Discovery and synthetic applications of novel silicon-carbon bond cleavage reactions based on the coordination number change of organosilicon compounds

Abstract

Some synthetically useful transformations of organosilicon compounds have been developed since the mid 1970s, based on the new concept that the silicon-carbon bonds are activated toward electrophilic cleavage via the formation of penta- and hexa-coordinate species. This review mainly consists of the following aspects: (1) a general concept for the activation of the silicon-carbon bond via penta- and hexa-coordinate species, (2) synthetic application of hexa-coordinate organopentafluorosilicates, and (3) development of the H2O2 oxidation of the silicon-carbon bond and its synthetic applications via the intramolecular hydrosilylation, silicon-tethered intramolecular radical cyclization and Diels-Alder reaction, and some silicon-containing organometallic reagents for nucleophilic hydroxymethylation and hydroxyallylation synthons.

Stereoselective synthesis of protected l- and d-dideoxysugars and analogues via Prins cyclisations

“…Whilst dimethylphenylsilanes have been widely used,10 Hosomi and co-workers reported the benzyldimethylsilyl group (BDMS) as an attractive alternative that is readily oxidised to alcohols 11. An important criterion for our synthetic strategy was that the electrophile should be stable and readily prepared on a synthetically valuable scale.…”

Si-C Coupling Reaction of Hydrosilane with Activated Organic Compounds: A Facile Synthetic Route to Organosilicon Compounds

“…At first, a trifunctional molecule containing one cobaltabisdicarbollide and three vinylsilane moieties has been de-veloped starting with tetravinylsilane. New type carbosilane dendrimer is prepared with peripheral multiple functionalities capable of being tied to a calix [4]arene unit, which can bind with a metal cation. It has been possible to apply this procedure to vinyl-terminated cyclocarbosiloxane dendrimers to yield metallodendrimers containing four and eight peripheral cobaltabisdicarbollide units [26].…”

“…The reaction of G2 with 12 mol of the linker-attached calix [4]arene 1c afforded the 2 st generation carbosilane attached to twelve calix [4]arene units (Fig. Hydrosilylation of G1 with 1a to give G2p with 12 Si-Cl units, then reacted with 12 allylmagnesium bromides to lead to G2 with 12 allyl groups.…”

“…Hydrosilylation of G1 with 1a to give G2p with 12 Si-Cl units, then reacted with 12 allylmagnesium bromides to lead to G2 with 12 allyl groups. Dendrimers G3-G5 tipped with allyl groups reacted with n-calix-(CH 2 ) 3 -SiMe 2 -SiMe 2 -H (1c ) to give the corresponding dendritic generations with calix [4]arenas [27]. 3).…”

“…Organosilicon compounds such as allylsilanes [1,2], arylsilanes, vinylsilanes [3], arylfluorosilanes and alkylfluorosilanes [4], and hydrosilanes [5] play an increasingly important role in synthetic organic chemistry [6]. Organosilicon compounds such as allylsilanes [1,2], arylsilanes, vinylsilanes [3], arylfluorosilanes and alkylfluorosilanes [4], and hydrosilanes [5] play an increasingly important role in synthetic organic chemistry [6].…”