Electrochemical Aerobic Oxygenation and Nitrogenation of Cyclic Alkenes via C═C Bond Cleavage or Oxygenation and Azidation of Open-Chain Alkenes

Abstract

An efficient strategy involving electrochemical CC double-bond cleavage and functionalization of cyclic alkenes for the synthesis of ketonitriles is described. This transformation features environmentally friendly conditions and utilizes relatively safe TMSN3 as the nitrogenation reagent and molecular oxygen as the oxidant. For the open-chain alkenes, the reaction gave 1,2-difunctionalized products. A wide range of cyclic alkenes and open-chain alkenes were found to be compatible, providing the corresponding ketonitriles and α-azido aromatic ketones in moderate to good yields.

Electrochemical primary amination of imidazopyridines with azidotrimethylsilane under mild conditions

“…16 Next, the addition of radical cation A to TMSN 3 generated the radical intermediate B . 20 The protonation of B and the following release of N 2 and deprotonation gave radical D or D′ . 10 Finally, cathodic reduction of D or D′ and subsequent protonation of E delivered the desired product 2a .…”

Electrochemical aerobic Wacker-type oxygenation of triaryl substituted alkenes to 1,2,2-triarylethanones

“…Simultaneously, one equivalent of ethylene oxide 6 is generated, which further rearranges to produce ketone 2. 27,28 In this study, we have developed a convenient protocol for electrochemical oxygenation of triaryl-substituted alkenes to 1,2,2-triarylethanones. This study represents the first expansion of the Wacker-type oxidation substrate scope to include triarylsubstituted alkenes.…”

“…Simultaneously, one equivalent of ethylene oxide 6 is generated, which further rearranges to produce ketone 2 . 27,28…”

Electrochemical cascade reactions: an account of recent developments for this modern strategic tool in the arsenal of chemical synthesis

“…A wide range of cyclic alkenes and open-chain alkenes were well-tolerated, providing the corresponding ketonitriles and α-azido aromatic ketones 192 in moderate to good yields (Scheme 74). 69 An electrochemical radical coupling process has been developed for the oxyphosphorylation of alkenes 193 and alkynes 196 with water, leading to the synthesis of β-ketophosphonates 195/197. The metal-and exogenous-oxidant-free oxidationinduced protocol was found to be compatible with a wide range of alkenes, alkynes, and diarylphosphorus derivatives.…”

“…A wide range of cyclic alkenes and open-chain alkenes were well-tolerated, providing the corresponding ketonitriles and α-azido aromatic ketones 192 in moderate to good yields (Scheme 74). 69…”