Stereodefined Synthesis of a New Type of 1,3-Dienes by Ligand-Controlled Carbon−Carbon and Carbon−Heteroatom Bond Formation in Nickel-Catalyzed Reaction of Diaryldichalcogenides with Alkynes

Abstract

We have found that ligand control over the carbon−carbon and carbon−heteroatom bond formation on the nickel center provides an easy and convenient route to symmetrical (minor) and unsymmetrical (major) isomers of sulfur- and selenium-substituted 1,3-dienes. The unsymmetrical product is a new type of 1,4-substituted conjugated diene, which was readily synthesized from alkynes and diaryldichalcogenides. The unique feature of this developed one-pot transformation is total stereodefined synthesis of the diene skeleton, controlling not only the configuration of the double bond but also the s-gauche conformation of the central C−C bond. The mechanistic study revealed the key feature of alkyne insertion into the Ni−E and Ni−C bonds (E = S, Se), which governs the direction of the chemical transformation.