Abstract
A transition-metal-free one-pot direct synthesis of tetrathiophosphates
(R1S)2P(S)SR2 from white phosphorus (P4), through inter-mediate S-sodium
S,S-dialkylphosphorotetrathioates (R1S)2P(S)SNa, is presented. In the
presence of NaSH, various disulfides such as diaryl disulfides and
dialkyl disulfides are easily coupled with P4 to give S-sodium
S,S-dialkylphosphorotetrathioates (R1S)2P(S)SNa in almost quantitative
yield, which react with alkyl halides in one pot to generate
(R1S)2P(S)SR2. Furthermore, S-(2-cyanoethyl)-substituted
tetrathiophosphates (R1S)2P(S)SCH2CH2CN are successfully designed as a
kind of tetrathiophosphorylation reagents to react with diaryl iodonium
salts involving deprotection-dealkylation process.