Synthesis and application of phosphonothioates, phosphonodithioates, phosphorothioates, phosphinothioates and related compounds

Direct Transformation of Propargylic Alcohols and O,O-Diethyl Phosphorothioic Acid into S-(2H-Chromen-4-yl) Phosphorothioates

“…Phosphorothioic acids [(RO) 2 P(O)SH], as a powerful P-S source, have played an increasingly important role in the formation of organothiophosphates. 5 Recently, the use of phosphorothioic acids as nucleophiles for the direct transformation with various electrophiles into a series of organothiophosphates has been investigated. 11 For example, in 2010, the Wu group developed a Ga(OTf) 3 - 11a or UV-mediated 11b reaction of allylic alcohols or their methyl ether with diethyl phosphorothioic acid [(EtO) 2 P(O)SH] to afford phosphorothioates (Scheme 1a).…”

“…Up to now, some methods have been developed through the formation of the P-S bond. [5][6][7][8][9][10] These examples can be mainly classified as the following categories: (a) the Michaelis-Arbuzov reaction of P(OR) 3 with RSO 2 Cl; 6 (b) the nucleophilic substitution of (RO) 2 P(O)Cl with RSH; 7 (c) the coupling-reductive reaction of (RO) 2 P(O)H and RSO 2 Cl; 8 (d) the dehydrogenative coupling reaction of (RO) 2 P(O)H and RSH; 9 and (e) the multicomponent reactions of alkyl halides, arylboronic acids, diazonium, or iodonium salts using elemental sulfur and (RO) 2 P(O)H compounds. 10 Despite these pioneering works in the synthesis of organothiophosphates, these reactions have some disadvantages, such as highly toxic reagents, harsh reaction conditions, limited substrate scope, or using strong oxidants.…”

“…C NMR (100 MHz, CDCl 3 ):  = 15.9 (q, J CP = 3.1 Hz), 64.4 (d, J CP = 6.3 Hz), 83. 5,116.7,121.3 (d,J CP = 3.2 Hz),121.6,122.2 (d,J CP = 8.6 Hz),125.7,126.5,128.0,129.4,129.5,130.7,131.7,132.2,135.5 (d…”

Two Routes for the Synthesis of Phosphorothioates via P‐S Coupling Reaction of Dialkyl Phosphites with Thiols or a Mixture of Alkyl Halides and Thiourea in the Presence of CaO

“…The coupling reaction of thiols, sulfonyl chlorides, and boronic acids with dialkyl phosphite in the presence of transition metal catalysts is a more easy and general one-pot process for the preparation of phosphorothioates. [27][28][29][30][31][32] Recently we have reported copper catalyst coupling reaction of thiols with dialkyl phosphite for the synthesis of thiophosphates. [33] Heterogeneous basic catalysts are green recoverable basic solids for the syntheses of organic compounds that conventionally need to large amounts unrecoverable bases such as NaOH and KOH.…”

A Robust Methodology for the Synthesis of Phosphorothioates, Phosphinothioates and Phosphonothioates

“…[10] These compounds also have broad application in synthetic chemistry, particularly in heterocyclic synthesis and in CÀ C and CÀ F bond-forming reactions. [11] The preparation of these compounds using PÀ S bond forming chemistry has been the subject of extensive study in recent years. Metal-catalysed coupling reactions employing copper, [12] rhodium, [13] palladium, [14] iron [15] and iridium [16] catalysts have been developed.…”