François Mathey

Latest Advances in Phosphole Chemistry

Abstract The chemistry of pyramidal phospholes is governed by their low aromaticity and the strong σ,π overlap between the P-R exocyclic bond and the dienic system. Hence, functionalisation of the ring is difficult but [1,51 sigmatropic shift of R is easy. These two complementary aspects of phosphole chemistry are explored. Two routes to α-functional phospholes are described. They involve either a C-Br to C-Li exchange reaction or the allylic metallation of 3,4-dimethylphosphole-borane complexes. The influence of the atom connected to P (sp2C, spC, N, O, S) and the substitution pattern of the phosphole ring upon the [1,5] sigmatropic migration is discussed. Finally, several applications of this chemistry for the synthesis of water-soluble phosphines and polyphospha-macrocycles are described.

Access to New Phosphorus Structures by the Way of the Transient Terminal Phosphinidene Complexes

Abstract The Tungstaphosphirenes, Phosphaalkenes, Phosphahexatrienes, η4-phosphabutadiene complexes and 1,2-dihydrophosphete ring have been synthesized by coupling reactions of carbyne or carbene complexes with the transient phenyl phosphinidene pentacarbonyl tungsten [PhP[dbnd]W(CO) 5]. The preparation of other heterocycles such as Dihydrodiphosphetes and Dihydrophosphepines has been realized from the vinylphosphinidene complexes via a 4π-electrocyclization and a Phospha-Cope rearrangement respectively.