Quelques Proprietes Chimiques Du Tris(Tertiobutyl)-2,4,6 Phenyldithiophosphorane

Lewis base-free thiophosphonium ion: a cationic sulfur atom transfer reagent

“…The limited substrate scope can be rationalised by the steric shielding of the reactive PQS double bond. The thionation reacions with the thiophosphonium cation [4] + are complementary to those with monomeric aryl-substituted dithiophosphoranes reported by the groups of Navech 9 and Yoshifuji. 4 The reaction is assumed to proceed via a four-membered thiadiphosphetane rings, which is equally conceivable for the cationic system.…”

“…In 1983, the groups of Appel, 6 as well as Majoral and Navech, 7 synthesised the first monomeric dithiophosphorane II (Scheme 1) by using a very bulky 2,4,6-tri-tert-butylphenyl group, which prevents dimerisation upon blocking both sides of the PS 2 plane but decomposes at 110 1C via isomerisation. 8,9 The group of Yoshifuji extended the scope of monomeric phenyl-substituted dithiophosphoranes by using amino groups to prevent dimerisation. 10 Furthermore, the group replaced one tert-butyl group adjacent to phosphorus in II with a methoxy group, resulting in a dithiophosphorane that is monomeric in solution but dimeric in the solid state.…”

The unusual influence of hetaryl groups on the direct conversion of some secondary alcohols into thiols with Lawesson’s reagent: elucidation of the reaction mechanism

“…After chromatographic separation, the less polar fraction was identified as the known diphenylmethanethiol (4a) [6] as the major product. The more polar fraction, obtained as the minor product, was isolated as a colorless solid, and the 31 P NMR spectrum indicated the presence of a P-atom by a signal at 78.2 ppm, i.e., in the region of aryltrithiophosphonates [17][18][19][20] for the respective H-atoms. Based on these data, structure 5 (Scheme 2) was attributed to this product (cf.…”