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.
The Arnold and Mabel Beckman Laboratory of Chemical Synthesis, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, USA.
Ian C
IC
Stewart
Benjamin K
BK
Keitz
Kevin M
KM
Kuhn
Renee M
RM
Thomas
Robert H
RH
Grubbs
D000475:Alkenes / Q000737:chemistry; D002384:Catalysis; D007700:Kinetics; D012428:Ruthenium / Q000737:chemistry*
D000475:Alkenes; D012428:Ruthenium