39864-62-5Relevant academic research and scientific papers
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.
Erzeugung und Nachweis des Silaethens Me2Si=C(SiMe3)2: Thermischer Zerfall von (Me3Si)2(Me2XSi)CLi (X z. B. Hal, OR, SR)
Wiberg, Nils,Preiner, Gerhard,Schieda, Oswald,Fischer, Gerd
, p. 3505 - 3517 (2007/10/02)
Thermal decomposition of Me2XSi-CLi(SiMe3)2 (1,LiX) in diethyl ether at -102 to 10 deg C leads under intramolecular LiX-elimination (X = Hal, TosO, Ph2POn, PhS) to 1,3-disilacyclobutane 2 (2).The reactive intermediate product is the silae
On the Way to Silaethene Me2Si=C(SiMe3)2: Trisilylated Methanes (Me3Si)2(Me2XSi)CY (X=e. g. Hal, RO, RS; Y e. g. Br, Li)
Wiberg, Nils,Preiner, Gerhard,Schieda, Oswald
, p. 2087 - 2103 (2007/10/02)
Bromotrisilylmethanes (Me3Si)2(Me2XSi)CBr (1 - 15) are formed as a result of the reaction of (Me3Si)2(Me2PhSi)CBr (16) with iodine monochloride, bromine and iodine (X = Cl, Br, I) respectively, and also through the reaction of (Me3Si)2(Me2BrSi)CBr (1) with AgX (X = F, p-TolSO2, p-TolSO3, MesSO3, Ph2PO2, Ph2PO3, Ph2PO4) or MX (M = H, Li, Na; X = HO, RO, RS, Bu, Ph).Butyl- as well as phenyllithium convert bromotrisilylmethanes 1 - 16 at low temperatures into lithium derivatives (Me3Si)2(Me2XSi)CLi (1a - 16a).These are in some cases (X = R, RO) thermostable, whereas, in other cases they decompose more or less readily under LiX elimination and lead (in many cases via silaethene Me2Si=C(SiMe3)2) to the disilacyclobutane derivative 2 (17).Acids HZ (e. g.HCl, HOMe, Me3CBr) protonate the lithium compounds into (Me3Si)2(Me2XSi)CH as well as (Me3Si)2(Me2ZSi)CH.Butyl bromide converts the more stable lithium compounds (Me3Si)2(Me2XSi)CLi (X = R, RO, F, Ph2POn) into butyl derivatives (Me3Si)2(Me2XSi)CBu.
