Addition reactions of ethoxycarbonylnitrene and ethoxycarbonylnitrenium ion to allylic ethers

Ethoxycarbonylnitrene (EtOCON) generated by α-elimination adds cleanly to allylic ethers giving substituted aziridines. Similar addition via nitrenium ion (EtOCONH⁺) gives derivatives of β-amino alcohols.     

Synthesis of β,β-branched β-amino ester derivatives through spiroaziridination of (α-trimethylsilanylmethyl)cyclohexylidene esters

The reaction of (α-trimethylsilanylmethyl)cyclohexylidene esters with NsONHCO₂Et and CaO produces the N-(ethoxycarbonyl)spiroaziridines which, after ring-opening, gives the corresponding β,β-disubstituted β-amino ester derivatives. The stereochemical outcome of the reaction is influenced by substituents on the cyclohexyl group.     

Synthesis of periphery-functionalized dendritic molecules using polylithiated dendrimers as starting material

A general method for the functionalization of Si-Cl terminated carbosilane dendritic molecules via organolithium or organomagnesium reagents is described. Quantitative exchange of the bromine atoms of 4-bromophenyl-functionalized dendrimers affords polylithiated species that are valuable starting materials for further functionalization, e.g., into pyridyl alcohols. The latter were successfully applied as catalyst precursors in a ruthenium-mediated ring-closure metathesis reaction.     

Unexpected and expeditious entry into trifluoromethyl aziridines from substituted beta-dicarbonyl compounds

[Reaction: see text]. One-pot aziridinations were obtained starting from substituted 2,2,2-trifluoroethyl beta-dicarbonyl compounds with nosyloxycarbamates in the presence of an excess of CaO as base. The unexpected ring closure reaction takes place at room temperature, leading to the N-protected alpha-trifluoromethyl aziridines with good yields. The reaction pathway seems to be influenced by the choice of the base.     

Functionalised enones as starting materials for the construction of aziridine scaffolds

alpha-Substituted beta-keto esters have been transformed by means of a straightforward procedure into aziridine-1,2-dicarboxylates, which have been efficiently converted into alkenyl aziridine-1,2-dicarboxylates through Wittig olefination reaction. The possibility of aziridine ring elaborations and the presence of an olefin function make these new molecules suitable scaffolds for further derivatisation into potential bioactive targets.     

Oscillatory melting temperature of the vortex smectic phase in layered superconductors

We report on transport measurements of YBa 2Cu 3O (7-delta) single crystals with different oxygen contents in the geometry B, J ||ab (J perpendicularB). Our data show that the vortices become confined between the Cu-O planes below a well-defined temperature at which the effective size 2xi of the vortex core is approximately equal to the period of the Cu-O layers. This confinement strongly increases the vortex liquid freezing temperature. A new melting line is found separating a vortex liquid and a smectic phase, which shows an oscillatory field dependence reflecting differences between commensurate and incommensurate smectic states.     

O-Arylsulfonyl hydroxylamines via a decarboxylative rearrangement

(E)-O-Arylsulfonyl-N-(2-nitroalk-2-enyl)hydroxylamines were easily obtained in good yields starting from (E)-nitro allylic alcohols, the crucial step being an inorganic base-catalyzed decarboxylative rearrangement of proposed labile unsaturated carbamates. A possible mechanism for the outcome of the reaction, characterized by the unusual retention of the sulfonyloxy group, is proposed.     

Synthesis of Novel Chiral Diol Ligands for the Enantioselective Reactions

The chiral diols ((,(,((,((-Tetraaryl-1,3-dioxolane-4,5-dimethanols) have been used for the formation of cyclic titanates and similar derivatives of Mg, Al and Zr. These complexes of oxophilic metal centers were employed in catalytic and stiochiometric enantioselective reactions such as enantioselective addition reactions of carbon-centered nucleophiles to aldehydes1, [2+2] cycloadditions2, and Diels-Alder reactions3. So far, the two hydrogen atoms of all this type of diols are in trans form…