Progress in the Chemistry of Phosphorothioates
Pp. 117-150 (34)
The present review focuses on the synthesis and applications of
phosphorothioates (phosphorothioic esters) with the general structure R2P(O)SR’,
which are molecules belonging to the large family of organophosphorus compounds.
They found important applications as biological active molecules, as well as synthetic
intermediates to access valuable phosphorus and/or sulfur-containing structures. The
reactivity of both heteroatoms, phosphorus and sulfur, is discussed by showing how
they are involved as electrophilic, nucleophilic, or radical species in different
transformations. The general methods for the preparation of phosphorothioates are
described according to the various strategies involving P-S bond formation from one
sulfur-reagent and one phosphorus-reagent, which include recent metal-catalyzed
cross-coupling reactions. Particular attention is paid to synthetic applications of
phosphorothioates occurring via the P-S bond cleavage, including for example anionic
rearrangements and cascades, formation of sulfur-heterocycles, homolytic processes for
olefins phosphorylation, and metal-catalyzed alkynes thiophosphorylation. The
literature of the last two decades is covered, highlighting selected contributions in the
chemistry of this class of compounds.
Anionic Rearrangement, Mercaptophosphonate, Phosphorus,
Phosphorothioates, Phosphorothioic esters, P-S Bond Cleavage, P-S Bond
Formation, P-S Coupling, Sulfur, Sulfur Heterocycles, Sigmatropic
Laboratoire d’Innovation Therapeutique (LIT, UMR 7200), Universite de Strasbourg, CNRS, 74 Route du Rhin, 67401 Illkirch, France.