α-Arylation of alkylamines with sulfonylarenes through a radical chain mechanism.

In the presence of a substoichiometric amount of a tert-butoxy radical precursor, the reaction of alkylamines with sulfonylarenes was found to give α-arylated alkylamines through homolytic aromatic substitution, where a radical chain is operative.

Base-promoted dehydrogenative coupling of benzene derivatives with amides or ethers.

Benzene derivatives are introduced into the dehydrogenative coupling via homolytic aromatic substitution (HAS) as arenes that couple with amides/ethers. NaOt-Bu is used as a critical promoter of HAS in combination with t-BuOOt-Bu as an oxidant.

TIPS-TTF as a precursor of low-symmetry TTF derivatives: steric protection strategy in the regioselective C-H modification of TTF.

Triisopropylsilyltetrathiafulvalene (TIPS-TTF) has been devised as a promising platform for the synthesis of low-symmetry TTF derivatives. The bulky TIPS group allows TIPS-TTF to undergo palladium-catalyzed direct diarylation as well as LDA-mediated dilithiation exclusively on the roomier dithiole ring. Subsequent fluoride-mediated protodesilylation provided vicinally difunctionalized TTF, which could undergo further functionalization.

Ruthenium-catalyzed transformation of aryl and alkenyl triflates to halides.

Aryl triflates were transformed to aryl bromides/iodides simply by treating them with LiBr/NaI and [Cp*Ru(MeCN)(3)]OTf. The ruthenium complex also catalyzed the transformation of alkenyl sulfonates and phosphates to alkenyl halides under mild conditions. Aryl and alkenyl triflates undergo oxidative addition to a ruthenium(II) complex to form η(1)-arylruthenium and 1-ruthenacyclopropene intermediates, respectively, which are transformed to the corresponding halides.