Highly diastereoselective syntheses of tetrasubstituted alkenes via nickel-catalyzed Suzuki-Miyaura cross-couplings of enol tosylates and arylboronic esters were developed.[1] By judicious choice of ligand and solvent, either the E- or Z- alkene products could be accessed selectively and in a convergent fashion from mixtures of enol tosylate diastereomers, with yields up to 94% and diastereomeric ratios up to 99:1. The monophosphine ligand controlling each reaction manifold was optimized by high-throughput screening and guided by chemical space investigation of the kraken library. Detailed analysis of the selectivity-determining stereoelectronic parameters, computational modeling, and experimental mechanistic studies provided key insights into the nature of the underlying isomerization process impacting selectivity in the cross-coupling.

Stereoconvergent and -divergent synthesis of tetrasubstituted alkenes by nickel-catalyzed cross-couplings

ACS Spring 2022

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