5410-07-1Relevant articles and documents
On the reactivity of silylboranes toward lewis bases: Heterolytic B-Si cleavage vs. adduct formation
Kleeberg, Christian,Borner, Corinna
, p. 2799 - 2806 (2013/07/11)
Silylboranes are important reagents in a variety of catalytic silylation and silaboration reactions. While transition-metal-catalyzed reactions are well established, organo-/Lewis base-catalyzed reactions of silylboranes have only recently emerged. For both catalytic processes the reactivity of silylboranes toward Lewis bases is of relevance. While for organo-catalyzed reactions Lewis base activation of the silylborane has been proposed, transition-metal- and especially copper-catalyzed reactions also frequently require the presence of Lewis basic alkali metal alkoxides. In the present study we explore the reaction of K(18-crown-6) tert-butoxide and the NHC 1,3-diisopropyl-4,5-dimethyl- imidazol-2-ylidene as exemplary Lewis bases with the two silylboranes pinB-SiMe2Ph and pinB-SiPh3 (pin = OCMe 2CMe2O). The reaction with K(18-crown-6) tert-butoxide results in activation of the boron-silicon bond. The isolated product of this activation is either the potassium silyl complex [K(18-crown-6)SiPh3] or [K(18-crown-6)(thf)2][pinB(SiMe2Ph)2], the formal Lewis acid/base adduct of [K(18-crown-6)SiMe2Ph] with pinB-SiMe2Ph. Both complexes react essentially as sources of nucleophilic silyl moieties in reactions with exemplary electrophiles. In contrast, usage of the carbene leads to the formation of isolable Lewis acid/base adducts of the type (NHC)pinB-SiR3, which do not react as sources of nucleophilic silyl moieties. The identification and characterization of these species appears of relevance for the mechanistic understanding and further development of Lewis base/organo- as well as transition-metal-catalyzed silyl transfer reactions. Copyright
Acceleration of the substitution of silanes with Grignard reagents by using either LiCl or YCl3/MeLi
Hirone, Naoki,Sanjiki, Hiroaki,Tanaka, Ryoichi,Hata, Takeshi,Urabe, Hirokazu
supporting information; experimental part, p. 7762 - 7764 (2010/12/25)
Getting up to speed: Both LiCl and the YCl3/MeLi catalyst system have an acceleration effect upon the substitution of silanes using Grignard reagents (see scheme). The method provides access to benzyl-, allyl-, and arylsilanes in good yields from the starting silanes.
Les triorganosilylpotasium: nouvelle voie d'acces et quelques aspects de leur reactivite
Corriu, R. J. P .,Guerin, C.,Kolani, B.
, p. 973 - 979 (2007/10/02)
We report here a new procedure for the convenient and easy preparation of silylanions and especially of Me3Si-.These undergo coupling reaction with halides and α-enone in good yields.Reactions with 5-bromo-1 hexene, benzophenone and carbon dioxide provide evidence for the ability of the silylpotassium to act as monoelectron transfer reagents.The course of these reactions varies substantially with the nature of the solvent.
SUBSTITUENT EFFECTS OF SOME ORGANOSILYLMETHYL GROUPS
Eaborn, Colin,Hancock, Alan R.,Stanczyk, Wlodzimierz A.
, p. 147 - 154 (2007/10/02)
The charge transfer frequencies for some tetracyanoethylene-PhX complexes have been used to derive ?+p constants and 13C NMR data to derive ?0R constants for the X groups, with the following results (X, -?+
Alkali Metal Hydrides: New Metallating Reagents at Silicon
Corriu, Robert J. P.,Guerin, Christian
, p. 168 - 169 (2007/10/02)
New procedures for the preparation of organo-silyl-sodium or potassium, which undergo coupling reactions with alkyl, allyl, and benzyl halides and α-enones, are reported.
