3147-20-4Relevant articles and documents
Lewis Acid Promoted Aerobic Oxidative Coupling of Thiols with Phosphonates by Simple Nickel(II) Catalyst: Substrate Scope and Mechanistic Studies
Xue, Jing-Wen,Zeng, Miao,Zhang, Sicheng,Chen, Zhuqi,Yin, Guochuan
, p. 4179 - 4190 (2019/04/30)
Exploring new catalysts for efficient organic synthesis is among the most attractive topics in chemistry. Here, using Ni(OAc)2/LA as catalyst (LA: Lewis acid), a novel catalyst strategy was developed for oxidative coupling of thiols and phosphonates to phosphorothioates with oxygen oxidant. The present study discloses that when Ni(OAc)2 alone was employed as the catalyst, the reaction proceeded very sluggishly with low yield, whereas adding non-redox-active metal ions such as Y3+ to Ni(OAc)2 dramatically promoted its catalytic efficiency. The promotional effect is highly Lewis acidity dependent on the added Lewis acid, and generally, a stronger Lewis acid provided a better promotional effect. The stopped-flow kinetics confirmed that adding Y(OTf)3 can obviously accelerate the activation of thiols by Ni(II) and next accelerate its reaction with phosphonate to generate the phosphorothioate product. ESI-MS characterizations of the catalyst disclosed the formation of the heterobimetallic Ni(II)/Y(III) species in the catalyst solution. Additionally, this Ni(II)/LA catalyst can be applied in the synthesis of a series of phosphorothioate compounds including several commercial bioactive compounds. This catalyst strategy has clearly supported that Lewis acid can significantly improve the catalytic efficiency of these traditional metal ions in organic synthesis, thus opening up new opportunities in their catalyst design.
Cs2CO3-Catalyzed Aerobic Oxidative Cross-Dehydrogenative Coupling of Thiols with Phosphonates and Arenes
Song, Song,Zhang, Yiqun,Yeerlan, Adeli,Zhu, Bencong,Liu, Jianzhong,Jiao, Ning
supporting information, p. 2487 - 2491 (2017/02/23)
An efficient Cs2CO3-catalyzed oxidative coupling of thiols with phosphonates and arenes that uses molecular oxygen as the oxidant is described. These reactions provide not only a novel alkali metal salt catalyzed aerobic oxidation, but also an efficient approach to thiophosphates and sulfenylarenes, which are ubiquitously found in pharmaceuticals and pesticides. The reaction proceeds under simple and mild reaction conditions, tolerates a wide range of functional groups, and is applicable to the late-stage synthesis and modification of bioactive molecules.
SYNTHESIS OF S-DIALKYLAMINO THIOPHOSPHATES
Petrov, K. A.,Rudnev, G. V.,Sorokin, V. D.
, p. 1012 - 1014 (2007/10/02)
O,O-Dialkyl S-(2-dialkylaminoethyl) thiophosphates are obtained by the reaction of dialkylamino sulfenyl chlorides, sulfenamides, thiobisamines, and amino disulfides with neutral and acidic alkyl phosphites; in the case of sulfenamides the synthesis is carried out under acid-catalysis conditions using zinc chloride.N,N-Dimethylthiobisamine reacts with the neutral phosphite to give O,O-diethyl S-dimethylamino thiophosphate, while the reaction of the amino disulfide with sodium diethyl phosphite leads to 2-diethylaminoethyl ethyl sulfide.