Metal-free hydrophosphorodithiolation of alkynes with P₄S₁₀ and alcohols leading to vinyl phosphorodithioates

Abstract

A facile and metal-free hydrophosphorodithiolation of alkynes with P4S10 and alcohols leading to vinyl phosphorodithioates has been developed under mild conditions.

Visible-Light Photoredox-Catalyzed Difunctionalization of Alkynes with Quinoxalin-2(1H)-Ones, P4S10, and Alcohols

“…These methods still require the use of metal catalysts or complex raw materials. Very recently, our group reported metal-free hydrophosphorodithiolation of alkynes with P 4 S 10 and alcohols leading to vinyl phosphorodithioates …”

Construction of β-Oximino Phosphorodithioates via (2,2,6,6-Tetramethylpiperidin-1-yl)oxyl-Promoted Difunctionalization of Alkenes with tert-Butyl Nitrite, P4S10, and Alcohols

“…On the basis of the above experiments and previous reports, − ,, a possible reaction mechanism was demonstrated in Scheme . First, O , O -diethyl S -hydrogen phosphorodithioate 6a was formed through the reaction of P 4 S 10 with EtOH.…”

“…Phosphorodithioates as an extraordinarily important class of phosphorus- and sulfur-containing compounds widely exist in many bioactive molecules and functional materials, which exhibit diverse physical and biological activities, including antiwear, insecticidal, antiviral, and butyrylcholinesterase- and acetylcholinesterase-inhibiting properties. Traditional methods for the construction of phosphorodithioates involved the substitution reactions of RX with ammonium/potassium salt of thiophosphate or the reactions of (RO) 2 P­(S)­Cl with RSH, in which strong base and multiple reaction steps were generally required. , P 4 S 10 is a readily available thionating reagent, which could serve as a useful synthetic precursor to construct various organosulfur compounds in synthetic chemistry . In our ongoing research interests in the development of new difunctionalization of alkenes, herein, we wish to present an efficient strategy for the synthesis of β-oximino phosphorodithioates through (2,2,6,6-tetramethylpiperidin-1-yl)­oxyl (TEMPO)-promoted four-component difunctionalization reactions of alkenes with tert -butyl nitrite, P 4 S 10 , and alcohols under mild conditions (strategy e of Scheme ).…”