An overview of recent progress in the Fujiwara-Moritani reaction, which is the palladium-catalyzed oxidative coupling of arenes with olefins to afford alkenyl arenes, is described. It is emphasized that regioselectivity on aryl ortho- or meta-CH activation could be controlled very well in the presence of Pd, Rh, or Ru catalysts with the assistance of various chelation groups on aromatic rings in this coupling reaction. Catalytic alkenylation of aryl CH bonds from simple arenes is also discussed, especially from electron-deficient arenes. These advanced protocols would not only make the Fujiwara-Moritani reaction more useful and applicable in organic synthesis but also light the way for the further development of the functionalization of normal CH bonds.

A one-pot protocol for the synthesis of highly enantiopure benzylic thioethers, thioacetates, and sulfones (94−99% ee) via a ligand-free, copper-catalyzed stereospecific C−S coupling reaction of thiols and enantioenriched tertiary benzylic amines via in situ activation by methyl triflate is developed. Various enantioenriched tertiary benzylic amines, including 1-arylalkylamines, 1-tetrahydronaphthylethylamine, heterocyclic amines (e.g., 1-(thiophen-2-yl)ethanamine), and amino acid esters containing a benzylamine moiety, are highly efficient substrates, and their chirality is efficiently transferred to the products (94−99% ee). The absolute configurations of the products are predictable and follow the pattern of S N 2-type substitutions; an inversion of the absolute configuration of the tertiary amines occurs during the C−S coupling reaction. Not only are various alkene-, arene-, and heteroarenethiols suitable for this C−S coupling reaction but also potassium thioacetate and sodium phenylsulfinate are as well. A plausible mechanism was proposed on the basis of the experimental results.

No abstract

No abstract