1160105-93-0Relevant academic research and scientific papers
Z -selective ethenolysis with a ruthenium metathesis catalyst: Experiment and theory
Miyazaki, Hiroshi,Herbert, Myles B.,Liu, Peng,Dong, Xiaofei,Xu, Xiufang,Keitz, Benjamin K.,Ung, Thay,Mkrtumyan, Garik,Houk,Grubbs, Robert H.
supporting information, p. 5848 - 5858 (2013/05/22)
The Z-selective ethenolysis activity of chelated ruthenium metathesis catalysts was investigated with experiment and theory. A five-membered chelated catalyst that was successfully employed in Z-selective cross metathesis reactions has now been found to be highly active for Z-selective ethenolysis at low ethylene pressures, while tolerating a wide variety of functional groups. This phenomenon also affects its activity in cross metathesis reactions and prohibits crossover reactions of internal olefins via trisubstituted ruthenacyclobutane intermediates. In contrast, a related catalyst containing a six-membered chelated architecture is not active for ethenolysis and seems to react through different pathways more reminiscent of previous generations of ruthenium catalysts. Computational investigations of the effects of substitution on relevant transition states and ruthenacyclobutane intermediates revealed that the differences of activities are attributed to the steric repulsions of the anionic ligand with the chelating groups.
Pheromone synthesis. Part 240: Cross-metathesis with Grubbs I (but not Grubbs II) catalyst for the synthesis of (R)-trogodermal (14-methyl-8-hexadecenal) to study the optical rotatory powers of compounds with a terminal sec-butyl group
Mori, Kenji
experimental part, p. 3900 - 3909 (2009/09/08)
(R)-Trogodermal (14-methyl-8-hexadecenal), the sex pheromone of Trogoderma species of pest insects against stored products, and its (S)-isomer were synthesized by using olefin cross-metathesis between (R)- or (S)-7-methyl-1-nonene and 8-nonenyl acetate as the key step. This step was successful with Grubbs I but not with Grubbs II catalyst. The latter caused randomization of the carbon skeleton to give a mixture of abnormal products with both longer or shorter carbon chains than the desired product. The specific rotations of 18 newly and 6 previously synthesized compounds with a terminal sec-butyl group were measured to conclude them to be [α]D +3.5 to +6.5 or -3.6 to -6.4.
