Stereoselective Synthesis of Trisubstituted Alkenes by Nickel-Catalyzed Benzylation and Alkene Isomerization

Catalytic strategies that provide stereoselective access to highly substituted alkenes from abundant monosubstituted substrates are exceedingly sought-after but rare. Here, we show that a N-heterocyclic carbene-Ni-I catalytic species mediates efficient union of electronically polarized terminal olefins with benzyl chlorides, in the presence of trimethylsilyl triflate and trimethylamine additives, to generate trisubstituted boron- and arene-containing trans alkenes in excellent regio- and stereoselectivities. Control experiments provide evidence for a mechanism involving branched-selective Heck-type benzylation that overrides substrate control, followed by trans-selective 1,3-hydrogen shift. The method represents a significant addition to the toolbox of reactions for the concise synthesis of unsaturated biologically active compounds.

Automated summary

In this study, a N-heterocyclic carbene-Ni-I catalytic species was used to achieve highly substituted alkenes from abundant monosubstituted substrates with excellent regio- and stereoselectivities. Trimethylsilyl triflate and trimethylamine additives were added to mediate the reaction, resulting in the generation of trisubstituted boron- and arene-containing trans alkenes. This method represents a significant addition to the toolbox of reactions for the concise synthesis of unsaturated biologically active compounds.