Herein, an unprecedented synthetic route to sulfilimines via a copper-catalyzed Chan–Lam-type coupling of sulfenamides is presented. A key to success in this novel transformation is the chemoselective S-arylation of S(II) sulfenamides to form S(IV) sulfilimines, overriding the competitive, and more thermodynamically favored, C–N bond formation that does not require a change in the sulfur oxidation state. Computations reveal that the selectivity arises from a selective transmetallation event where bidentate sulfenamide coordination through the sulfur and oxygen atoms favors the S-arylation pathway. The mild and environmentally benign catalytic conditions enable broad functional group compatibility, allowing a variety of diaryl or alkyl aryl sulfilimines to be efficiently prepared. The Chan–Lam coupling procedure could also tolerate alkenylboronic acids as coupling partners to afford alkenyl aryl sulfilimines, a class of scaffolds that cannot be directly synthesized via conventional imination strategies. The benzoyl-protecting groups could be conveniently removed from the product, which, in turn, could be readily transformed into several S(IV) and S(VI) derivatives.

A novel palladium-catalyzed aryl-furanylation of alkenes is described. This protocol provided a straightforward route to the synthesis of various benzofuran-containing 3,3-disubstitutedoxindole derivatives bearing a quarternary carbon center. In the cascade process, one C­(sp2)–O bond, two C­(sp2)–C­(sp3) bonds, an oxindole, and a furan ring are formed in a single chemical operation.

of main observation and conclusion An efficient strategy for the formation of alkenyl-functionalized spirocarbocyclic scaffolds from alkyne-containing phenol-based biaryls via sequential iodine-induced cyclization/dearomatization and Pd-catalyzed coupling of N-tosylhydrazones is developed. The approach provides various spirocarbocyclic compounds in moderate to excellent yields with good functional tolerance. The results also demonstrate the feasibility for the direct cross-couplings of N-tosylhydrazones with sterically congested tetrasubstituted alkenyl halides.

Herein, an unprecedented synthetic route to sulfilimines via a copper-catalyzed Chan-Lam-type coupling of sulfenamides is presented. A key to success in this novel transformation is the chemoselective S-arylation of S(II) sulfenamides to form the S(IV) sulfilimines, overriding the competitive C-N bond formation that does not require a change in sulfur oxidation state. The mild and environmentally benign catalytic conditions enable broad functional group compability. A variety of diaryl or alkyl aryl sulfilimines could be efficiently prepared. The Chan-Lam coupling procedure could also tolerate alkenylboronic acids as coupling partners to afford alkenyl aryl sulfilimines, a class of scaffolds which cannot be directly synthesized via conventional imination strategies. The benzoyl protecting groups could be conveniently removed from the product which, in turn, could be readily transformed to several S(IV) and S(IV) derivatives.