title: Highly Z-selective metathesis homocoupling of terminal olefins.
abstract: Mo and W MonoAryloxide-Pyrrolide (MAP) olefin metathesis catalysts can couple terminal olefins to give as high as >98% Z-products in moderate to high yields with as little as 0.2% catalyst. Results are reported for 1-hexene, 1-octene, allylbenzene, allyltrimethylsilane, methyl-10-undecenoate, methyl-9-decenoate, allylB(pinacolate), allylOBenzyl, allylNHTosyl, and allylNHPh. It is proposed that high Z-selectivity is achieved because a large aryloxide only allows metallacyclobutanes to form that contain adjacent cis substituents and because isomerization of Z-product to E-product can be slow in that same steric environment.
authors.affiliation: Department of Chemistry 6-331, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA.
authors.forename: Annie J
authors.initials: AJ
authors.lastname: Jiang
authors.forename: Yu
authors.initials: Y
authors.lastname: Zhao
authors.forename: Richard R
authors.initials: RR
authors.lastname: Schrock
authors.forename: Amir H
authors.initials: AH
authors.lastname: Hoveyda
mesh_terms: D000475:Alkenes / Q000737:chemistry*; D002384:Catalysis
chemical_list: D000475:Alkenes