Abstract
Under irradiation of 456 nm blue light-emitting diodes, PPh3 catalyzes the iododecarboxylation of aliphatic carboxylic acid derived N-(acyloxy)phthalimide with lithium iodide as an iodine source. The reaction delivers primary, secondary, and bridgehead tertiary alkyl iodides in acetone solvent, and the alkyl iodide products were easily used to generate C-N, C-O, C-F, and C-S bonds to allow various decarboxylative transformations without using transition-metal or organic-dye-based photocatalysts.
Highlights
Decarboxylative transformations1–4 that convert a carboxylate group into a functionality that is a versatile handle for various further transformations, such as the recent development of alkylative decarboxylative borylation5,6, are of great significance in organic synthesis
Photoactivation of an electron donor–acceptor encounter complex in an organic solvent cage, a phenomenon that has been described in Mulliken theory, has been known for decades, but it has not been employed as a photoactivation step in the design of photocatalysis for organic synthesis until recent years
We report an iododecarboxylation reaction that applies this concept for photoactivation by using a catalyst to facilitate electron transfer and to suppress back electron transfer in the photoexcited state
Summary
Decarboxylative transformations that convert a carboxylate group into a functionality that is a versatile handle for various further transformations, such as the recent development of alkylative decarboxylative borylation, are of great significance in organic synthesis. Solvation and noncovalent interactions between substrates play crucial roles in determining the productive photoactivation and subsequent diffusion process24–27 This principle of photoactivation can be utilized to design a catalytic cycle for bond formation with a catalyst that facilitates electron transfer from a donor moiety to an acceptor moiety and to suppress undesired back electron transfer to induce further fragmentation of radical ion species (Fig. 1B). We implement this hypothesis to design a decarboxylative iodination of aliphatic carboxylates
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