Oxidation of alkyl radicals from decarboxylation of acids by lead(IV) and copper(II)

An Unexplored O2‐Involved Pathway for the Decarboxylation of Saturated Carboxylic Acids by TiO2 Photocatalysis: An Isotopic Probe Study

“…(2) and (3)] [5] (e À cb is a photogenerated electron in the conduction band). Such phenomena have also been observed in the thermal oxidative decarboxylation of these acids by high-valence metal ions, such as Co III , [7] Pb IV , [8] and Mn III , [9] although the main decarboxylation products were alkenes rather than alkanes since no reductive species [like the electrons shown in Eq. (3)] were involved.…”

Decarboxylation‐Initiated Intermolecular Carbon‐Heteroatom Bond Formation

“…Already in the 1960s, Kochi and others systematically investigated the oxidative decarboxylation of aliphatic carboxylic acids under thermal or photochemical conditions which led to the formation of esters. These reactions require stoichiometric amounts of high‐valent metal reagents as oxidants, such as Pb(IV), [245–248] Mn(III), [249] Tl(III), [250] Ce(IV), [251,252] Co(III), [253] and Ag(II) [254,255] . It was believed that the carboxylates initially undergo a SET oxidation with these metal oxidants, followed by an immediate decarboxylation to form alkyl radicals.…”

Hypervalent iodine(III)-mediated decarboxylative acetoxylation at tertiary and benzylic carbon centers

“…However, despite these advances, the oxidative decarboxylation coupled with C–O bond formation has received considerably less attention, even though it represents a promising strategy for the synthesis of valuable alcohol derivatives. One of the classical methods for the decarboxylative C–O bond formation of aliphatic carboxylic acids involves the use of stoichiometric amounts of heavy metal oxidants under high-temperature conditions [ 14 – 15 ]. Because these oxidants are typically highly toxic, their use has remained limited in organic synthesis.…”