Sustainable electrochemical decarboxylative acetoxylation of aminoacids in batch and continuous flow

Abstract

Introduction of acetoxy groups to organic molecules is important for the preparation of many active ingredients and synthetic intermediates. A commonly used and attractive strategy is the oxidative decarboxylation of...

Sustainable Synthesis of Noroxymorphone via a Key Electrochemical N-Demethylation Step

“…This material typically features improved yields, as the reaction mixture cannot penetrate the electrode, compared to normal graphite. Moreover, its leak-proof properties make it ideal for the translation of the process to a flow cell (vide infra) …”

Recent progress in catalytic acyloxylation of C(sp3)‐H bonds

“…Cantillo with coworkers reported electrochemical decarboxylative acetoxylation of amino acids of the type 155 via the Hofer–Moest reaction. [ 114 ] The reaction generates carbocation by two‐electron anodic oxidation and decarboxylation of substituted carboxylic acids, which is further trapped by a nucleophile such as acetate anion. So, using inexpensive electrode materials and simple electrolysis of amino‐ and carboxylic acids in AcOH/NaOAc, one could obtain the target acetoxylated compounds 156 in good to excellent yields (Scheme 29).…”

Electrochemical Decarboxylative Oxygenation of Carboxylic Acids

“…Synthetic electrochemistry − has been illustrated as a versatile and sustainable synthetic tool, which utilized renewable electrons as reagents without the need of transition metals and stoichiometric oxidants to generate radical intermediates. In particular, electrochemical decarboxylative transformation of carboxylic acids without employing elaborate redox-active esters has experienced some breakthroughs. − Pioneering work of Baran demonstrated decarboxylative etherification through interception of electrogenerated carbocations with alcohols . Recent reports from Wang and Echavarren, Baran, Waldvogel, Brown, and Cantillo employed a similar decarboxylative strategy for C–N, C–F, and C–O bond formation.…”

“…In particular, electrochemical decarboxylative transformation of carboxylic acids without employing elaborate redox-active esters has experienced some breakthroughs. − Pioneering work of Baran demonstrated decarboxylative etherification through interception of electrogenerated carbocations with alcohols . Recent reports from Wang and Echavarren, Baran, Waldvogel, Brown, and Cantillo employed a similar decarboxylative strategy for C–N, C–F, and C–O bond formation. Inspired by these works, we envisioned that the valuable electrodecarboxylative strategy could be applicable to the preparation of carbonyls directly from carboxylic acids (Scheme C).…”