Transition-metal-free decarboxylative thiolation of stable aliphatic carboxylates

Abstract

A transition-metal-free decarboxylative thiolation protocol is reported in which (hetero)aryl acetates and α-CN substituted acetates undergo smoothly, to deliver a variety of functionalized aryl alkyl sulfides in moderate to excellent yields.

Catalyst-free decarboxylative alkylation: access to quaternary center

“…It is well known that alkyl carboxylic acids could undergo radical decarboxylation via single electron oxidation to generate alkyl radicals [12][13][14] . When treated with base, the nucleophilic C(sp 3 ) intermediates can be generated by ionic decarboxylation [15][16][17][18][19][20] . Based on the previous work, a plausible mechanistic pathway is proposed in Scheme 2.…”

Transition metal-free decarboxylative olefination of carboxylic acid salts

“… 5 Since the pioneering work of Kolbe demonstrating the formation of carbon-centered radicals through decarboxylation from carboxylic acids, 6 decarboxylative strategies have been shown to provide access to a large variety of functionally interesting products. 7 Classically, the barton decarboxylation allows for the direct access of alkanes and arenes from carboxylic acids, 8 and the Hunsdiecker–Borodin reaction allows for the direct conversion of silver carboxylates into halides. 9 More recently, coupling reactions have utilized decarboxylative metalation to generate organometallics that couple to form new C–C, C–N, C–S, and C–O bonds, providing alternatives to traditional cross-coupling reactions.…”