The reaction of [ClP(μ-PMes*)]2 (1) with the Lewis acid GaCl3 yielded a hitherto unknown tetraphosphabicyclo[1.1.0]butan-2-ium salt, [Mes*P4(Cl)Mes*][GaCl4] (3[GaCl4]), which incorporates a positively charged phosphonium center within its bicyclic P4 scaffold. The formation of the title compound was studied by means of low-temperature NMR experiments. This led to the identification of an intermediate cyclotetraphosphenium cation, which was trapped by reaction with dimethylbutadiene (dmb). All of the compounds were fully characterized by experimental and computational methods.

Different reactions of Mes* substituted phosphanes (Mes* = 2,4,6-tri-tert-butylphenyl) led to the formation of the bicyclic tetraphosphane Mes*P4Mes* (5) and its unknown Lewis acid adduct 5·GaCl3. In this context, the endo-exo isomer of 5 was fully characterized for the first time. The synthesis was achieved by reactions involving "self-assembly" of the P4 scaffold from P1 building blocks (i.e. primary phosphanes) or by reactions starting from P2 or P4 scaffolds (i.e. a diphosphene or cyclic tetraphosphane). Furthermore, interconversion between the exo-exo and endo-exo isomer were studied by (31)P NMR spectroscopy. All compounds were fully characterized by experimental as well as computational methods.

A novel high yielding, enantio- and diastereoselective protocol for the synthesis of α-allylated highly functionalised β-amino acid derivatives by adding isoxazolidin-5-ones to MBH carbonates under asymmetric phase-transfer catalysis has been developed.

Scheme 1. Mechanism of polyolefin hydrocracking, during which CÀ C bonds are dehydrogenated, cracked via carbocation chemistry, and re-hydrogenated over a bifunctional metal-acid catalyst.