Electrochemical Aerobic Oxidation of Aminocyclopropanes to Endoperoxides

Access to New Endoperoxide Derivatives by Electrochemical Oxidation of Substituted 3‐Azabicyclo[4.1.0]hept‐4‐enes

“…The decrease of the peak current of Ox 1 under aerobic conditions had already been observed with related aminocyclopropane derivatives in our previous studies 4. 7 It typically reveals an electron catalytic process in which the starting compound can also be chemically oxidised by an intermediate species, thereby reducing the required amount of electrons 18.…”

“…Trapping with dioxygen and 5‐ exo ‐ trig cyclisation leads to radical cation C . This species has been shown to oxidise the starting material A , which closes a catalytic cycle to yield the α‐aminoendoperoxide product D 3–4…”

“…We then developed an original electrochemical method that provides a more‐general access to α‐aminoendoperoxides. This procedure is fast, convenient and flexible: the potential applied is adjusted to the optimal value for each substrate, which ensures good yields and selectivity (Scheme ) 4. 7…”

“… Synthesis of bicyclic α‐aminoendoperoxides by electrochemical aerobic oxidation of 2‐azabicyclo[3.1.0]hexane derivatives 4. 7 …”

Organic Electrosynthesis: Applications in Complex Molecule Synthesis

“…The Buriez group showed that electrochemical aerobic oxidation of aminocyclopropane 40 underwent cyclopropane ring opening to furnish a distonic radical cation ( 42 ). This adduct readily reacts with molecular oxygen to ultimately afford α‐amino endoperoxide 43 (Scheme ), which were demonstrated to exhibit antimalarial activity . The Shono oxidation has also been utilized for the synthesis of an array of alkaloid skeletons, such as the intermolecular oxidative coupling of corypalline and intramolecular coupling of laudanosine …”