Oligonucleotide

Catalysis

Enantioselective synthesis

Allylic rearrangement

Chromatography

Receptor

Palladium

Crystal structure

Alkyl

Biochemistry

Medicinal chemistry

Combinatorial chemistry

Phosphoramidite

Ligand (biochemistry)

Organic chemistry

Denticity

Sulfonyl

Regioselectivity

Chemistry

Sulfone

Hydrazine (antidepressant)

Angewandte Chemie International Edition

A highly enantio‐ and regioselective hydrosulfonylation of 1,3‐dienes with sulfonyl hydrazides has been realized by using a palladium catalyst containing a monodentate chiral spiro phosphoramidite ligand. The reaction provided an efficient approach to synthetically useful chiral allylic sulfones. Mechanistic studies suggest that the reaction proceeds through the formation of an allyl hydrazine intermediate and subsequent rearrangement to the chiral allylic sulfone product. The transformation of the allyl hydrazine intermediate to the product is the enantioselectivity‐determining step.

Palladium‐Catalyzed Asymmetric Hydrosulfonylation of 1,3‐Dienes with Sulfonyl Hydrazides