methods now playing a crucial role in organic synthesis. Electrochemistry allows the direct manipulation of electrons, enabling redox reactions that are fundamental to organic chemistry. The history of electroorganic chemistry dates back to the 1800s, with early experiments such as the Kolbe electrolysis and the Tafel rearrangement laying the foundation for modern electrochemical techniques. These methods have evolved to include various electrochemical setups, such as direct electrolysis, mediated electrolysis, and cation pool strategies, which allow for the controlled generation and manipulation of reactive intermediates.
Anodic oxidation is a key area of electrochemical synthesis, with applications in the formation of N-centered radicals and nitrenes. The Kolbe reaction, for example, involves the anodic oxidation of carboxylates to form alkyl radicals, which can undergo decarboxylation and dimerization. Recent developments have expanded the scope of this reaction, including the synthesis of complex natural products and the use of cation pools to enhance reactivity. The Shono oxidation, another important electrochemical process, allows for the formation of iminium ions, which can be further functionalized through nucleophilic trapping. This method has been used to synthesize a wide range of compounds, including natural products and drug analogs.
Reductive processes, such as cathodic reduction, have also been refined, with techniques like the use of sacrificial anodes and redox mediators enabling the controlled reduction of organic compounds. The use of electroauxiliaries has further enhanced the selectivity and efficiency of electrochemical reactions, allowing for the precise control of regio- and chemoselectivity. Additionally, the development of electrochemical mediators, such as TEMPO and other nitroxyl radicals, has expanded the range of substrates that can be oxidized or reduced under electrochemical conditions.
Overall, electrochemical methods have become increasingly important in synthetic organic chemistry, offering efficient, scalable, and environmentally friendly approaches to the synthesis of complex molecules. The continued development of these methods promises to further revolutionize the field of organic synthesis.Synthetic organic electrochemistry has seen significant advancements since 2000, with electrochemical methods now playing a crucial role in organic synthesis. Electrochemistry allows the direct manipulation of electrons, enabling redox reactions that are fundamental to organic chemistry. The history of electroorganic chemistry dates back to the 1800s, with early experiments such as the Kolbe electrolysis and the Tafel rearrangement laying the foundation for modern electrochemical techniques. These methods have evolved to include various electrochemical setups, such as direct electrolysis, mediated electrolysis, and cation pool strategies, which allow for the controlled generation and manipulation of reactive intermediates.
Anodic oxidation is a key area of electrochemical synthesis, with applications in the formation of N-centered radicals and nitrenes. The Kolbe reaction, for example, involves the anodic oxidation of carboxylates to form alkyl radicals, which can undergo decarboxylation and dimerization. Recent developments have expanded the scope of this reaction, including the synthesis of complex natural products and the use of cation pools to enhance reactivity. The Shono oxidation, another important electrochemical process, allows for the formation of iminium ions, which can be further functionalized through nucleophilic trapping. This method has been used to synthesize a wide range of compounds, including natural products and drug analogs.
Reductive processes, such as cathodic reduction, have also been refined, with techniques like the use of sacrificial anodes and redox mediators enabling the controlled reduction of organic compounds. The use of electroauxiliaries has further enhanced the selectivity and efficiency of electrochemical reactions, allowing for the precise control of regio- and chemoselectivity. Additionally, the development of electrochemical mediators, such as TEMPO and other nitroxyl radicals, has expanded the range of substrates that can be oxidized or reduced under electrochemical conditions.
Overall, electrochemical methods have become increasingly important in synthetic organic chemistry, offering efficient, scalable, and environmentally friendly approaches to the synthesis of complex molecules. The continued development of these methods promises to further revolutionize the field of organic synthesis.