Visible Light-Assisted Ring-Opening of Cyclic Ethers with Carboxylic Acids Mediated by Triphenylphosphine and N-Halosuccinimides.

The ring-opening of cyclic ethers (epoxide, oxetane, THF, and THP) by carboxylic acids was achieved by using N-iodosuccinimide (NIS) or N-bromosuccinimide (NBS) and triphenylphosphine under blue light. The corresponding ω-haloalkyl carboxylates were obtained under mild reaction conditions. The reaction is believed to work through a halogen bond complex between NIS (or NBS) and triphenylphosphine, which, upon irradiation with blue light, produces the key phosphine radical cation intermediate that initiates the ring-opening reactions.

Visible light-assisted organocatalytic α-acyloxylation of ketones using carboxylic acids and N-halosuccinimides.

The α-acyloxylcarbonyl motif can be found in many important pharmaceuticals and biologically active natural products and their derivatives. In this manuscript, the direct synthesis of α-acyloxylketones from ketones and readily available carboxylic acids was realized using a photo-assisted halogen bond-mediated organocatalytic α-acyloxylation reaction. The desired α-acyloxylation products were obtained in good to high yields.