113427-81-9Relevant articles and documents
Synthesis of Organolithium Compounds from Phenyl Selenides
Krief, Alain,Nazih, Abdesslame,Hobe, Myriam
, p. 8111 - 8114 (1995)
Alkyl aryl selenides react with lithium arenides to produce, regioselectively, alkyllithiums and lithium arylselenolates.Experimental conditions, especially the temperature, have a profound effect on the course of this reaction and on the nature of the products.
Stereoselective syntheses of 1,2-dialkyl-1-phenyl cyclopentanes involving intramolecular carbolithiation of olefins
Krief, Alain,Kenda, Benoit,Maertens, Christophe,Remacle, Bruno
, p. 7465 - 7473 (1996)
2-Ethyl-1-methyl-1-phenyl cyclopentane, unavailable by butyllithium-promoted carbocyclisation of the carbocyclisation of 6-phenyl-6-methylseleno-1-heptene as the key step.
Stereochemical outcome of benzyllithiums synthesis from selenides
Krief, Alain,Hobe, Myriam,Dumont, Willy,Badaoui, Elie,Guittet, Eric,Evrard, Guy
, p. 3381 - 3384 (2007/10/02)
Epimerisation usually occurs during the synthesis of arylalcanes from the corresponding benzylselenides which involves benzyllithiums as intermediates. This has been used to produce stereoselectively arylcyclopentanes and arylcyclopropanes. γ-Benzenesulfonyloxyalkyl selenides substituted on the carbon bearing the benzenesulfonyl group behave differently and lead stereospecifically to arylcyclopropane derivatives.
ORIGINAL REACTIONS OF α,α-DITHIO ARYL ALKANES WITH BUTYLLITHIUMS
Krief, Alain,Kenda, Benoit,Barbeaux, Philippe
, p. 2509 - 2512 (2007/10/02)
Thioacetals derived from aromatic ketones react with butyllithiums already at -78 deg C and produce via a reductive process the corresponding α-thiobenzyllithiums in high yields.The same reaction also takes place selectively, under suitable conditions, wi
Intramolecular Nucleophilic Addition to Unsaturated Carbon. Dependence of Cyclization Efficiency on the Method of Carbon-Carbon Bond Cleavage Utilized To Generate the Reactive Species
Paquette, Leo A.,Gilday, John P.,Maynard, George D.
, p. 5044 - 5053 (2007/10/02)
The following three reactions have been studied for the purpose of comparing their intrinsic ability to generate carbanionic intermediates capable of intramolecular cyclization: (a) the Haller-Bauer cleavage of ketones 15a and 15b, as well as the (S)-(+)-antipode of 15a (viz. 47); (b) the base-promoted cleavage of 1,1-diarylcarbinols 16a and 16b; (c) decarboxylative elimination within the methyllithium adducts of carboxylic acids 17a and 17b.The Haller-Bauer process proceeds predominantly via carbanion intermediates, which most often experience protonation to give 18 an d 21.Cyclization becomes possible, however, under certain circumstances and reaches a maximum of 33percent with NaNH2 in benzene.Using (+)-47 as a probe, it has been possible to ascertain that 56percent of the reactive intermediate molecules racemize and that only the racemic species generates cyclic product.On the other hand, the Cram-type cleavages of 16a and 16b proceed mainly by homolytic cleavage to generate the benzophenone radical anion and free-radical intermediate.The latter dimerize, capture solvent, and abstract hydrogen to varying degrees depending upon counterion and solvent.Finally, reactions of type c are the most efficient at effecting intramolecular ring closure.
Original Syntheses of Arylcycloalkanes
Krief, Alain,Barbeaux, Philippe
, p. 1214 - 1216 (2007/10/02)
Arylcycloalkanes have been prepared from acetophenone by a three-step sequence involving the synthesis of α-phenyl(ω-alkenyl)methylselenides and their reaction with butyl-lithium reagents to give an intermediate which adds across the C=C double bond to gi
