Bimolecular Cross-Metathesis of a Tetrasubstituted Alkene with Allylic Sulfones

Abstract

Exquisite control of catalytic metathesis reactivity is possible through ligand-based variation of ruthenium carbene complexes. Sterically hindered alkenes, however, remain a generally recalcitrant class of substrates for intermolecular cross-metathesis. Allylic chalcogenides (sulfides and selenides) have emerged as “privileged” substrates that exhibit enhanced turnover rates with the commercially available second-generation ruthenium catalyst. Increased turnover rates are advantageous when competing catalyst degradation is limiting, although specific mechanisms have not been defined. Herein, we describe facile cross-metathesis of allylic sulfone reagents with sterically hindered isoprenoid alkene substrates. Furthermore, we demonstrate the first example of intermolecular cross-metathesis of ruthenium carbenes with a tetrasubstituted alkene. Computational analysis by combined coupled cluster/DFT calculations exposes a favorable energetic profile for metallacyclobutane formation from chelating ruthenium β-chalcogenide carbene intermediates. These results establish allylic sulfones as privileged reagents for a substrate-based strategy of cross-metathesis derivatization.