75-76-3Relevant articles and documents
Structural tracking of the potassium-mediated magnesiation of anisole
Clegg, William,Conway, Ben,Garcia-Alvarez, Pablo,Kennedy, Alan R.,Mulvey, Robert E.,Russo, Luca,Sassmannshausen, Joerg,Tuttle, Tell
, p. 10702 - 10706 (2009)
Final destination: The potassium-mediated magnesiation of anisole has been monitored by a combination of X-ray crystallographic and NMR spectroscopic studies. Departing from a heteroleptic alkyl-amido base and anisole, the reaction first stops at an ortho
Catalytic Difunctionalization of Unactivated Alkenes with Unreactive Hexamethyldisilane through Regeneration of Silylium Ions
Wu, Qian,Roy, Avijit,Irran, Elisabeth,Qu, Zheng-Wang,Grimme, Stefan,Klare, Hendrik F. T.,Oestreich, Martin
, p. 17307 - 17311 (2019)
A metal-free, intermolecular syn-addition of hexamethyldisilane across simple alkenes is reported. The catalytic cycle is initiated and propagated by the transfer of a methyl group from the disilane to a silylium-ion-like intermediate, corresponding to the (re)generation of the silylium-ion catalyst. The key feature of the reaction sequence is the cleavage of the Si?Si bond in a 1,3-silyl shift from silicon to carbon. A central intermediate of the catalysis was structurally characterized by X-ray diffraction, and the computed reaction mechanism is fully consistent with the experimental findings.
Polymer and metal oxide supported alkali metal naphthalenides: Application in the generation of lithium and sodium reagents
Van Den Ancker, Tania R.,Raston, Colin L.
, p. 283 - 300 (1998)
Highly coloured paramagnetic polymer supported lithium 5,5′ and sodium 6,6′ naphthalenide complexes have been prepared from the reaction of THF solutions of lithium and sodium biphenylide with polystyrene bearing -CH2SiMe2(C10H7) groups. Treating chloropropyl functionalised silica, alumina and titania surfaces with H3Al · NMe3 or H3Ga · NMe3 afford hydroxyl depleted surfaces. Successive treatment with lithium biphenylide, 1-(chlorodimethylsilyl)naphthalene and an alkali biphenylide affords supported alkali naphthalenide complexes which generate in high yield lithium and sodium reagents when treated with a range of organic halides, nitriles and phosphates, as found for 6,6′ and 7,7′.
Bildung siliciumorganischer Verbindungen. CVII. Bildung und Struktur des trans-trans-trans-Nonamethyl-hexasilaperhydrophenalens
Fritz, G.,Volk, H.,Straub, M.,Schnering, H. G. von,Peters, K.,Peters, E.-M.
, p. 109 - 118 (1988)
trans-trans-trans-2,2,4,6,6,8,10,10,12-Nonamethyl-2,4,6,8,10,12-hexasilaperhydrophenalene 6 (m.p. 170 deg C) is formed from the substituted cyclic carbosilane 3 at 25 deg C (5 h) in the presence of AlBr3 by elimination of SiMe4.At 35 deg C (5 h) the formation of the all-cis-isomer 6a is observed in addition to 6.On the other hand the thermal transformation of 6 into 6a was not observed below 420 deg C.None of the other possible isomers were detected.Compound 6 reacts with MeLi to give 7 via lithiation of the central C atom.The hydrolysis of 7 leads to a mixture of 6 and 6a in a 2/1 ratio.Compound 6 crystallizes orthorhombically space group P212121 (no.19); a = 2221.3, b = 1651.3, c = 667.3 pm; Z = 4; 2169 hkl; R = 0.053).Owing to the different size of the substituents on both sides of the polycyclic system the molecule is arched and the six-membered rings are flattened.The Si-C bond lengths decrease progressively from the central C atom to the periphery of the molecule(188.5 to 186.2 pm).It is shown that only the curvature of the polycyclic system causes a decrease in the endocyclic bond angles at the Si atoms (to 108.2 deg) and an increase in those at the C atoms (to 118.0 deg) as well as the flattening of the six-membered rings.
A General and Selective Synthesis of Methylmonochlorosilanes from Di-, Tri-, and Tetrachlorosilanes
Naganawa, Yuki,Nakajima, Yumiko,Sakamoto, Kei
supporting information, p. 601 - 606 (2021/01/13)
Direct catalytic transformation of chlorosilanes into organosilicon compounds remains challenging due to difficulty in cleaving the strong Si-Cl bond(s). We herein report the palladium-catalyzed cross-coupling reaction of chlorosilanes with organoaluminum reagents. A combination of [Pd(C3H5)Cl]2 and DavePhos ligand catalyzed the selective methylation of various dichlorosilanes 1, trichlorosilanes 5, and tetrachlorosilane 6 to give the corresponding monochlorosilanes.
Hydrodechlorination of (CH3)3SiCHCl2 over Pd, Ni, Co and Fe supported on AlF3
Hina, Rateb,Arafa, Isam,Ennab, Omar
, p. 353 - 358 (2017/03/23)
Gas phase hydrodechlorination (HDC) process of Me3SiCHCl 2 was studied in a flow reactor at 200 °C using a 2% metal loading (w/w) of four different monometallic catalysts (Pd/AlF 3, Ni/AlF 3,Co/AlF 3 and Fe/AlF 3). The catalysts were prepared by sol-gel method and structurally examined by BET method, FT-IR and XPS techniques. The XPS technique showed that Ni II, Fe III and Co III exist as oxides. The major products in the HDC process of Me 3SiCHCl 2 were identified by GC and GC-MS and found to include Me 3SiCH 2Cl, Me 3SiCl, and Me 4Si. The effect of these catalysts on the quantitative conversion, selectivity and conversion rates are reported. [Figure not available: see fulltext.]
