125722-52-3Relevant academic research and scientific papers
Reactions of a Dilithiomethane with CO and N2O: An Avenue to an Anionic Ketene and a Hexafunctionalized Benzene
Xu, Maotong,Wang, Tongtong,Qu, Zheng-Wang,Grimme, Stefan,Stephan, Douglas W.
supporting information, p. 25281 - 25285 (2021/10/25)
Synthesis of value-added products from simple C1 feedstocks is an attractive alternative avenue to traditional fossil fuels. Hexa-substituted benzene derivatives are highly useful molecules but are often challenging to prepare. Herein, we report that the lithium complex [(Ph2P(S))2CLi2(THF)]2 1 reacts with CO lead to C?C bond formation and migration of a Ph2P(S)-fragment affording 2. Subsequent reaction with N2O results in oxidative cleavage of a P?C bond affording [Ph2P(S)OLi(THF)2]2 4 and the anionic ketene-derivative Ph2P(S)CCOLi(THF)2 5. Heating 5 prompts cyclotrimerization giving the hexa-substituted benzene derivative [Ph2P(S)CCOLi(THF)2]3 6 regioselectively. This transition metal-free protocol to a hexa-substituted benzene is viable on a gram scale and permits the incorporation of 13C labels. The mechanisms of these reactions are detailed via extensive DFT computations.
OPTICALLY ACTIVE SILYL ESTERS OF PHOSPHOROUS. II. STEREOCHEMISTRY OF REACTIONS WITH NUCLEOPHILES
Wozniak, Lucyna,Cypryk, Marek,Chojnowski, Julian
, p. 4403 - 4414 (2007/10/02)
We report the stereochemistry of reactions of various nucleophiles with optically active silyl esters of phosphorus of general formula: tBuPhP(X)OSiMePhNp X= -(1), Oxygen (2), Sulfur (3), Selenium (4).The list of nucleophiles includes O,S,N,C nucleophiles as well as halides.The nucleophilic attack is essentially directed towards silicon.The phosphinuos and phosphonic acid esters react with predominant retention of configuration at silicon atom, whereas the thiono and seleno crossover is explained in terms of possible interaction of the electrophilic part of the nucleophile with the oxyphosphoryl group or tricoordinate phosphorous.
