Nonproductive events in ring-closing metathesis using ruthenium catalysts.
The relative TONs of productive and nonproductive metathesis reactions of diethyl diallylmalonate are compared for eight different ruthenium-based catalysts. Nonproductive cross metathesis is proposed to involve a chain-carrying ruthenium methylidene. A second more-challenging substrate (dimethyl allylmethylallylmalonate) that forms a trisubstituted olefin product is used to further delineate the effect of catalyst structure on the relative efficiencies of these processes. A steric model is proposed to explain the observed trends.
Stewart
Ian C
IC
The Arnold and Mabel Beckman Laboratory of Chemical Synthesis, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, USA.
Keitz
Benjamin K
BK
Kuhn
Kevin M
KM
Thomas
Renee M
RM
Grubbs
Robert H
RH
D000475:Alkenes / Q000737:chemistry; D002384:Catalysis; D007700:Kinetics; D012428:Ruthenium / Q000737:chemistry*
D000475:Alkenes; D012428:Ruthenium