Ni-Catalyzed Oxygen Transfer from N2O onto sp3-Hybridized Carbons.

Herein we disclose a catalytic synthesis of cycloalkanols that harnesses the potential of N2O as an oxygen transfer agent onto sp3-hybridized carbons. The protocol is distinguished by its mild conditions and wide substrate scope, thus offering an opportunity to access carbocyclic compounds from simple precursors even in an enantioselective manner. Preliminary mechanistic studies suggest that the oxygen insertion event occurs at an alkylnickel species and that N2O is the O transfer reagent.

Decarboxylative Alkynylation and Cyanation of Carboxylic Acids using Photoredox Catalysis and Hypervalent Iodine Reagents.

Alkynes and nitriles are important functional groups that serve as versatile building blocks in organic synthesis and find applications in material and medicinal sciences. A convenient and straightforward access to both classes of compounds under mild conditions is, therefore, highly desirable. Herein, we disclose the decarboxylative alkynylation and cyanation of broadly available carboxylic acids using photoredox catalysis and hypervalent iodine reagents. Choices of both catalysts and reagents were crucial. Computational and experimental studies revealed two different possible mechanisms that are dictated by the oxidation potential of the reagents: radical for alkynylation, ionic for cyanation.