title: Molybdenum chloride catalysts for Z-selective olefin metathesis reactions.
abstract: The development of catalyst-controlled stereoselective olefin metathesis processes has been a pivotal recent advance in chemistry. The incorporation of appropriate ligands within complexes based on molybdenum, tungsten and ruthenium has led to reactivity and selectivity levels that were previously inaccessible. Here we show that molybdenum monoaryloxide chloride complexes furnish higher-energy (Z) isomers of trifluoromethyl-substituted alkenes through cross-metathesis reactions with the commercially available, inexpensive and typically inert Z-1,1,1,4,4,4-hexafluoro-2-butene. Furthermore, otherwise inefficient and non-stereoselective transformations with Z-1,2-dichloroethene and 1,2-dibromoethene can be effected with substantially improved efficiency and Z selectivity. The use of such molybdenum monoaryloxide chloride complexes enables the synthesis of representative biologically active molecules and trifluoromethyl analogues of medicinally relevant compounds. The origins of the activity and selectivity levels observed, which contradict previously proposed principles, are elucidated with the aid of density functional theory calculations.
authors.affiliation: Department of Chemistry, Merkert Chemistry Center, Boston College, Chestnut Hill, Massachusetts 02467, USA.
authors.forename: Ming Joo
authors.initials: MJ
authors.lastname: Koh
authors.affiliation: Department of Chemistry, Merkert Chemistry Center, Boston College, Chestnut Hill, Massachusetts 02467, USA.
authors.forename: Thach T
authors.initials: TT
authors.lastname: Nguyen
authors.affiliation: Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA.
authors.forename: Jonathan K
authors.initials: JK
authors.lastname: Lam
authors.affiliation: Department of Chemistry, Merkert Chemistry Center, Boston College, Chestnut Hill, Massachusetts 02467, USA.
authors.forename: Sebastian
authors.initials: S
authors.lastname: Torker
authors.affiliation: Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA.
authors.forename: Jakub
authors.initials: J
authors.lastname: Hyvl
authors.affiliation: Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA.
authors.forename: Richard R
authors.initials: RR
authors.lastname: Schrock
authors.affiliation: Department of Chemistry, Merkert Chemistry Center, Boston College, Chestnut Hill, Massachusetts 02467, USA.
authors.forename: Amir H
authors.initials: AH
authors.lastname: Hoveyda
mesh_terms: D000475:Alkenes / Q000138:chemical synthesis* / Q000737:chemistry*; D002384:Catalysis; D002712:Chlorides / Q000737:chemistry*; D005466:Fluorocarbons / Q000737:chemistry; D008024:Ligands; D008982:Molybdenum / Q000737:chemistry*
chemical_list: D000475:Alkenes; D002712:Chlorides; D005466:Fluorocarbons; D008024:Ligands; D008982:Molybdenum; C085192:molybdenum chloride