59671-58-8Relevant academic research and scientific papers
Reactions of Carbonyl Compounds with Grignard Reagents in the Presence of Cerium Chloride
Imamoto, Tsuneo,Takiyama, Noboyuki,Nakamura, Kimikazu,Hatajima, Toshihiko,Kamiya, Yasuo
, p. 4392 - 4398 (2007/10/02)
The addition of Grignard reagents to ketones is significantly enhanced by cerium chloride with remarkable supression of side reactions, particularly enolization.Some esters, which are prone to side reactions, also react readily with Grignard reagents in the presence of cerium chloride to give normal reaction products in reasonable to high yields.
Electron Transfer in Reactions of Ketones with Organolithium Reagents. A Carbon-14 Kinetic Isotope Effect Probe
Yamataka, Hiroshi,Fujimura, Naoya,Kawafuji, Yukie,Hanafusa, Terukiyo
, p. 4305 - 4308 (2007/10/02)
Kinetic isotope effects have been determined for reactions of ketones labeled with carbon-14 at the carbonyl carbon with MeLi and Me2CuLi in diethyl ether at 0 deg C.Observed isotope effects were as follows: (C6H5)2C=O + MeLi, 12k/14k = 1.000 +/- 0.002; (C6H5)2C=O + Me2CuLi, 1.029 +/- 0.005; 2,4,6-Me3C6H2COC6H5 + MeLi, 1.023 +/- 0.004.The relative reactivities of ortho-, meta-, and para-substituted benzophenones with these reagents were also determined by the competition experiments.These results are consistent with an electron transfer step which is followed by a carbon-carbon bond-formimg step that is or is not rate determining depending on the structure of ketones and reagents.The reaction of benzophenone with MeLi proceeds via rate-determining electron transfer; the change in nucleophile from MeLi to Me2CuLi shifts the rate-determining step from electron-transfer to recombination; the change in ketone from benzophenone to 2,4,6-trimethylbenzophenone also shifts the rate-determining step from electron transfer to recombination because the latter step becomes slower for the more hindered ketone.The extent of the geometrical change of the substrate at the electron-transfer transition state of the reaction of benzophenone with MeLi was estimated to be small on the basis of the magnitude of the KIE and teh ρ value of the Hammett correlation.
ARYLVANADIUM-VERBINDUNGEN. XI. ZUR REAKTION VON TRIMESITYLVANADIUM MIT KETONEN
Kreisel, G.,Seidel, W.
, p. 301 - 306 (2007/10/02)
Trimesitylvanadium in solution reacts with a series of ketones.Depending upon the structures of the ketones these reactions yield olefins, alcohols or a radical, respectively.Sterically hindered ketones only form coordination compounds with trimesitylvana
