89229-73-2Relevant articles and documents
A new set of nickelacyclic carboxylates ( nickelalactones ) containing pyridine as supporting ligand: Synthesis, structures and application in C-C- and C-S- linkage reactions
Langer, Jens,Fischer, Reinald,G?rls, Helmar,Walther, Dirk
, p. 2952 - 2962 (2004)
Nickelacycles of the type [(py)2Ni(CH2 COO)](1a), [(py) 2Ni(C(Et) C(Et)=COO)] (2a), and [(py)Ni (CH2)-CH2-COO)] (3a) were synthesized and structurally investigated by NMR, IR spectroscopy and in case of 1a and 2a by X-ray diffraction analysis. In 1a and 2a the Ni(II) ion has square-planar geometry, in contrast to the η3 allyl compound [(bipy)Ni(CH2)-CH2-COO)] (3b), in which nickel center adopts square-pyramidal geometry. 1a reacts with di(2-pyridyl)dimethylsilane (Me2(2-py)2Si) under exchange of the pyridine ligands to give 1c. 1a-3a and their bipy derivatives react with di-p-tolyldisulfide to form β-thioesters upon workup. Furthermore, reaction of 2-bromopropiophenone with nickelacycles of the type 2 results in the formation of 3,4-diethyl-6-hydroxy-5-methyl-6-phenyl-5,6-dihydro-2H-pyrane-2-one in good yields (64-75%). These reactions offer attractive new preparative routes for functionalized organic compounds.
ETUDE DES PETITS CYCLES-XLIV. UNE VOIE DE SYNTHESE DES ACYL-2 CYCLOBUTANONES
Lechevallier, A.,Huet, F.,Conia, J.M.
, p. 3329 - 3336 (2007/10/02)
Organic peracid oxidation of α-cyclopropylidene ketones and acetals substituted in the vinylic position leads to the corresponding oxaspiropentyl ketones and acetals.Esters are also formed from the products of the Baeyer-Villiger oxidation; they are easily removed from the crude product.Unsubstituted oxaspiropentyl ketones are not obtained by this method; they are obtained by oxidation of oxaspiropentyl alcohols ( formed by epoxidation of α-cyclopropylidene alcohols).The isomerisation, either spontaneous or through reaction with lithium halides, of oxaspiropentyl ketones and acetals, gives 2-acyl-cyclobutanones and corresponding mono-acetals.These new unstable 1,3-diones must be stored in CCl4 solution.They are present in the dione form only.They add water and methanol, in acidic and even in neutral medium, leading to ring opening products. 2-Benzoyl cyclobutanone 4g is easily rearranged into 3,4-dihydro-6-phenyl 2-pyrone 12.Deacetalization of the 2-acyl-cyclobutanones mono-acetals 7B-11b into the corresponding diones is not possible even by the moist silicagel technique.