Advanced Synthesis & Catalysis

This review article summarizes reports for Z ‐selective olefin metathesis reactions by molybdenum, tungsten, ruthenium, and vanadium catalysts. It is clearly demonstrated that the ligand modifications play essential roles in achieving the stereospecific olefin metathesis reactions. In particular, Mo‐ and W‐alkylidene based complex catalysts having pyrrolide‐aryloxide [or bis(aryloxide)] were highly effective in the efficient enantioselective ring opening/cross‐metathesis (EROCM), cross metathesis (CM), homodimerization, ring‐opening metathesis polymerization (ROMP), and in ring closing metathesis (RCM) with high Z ‐ selectivities (∼&gt;98%). Ruthenium‐carbene catalysts having cycloadamantyl, catechothiolate, phenolate and thiophenolate ligands display pronounced Z ‐selectivity (&gt;98%) in efficient CM, ROCM, AROCM, RCM, ROMP reactions. Halogenated (arylimido)‐alkoxo vanadium‐alkylidenes were thermally robust and effective for efficient highly cis ‐specific ROMP of cyclic olefins to afford end‐functionalized ring‐opened polymers. magnified image

Recent Developments in Z‐Selective Olefin Metathesis Reactions by Molybdenum, Tungsten, Ruthenium, and Vanadium Catalysts