Neutral nickel-catalyzed dehydrosulfonylation of unactivated allylic alcohols under mild conditions.

Allyl sulfones are important sulfur-containing compounds that have widespread applications in organic synthesis, medicinal chemistry and materials science. Herein, nickel-catalysed dehydrosulfonylation of unactivated allyl alcohols with aryl sulfonyl hydrazides without additional active agents under mild conditions was developed. A variety of functional allyl sulfones could be efficiently synthesized in the presence of air-stable Ni(acac)2 as the catalyst and 1,1'-bis(diphenylphosphino)ferrocene (DPPF) as the ligand.

Base-promoted synthesis of diarylsulfones from sulfonyl hydrazines and diaryliodonium salts.

An efficient and concise method for the synthesis of diverse substituted sulfones was developed with high selectivity. Using n-PrOH as the solvent, diaryl sulfones are formed even on a gram scale via metal-free coupling from sulfonyl hydrazines with symmetrical or unsymmetrical diaryliodonium salts.

Synthesis of Mannich-type derivatives from amides activated by hydrogen bonding with ZnCl2.

The amide group has one of the most significant functionalities found in many natural products. Herein, low-nucleophilic amides are used in a Mannich-type reaction to synthesize N-acyl-protected amine derivatives. A highly efficient synthetic method utilizing simple aldehydes, N-substituted anilines, and amides as substrates was established through a one-pot amide pathway activated by hydrogen bonding between the ZnCl2 and amide under solvent-free conditions. This strategy can be broadly applied to medicinal chemistry. More importantly, compared with the previous Lewis acid catalyzed reaction, we proposed a new application of zinc chloride.