Improved Ruthenium Catalysts for strongZstrong-Selective Olefin Metathesis.pdfVIP

Article /JACS Improved Ruthenium Catalysts for Z-Selective Olefin Metathesis Benjamin K. Keitz,‡ Koji Endo,‡ Paresma R. Patel, Myles B. Herbert, and Robert H. Grubbs* Arnold and Mabel Beckman Laboratories of Chemical Synthesis, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, United States S *Supporting Information ABSTRACT: Several new C−H-activated ruthenium catalysts for Z-selective olefin metathesis have been synthesized. Both the carboxylate ligand and the aryl group of the N-heterocyclic carbene have been altered and the resulting catalysts evaluated using a range of metathesis reactions. Substitution of bidentate with monodentate X-type ligands led to a severe attenuation of metathesis activity and selectivity, while minor differences were observed between bidentate ligands within the same family (e.g., carboxylates). The use of nitrato-type ligands in place of carboxylates afforded a significant improvement in metathesis activity and selectivity. With these catalysts, turnover numbers approaching 1000 were possible for a variety of cross-metathesis reactions, including the synthesis of industrially relevant products. ■ INTRODUCTION Olefin metathesis is a powerful tool for the construction of new carbon−carbon bonds.1 The development of robust metathesis catalysts,2 which carry out this transformation, has facilitated the adoption of this methodology by a variety of fields including polymer chemistry,3 organic synthesis,4 biochemis- 5