Synthesis and Activity of Six-Membered Cyclic Alkyl Amino Carbene–Ruthenium Olefin Metathesis Catalysts

Ru–cyclic alkyl amino carbene (Ru–CAAC) olefin metathesis catalysts perform extraordinarily in metathesis macrocyclization and ethenolysis, but previous studies have been limited to the use of five-membered CAAC (CAAC-5) ligands. In this work, we synthesized a different group of ruthenium catalysts with more σ-donating and π-accepting six-membered CAAC (CAAC-6) ligands, and their metathesis activity was probed through initiation studies, ring-closing metathesis (RCM), cross-metathesis, and ethenolysis. These catalysts display higher initiation rates than analogous Ru–CAAC-5 complexes but demonstrate lower activity in RCM and ethenolysis

Synthesis and Activity of Six-Membered Cyclic Alkyl Amino Carbene–Ruthenium Olefin Metathesis Catalysts

Ru–cyclic alkyl amino carbene (Ru–CAAC) olefin metathesis catalysts perform extraordinarily in metathesis macrocyclization and ethenolysis, but previous studies have been limited to the use of five-membered CAAC (CAAC-5) ligands. In this work, we synthesized a different group of ruthenium catalysts with more σ-donating and π-accepting six-membered CAAC (CAAC-6) ligands, and their metathesis activity was probed through initiation studies, ring-closing metathesis (RCM), cross-metathesis, and ethenolysis. These catalysts display higher initiation rates than analogous Ru–CAAC-5 complexes but demonstrate lower activity in RCM and ethenolysis

Synthesis and Activity of Six-Membered Cyclic Alkyl Amino Carbene–Ruthenium Olefin Metathesis Catalysts

Ru–cyclic alkyl amino carbene (Ru–CAAC) olefin metathesis catalysts perform extraordinarily in metathesis macrocyclization and ethenolysis, but previous studies have been limited to the use of five-membered CAAC (CAAC-5) ligands. In this work, we synthesized a different group of ruthenium catalysts with more σ-donating and π-accepting six-membered CAAC (CAAC-6) ligands, and their metathesis activity was probed through initiation studies, ring-closing metathesis (RCM), cross-metathesis, and ethenolysis. These catalysts display higher initiation rates than analogous Ru–CAAC-5 complexes but demonstrate lower activity in RCM and ethenolysis

Efficient Z-Selective Olefin-Acrylamide Cross-Metathesis Enabled by Sterically Demanding Cyclometalated Ruthenium Catalysts

The efficient Z-selective cross-metathesis between acrylamides and common terminal olefins has been developed by the use of novel cyclometalated ruthenium catalysts with bulky N-heterocyclic carbene (NHC) ligands. Superior reactivity and stereoselectivity are realized for the first time in this challenging transformation, allowing streamlined access to an important class of cis-Michael acceptors from readily available feedstocks. The kinetic preference for cross-metathesis is enabled by a pivalate anionic ligand, and the origin of this effect is elucidated by density functional theory calculations