201345-00-8Relevant academic research and scientific papers
Catalytic Reductive Vinylidene Transfer Reactions
Pal, Sudipta,Zhou, You-Yun,Uyeda, Christopher
, p. 11686 - 11689 (2017)
Methylenecyclopropanes are important synthetic intermediates that possess strain energies exceeding those of saturated cyclopropanes by >10 kcal/mol. This report describes a catalytic reductive methylenecyclopropanation reaction of simple olefins, utilizing 1,1-dichloroalkenes as vinylidene precursors. The reaction is promoted by a dinuclear Ni catalyst, which is proposed to access Ni2(vinylidenoid) intermediates via C - Cl oxidative addition.
Reactions of the Lithium Salts of the Tribenzylidenemethane Dianion, Diphenylacetone Dianion, and Related Compounds
Witt, Ortrun,Mauser, Harald,Friedl, Thomas,Wilhelm, Dieter,Clark, Timothy
, p. 959 - 967 (2007/10/03)
Potentially synthetically useful reactions of the dilithium salts of the title dianions have been investigated. Electrophilic quenching with a variety of reagents usually leads to the expected products in good yield. Quenching the diphenylacetone dianion with 1 equiv of trimethylchlorosilane, however, gives a good yield of 1,3-diphenylallene obtained by formal elimination of a trimethylsiloxy anion from an intermediate monoquenched monoanion salt. NMR studies, however, do not reveal the intermediacy of the 1,3-diphenyl-2-(trimethylsiloxy)allyl anion but rather suggest that the initial reaction site is at carbon, rather than oxygen. Oxidation of the dianions leads either to ring closure or dimerization for the tribenzylidenemethane dianion and to dimerization for the diphenylacetone dianion. The dimerization reactions are stereospecific, both with respect to the two new stereocenters produced and for the double bonds of the bis-silyl enol ether products if the dimeric bis-enolate dianion products are quenched with trimethylchlorosilane.
