An assembled complex of palladium and non-cross-linked amphiphilic polymer: a highly active and recyclable catalyst for the Suzuki-Miyaura reaction

An insoluble and assembled catalyst of palladium and a non-cross-linked amphiphilic polymer were developed. In the presence of 50-500 ppm mol equiv of catalyst, the Suzuki-Miyaura reaction proceeded efficiently under organic solvent-free conditions. The catalyst was reused 10 times without any decrease in activity and was recycled without any special treatment.[structure: see text]     

Novel synthesis of L-ribose from D-mannono-1,4-lactone

[reaction: see text] D-Mannono-1,4-lactone was efficiently converted into L-ribose in eight steps. A key step of this synthesis is the cyclization of a gamma-hydroxyalkoxamate under Mitsunobu conditions. It is noteworthy that the O-alkylation product was obtained in 94% yield and that none of the N-alkylation product was detected in this cyclization.     

Reaction of zirconacycles with 3-iodopropenoates and 3-iodocycloenones in the presence of CuCl: A new pathway for the formation of cyclopentadienes and spirocyclic compounds

Formation of cyclic compounds from zirconacycles has been performed by a combination of Michael addition and coupling with an alkenyl iodide moiety in the presence of a stoichiometric amount of CuCl. The reaction of 3-iodopropenoates with various zirconacyclopentadienes in the presence of a stoichiometric amount of CuCl afforded penta- and hexasubstituted cyclopentadienes. The reaction of 3-iodocycloenones with zirconacyclopentadienes, zirconacyclopentenes, or zirconacyclopentanes gave spirocyclic compounds in good yields.     

Nuclear magnetic resonance spectra of carbanions—VI. Cumyl-, α-methylbenzyl- and benzyl carbanions

The proton magnetic resonance spectra of the three title carbanions have been observed in THF with potassium as a counter ion. The ortho-protons in the α-methylbenzyl carbanion are nonequivalent at room temperature. This shows that the α-carbon in this carbanion is in the near-sp² configuration. The aromatic proton chemical shifts of the benzylpotassium obtained here are at higher shielding than those of benzyllithium reported previously by Sandel and Freedman. This seems to arise from the different ionic nature of the bonds between carbon and metal in the carbanions.     

New bis- and tris-annulation reagents for the syntheses of CD rings of steroids,bearing a functionalized 18-methyl group,by the palladium-catalyzed cyclization

2-Substituted 2-alkoxycarbonyl-3-vinylcyclopentanones (2), easily prepared by the palladium-catalyzed cyclization of 2-substituted 3-oxo-8-phenoxy-6-octenoates (1), are very suitable building blocks for CD rings of steroids, bearing particularly a functionalized 18-methyl group.