Search

A radical cyclization and ring-opening of oxime esters with diselenides was developed. Both Ni(0) and Fe(II) catalysts could be employed for the selenylation of olefin-containing and cyclic oxime ester derivatives. With this method, a variety of functionalized pyrrolines and alkyl nitriles were synthesized in good yields. Moreover, a mechanism involving iminyl radical and carbon-centered radical intermediates was proposed.

A N-heterocyclic carbene-phosphine iridium complex is presented for the efficient and selective mono-N-alkylation of sulfonamides with alcohols based on a borrowing hydrogenation strategy. Herein, water is the only by-product and this methodology thus offers a more environmentally benign and interesting alternative to the use of traditional alkylating reagents. This facile protocol tolerates a large number of (hetero) aromatic and aliphatic sulfonamides as well as (hetero) aromatic and aliphatic alcohols to obtain the desired product is high isolated yield (up to 98%). The alkylation completely retards after the formation of the secondary sulfonamide and no over-alkylation was observed in all cases. The option to run the reaction under solvent-free conditions as well as the scalability of this borrowing hydrogenation are key features of this protocol.

Fluoromethyl groups possess specific steric and electronic properties and serve as a bioisostere of alcohol, thiol, nitro, and other functional groups, which are important in an assortment of molecular recognition processes. Herein we report a catalytic method for the asymmetric synthesis of a variety of enantioenriched products bearing fluoromethylated stereocenters with excellent yields and enantioselectivities. Various N,P-ligands were designed and applied in the hydrogenation of fluoromethylated olefins and vinyl fluorides.