New Protocol for the Synthesis of S-Thioesters from Benzylic, Allylic and Tertiary Alcohols with Thioacetic Acid.

A new one-pot solvent-less reaction to convert benzylic, allylic, ferrocenyl or tertiary alcohols into S-thioesters, bench-stable and less odorous precursors of the corresponding thiols, which is based on reactions in neat thioacetic acid in the presence of tetrafluoroboric acid, is presented. Reaction monitoring by NMR and GC of the benzyl alcohol conversion indicated the intermediate formation of benzyl acetate and benzyl thionoacetate (PhCH OC(S)CH ) prior to the slower conversion to the final S-benzyl thioacetate product. Increasing the HBF concentration enhanced the reaction rate, giving good to excellent yield (up to 99 %) for a large scope of alcohols.

The cocrystal rac-1-[(N,4-dimethylbenzenesulfonamido)methyl]-2-(diphenylphosphoryl)ferrocene-rac-1-[(N,4-dimethylbenzenesulfonamido)methyl]-2-(diphenylphosphanyl)ferrocene (0.45/0.55).

As part of our interest in the synthesis and catalytic applications of chiral (diphenylphosphanyl)ferrocene ligands, we designed a number of P,N-containing ligands for use in asymmetric transfer hydrogenation (ATH). During the synthetic procedure to obtain rac-1-[(N,4-dimethylbenzenesulfonamido)methyl]-2-(diphenylphosphanyl)ferrocene, the title compound, [Fe(C5H5)(C26H25NO2PS)]0.55 · [Fe(C5H5)(C26H25NO3PS)]0.

1-(Diphenyl-phosphinothio-yl)-2-[(4-methyl-phen-yl)meth-oxy-meth-yl]ferrocene.

Following our continuing inter-est in developing new chiral phosphine-containing ferrocenyl ligands, we synthesized the title compound, [Fe(C(5)H(5))(C(26)H(24)OPS)], in which there are two nearly identical mol-ecules in the asymmetric unit. The conformation of the cyclo-penta-dienyl (Cp) rings in each ferrocenyl group are inter-mediate between eclipsed and staggered, with twist angles of 16.6 (2) and 8.