Facile Pd(II)- and Ni(II)-catalyzed isomerization of terminal alkenes into 2-alkenes.
Mono- and 2,2'-disubstituted terminal alkenes can be isomerized into the more stable internal (Z)- and (E)-alkenes by treating them with catalytic amounts of [(allyl)PdCl](2) or [(allyl)NiBr](2), a triarylphosphine, and silver triflate at room temperature. The isomeric ratio (E:Z) depends on the alkenes, the E-isomer being the major one. The reaction is tolerant to a wide variety of functional groups including other reactive olefins. Unlike the more reactive Ir catalysts, monosubstituted alkenes give almost exclusively the 2-alkenes. Direct comparison to two of the best-known catalysts for this process {[Ir(PCy(3))(3)](+)[BPh(4)](-) and Grubbs generation II metathesis catalyst} is also described.
Department of Chemistry, The Ohio State University, 100 W. 18th Avenue, Columbus, Ohio 43210, USA.
Hwan Jung
HJ
Lim
Craig R
CR
Smith
T V
TV
RajanBabu
D000475:Alkenes / Q000737:chemistry*; D000498:Allyl Compounds / Q000737:chemistry; D001555:Benzene Derivatives / Q000737:chemistry; D001965:Bromides / Q000737:chemistry; D002712:Chlorides / Q000737:chemistry; D053138:Cyclohexenes / Q000737:chemistry; D054833:Isoindoles / Q000737:chemistry; D007536:Isomerism; D009532:Nickel; D010165:Palladium
D000475:Alkenes; D000498:Allyl Compounds; D001555:Benzene Derivatives; D001965:Bromides; D002712:Chlorides; D053138:Cyclohexenes; D054833:Isoindoles; D010165:Palladium; D009532:Nickel