Photoexcitation of (diarylmethylene)amino benziodoxolones for alkylamination of styrene derivatives with carboxylic acids.

The alkylamination of alkenes using pristine carboxylic acids was achieved by the photoexcitation of (diarylmethylene)amino benziodoxolones (DABXs), which serve as both an oxidant and an aminating reagent (an iminyl radical precursor). The developed method is a simple photochemical reaction without the need for external photosensitizers and shows a broad substrate scope for aliphatic carboxylic acids leading to the formation of primary, secondary, and tertiary alkyl radicals, thus enabling the facile synthesis of various structurally complex amines. Mechanistic investigations including transient absorption spectroscopy measurements using a laser flash photolysis (LFP) method disclosed the unique photochemical reactivity of DABXs, which undergoes homolysis of their I-N bonds to give an iminyl radical and -iodobenzoyloxy radical, the latter of which participates in the single-electron oxidation of carboxylates.

Electrophilic cyanation of allylic boranes: synthesis of β,γ-unsaturated nitriles containing allylic quaternary carbon centers.

The electrophilic cyanation of allylic boranes, a process that is applicable to the construction of allylic quaternary carbon centers, is reported. The reaction has a broad substrate scope with a high functional group tolerance. The results represent an unprecedented and powerful tool for preparing synthetically useful β,γ-unsaturated nitriles, including derivatives that have been difficult to access using existing methods.

C-H oxygenation at tertiary carbon centers using iodine oxidant.

An oxidation system in which iodic acid (HIO3) is used as an oxidant in the presence of N-hydroxyphthalimide (NHPI) permitted the selective hydroxylation of tertiary C-H bonds and the lactonization of carboxylic acids containing a tertiary carbon center. These reactions are operationally simple and proceed under metal-free conditions using commercially available reagents, thus offering an ideal tool for the efficient oxidation of C-H bonds at tertiary carbon centers.

Ritter-type amination of C-H bonds at tertiary carbon centers using iodic acid as an oxidant.

The Ritter-type amination of a tertiary C-H bond using iodic acid (HIO) as an oxidant, in the presence of N-hydroxyphthalimide (NHPI) is reported. This operationally simple method is conducted under metal-free conditions, is scalable, and efficiently provides valuable α-tertiary amine derivatives.

Electrophilic Cyanation of Boron Enolates: Efficient Access to Various β-Ketonitrile Derivatives.

The highly efficient electrophilic cyanation of boron enolates using readily available cyanating reagents, N-cyano-N-phenyl-p-toluenesulfonamide (NCTS) and p-toluenesulfonyl cyanide (TsCN), is reported. Various β-ketonitriles were prepared by this new protocol, which has a remarkably broad substrate scope compared to existing methods. The present method also allowed efficient synthesis of β-ketonitriles containing a quaternary α-carbon center.

Synthesis and Structure of Hypervalent Iodine(III) Reagents Containing Phthalimidate and Application to Oxidative Amination Reactions.

A new class of hypervalent iodine reagents containing phthalimidate was synthesized, and structurally characterized by X-ray analysis. The benziodoxole-based reagent displays satisfactory solubility in common organic solvents and is reasonably stable in solution as well as in the solid state. The reagent was used for the oxidative amination of the C(sp(3))-H bond of N,N-dimethylanilines.