Small exponent asymptotics

We study the surprisingly complicated asymptotic character ofa simple first-order differential equation, which involves aterm with a low exponent of the dependent variable. While numericalsolutions and straightforward asymptotic expansions indicatea clearly defined boundary layer type transition, we find thatthe correct asymptotic structure involves a 'hidden' boundarylayer, and that a straightforward approach cannot discern this.     

Evidence of Phosphonium‐Carbenium Dication Formation in a Superacid: Precursor to Fluorinated Phosphine Oxides

Unambiguously confirmed by low‐temperature in situ NMR experiments, X‐ray diffraction and vibrational spectroscopy, phosphonium‐carbenium superelectrophiles are shown to be generated in strong acidic conditions. Representing crucial intermediates, their exploitation allows for the synthesis of unprecedented fluorinated (cyclic) phosphine oxides.     

Palladium-catalyzed C-P coupling reactions between vinyl triflates and phosphine-boranes: efficient access to vinylphosphine-boranes

Vinylphosphine-borane complexes are easily synthesized by palladium-catalyzed C-P cross-coupling of vinyl triflates with secondary phosphine-boranes. This method allows the synthesis of phosphine derivatives not always easily accessible by other approaches. The vinylphosphine derivatives are purified by chromatography on silica gel. The versatility of the method is proved by using various triflates and diaryl-, dialkyl- and alkylarylphosphine-borane precursors. Chiral enantiopure phosphine-boranes are synthesized from chiral triflates.     

Organocatalytic asymmetric synthesis of sulfoxides from sulfenic acid anions mediated by a Cinchona-derived phase-transfer reagent

Preliminary results concerning a conceptually novel route to chiral sulfoxides based on the asymmetric alkylation of sulfenate salts with alkyl halides mediated by a chiral phase-transfer catalyst are described. As a representative example, o-anisyl methyl sulfoxide was produced in 96% yield and with an enantiomeric excess of 58% using commercial cinchonidinium derivative 2a.