18001-47-3Relevant articles and documents
Tris(trimethylsilyl) titanacyclobutene: A new mild reagent for the conversion of carbonyls to alkenyl silanes
Petasis, Nicos A.,Staszewski, James P.,Fu, Dian-Kui
, p. 3619 - 3622 (1995)
Thermolysis of Cp2Ti(CH2SiMe3)2 in the presence of Me3SiC≡CSiMe3 forms tris(trimethylsilyl) titanacyclobutene. Unlike other titanacyclobutenes which undergo insertion with carbonyl compounds, this reagent serves as a precursor to Cp2Ti=CHSiMe3, converting carbonyl compounds to the corresponding alkenyl silanes. This olefination takes place under mild conditions even at room temperature and works with aldehydes, ketones, esters, thioesters and lactones.
Design, Synthesis, and Implementation of Sodium Silylsilanolates as Silyl Transfer Reagents
Yamagishi, Hiroki,Saito, Hayate,Shimokawa, Jun,Yorimitsu, Hideki
, p. 10095 - 10103 (2021/08/18)
There is an increasing demand for facile delivery of silyl groups onto organic bioactive molecules. One of the common methods of silylation via a transition-metal-catalyzed coupling reaction employs hydrosilane, disilane, and silylborane as major silicon sources. However, the labile nature of the reagents or harsh reaction conditions sometimes render them inadequate for the purpose. Thus, a more versatile alternative source of silyl groups has been desired. We hereby report a design, synthesis, and implementation of storable sodium silylsilanolates that can be used for the silylation of aryl halides and pseudohalides in the presence of a palladium catalyst. The developed method allows a late-stage functionalization of polyfunctionalized compounds with a variety of silyl groups. Mechanistic studies indicate that (1) a nucleophilic silanolate attacks a palladium center to afford a silylsilanolate-coordinated arylpalladium intermediate and (2) a polymeric cluster of silanolate species assists in the intramolecular migration of silyl groups, which would promote an efficient transmetalation.
Copper-NHC-Mediated Semihydrogenation and Hydroboration of Alkynes: Enhanced Catalytic Activity Using Ring-Expanded Carbenes
Hall, Jonathan W.,Unson, Darcy M. L.,Brunel, Paul,Collins, Lee R.,Cybulski, Mateusz K.,Mahon, Mary F.,Whittlesey, Michael K.
supporting information, p. 3102 - 3110 (2018/09/12)
A series of two-coordinate copper tert-butoxide complexes bearing five-, six-, and seven-membered ring N-heterocyclic carbenes, prepared by protonolysis of (NHC)CuMes with tBuOH, have been used as catalytic precursors in the semihydrogenation of alkynes with silanes/tBuOH and the hydroboration of alkynes with HBPin. Both processes proceed with high regioselectivity and show enhancements with six- and seven-membered ring carbenes.
Phenylethenyl-substituted silicones via Heck coupling reaction
Czech, Anna,Ganicz, Tomasz,Noskowska, Ma?gorzata,Stańczyk, W?odzimierz A.,Szelag, Anna
experimental part, p. 3386 - 3389 (2010/01/11)
Systematic studies of several palladium complexes (Pd(OAc)2, [PdCl2(cod)], [Pd2(dba)3], [Pd(PPh3)4], [PdCl(SnCl3)(P{p-Tol}3)2], [Pd2Cl2(SnCl3)su