A new method for the preparation of 1-(chloromethyl)- and 1-(dichloromethyl)silatranes

Lazareva, N. F.; Lazarev, I. M.

doi:10.1007/s11172-018-2285-2

Cited by 2 publications

(1 citation statement)

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“…In terms of synthesis, in most cases the hypercoordinate silicon compounds featuring a chloromethyl group are obtained from the corresponding chloromethylsilane derivatives bearing three alkoxy groups or halogens on the silicon [ 5 , 6 , 7 , 8 , 9 , 10 ]. The direct introduction of the chloromethyl group to the silicon part has been described only once by the group of Lazareva for the formation of chloromethylsilatrane [ 11 ]. In this procedure, the chloromethyl group is introduced by mixing bromochloromethylene and a tris(amino)phosphine in the presence of a chlorosilatrane at high temperature ( Figure 1 ).…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Reactivity of Martin’s Spirosilane-Derived Chloromethylsilicate

et al. 2022

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Pentacoordinate silicon derivatives with a chloromethyl ligand are versatile compounds that are usually obtained from the corresponding tetravalent trialkoxy- or trihalogeno(chloromethyl)silane. We describe herein the synthesis of a chloromethylsilicate bearing two Martin’s ligands readily obtained by addition of in situ generated chloromethyllithium to a spirosilane. The reactivity of this new species was evaluated and it has been established that the chloride is displaced by strong nucleophiles such as alkyllithiums and (hetero)aryllithiums. In Lewis acidic conditions, the pentacoordinate silicon species rearranges through a formal insertion of a methylene into one Si–C bond, to form a new tetravalent spirosilane with a six-membered ring. The same kind of rearrangement can be triggered also by addition of a Lewis base. The mechanism of the rearrangement in both conditions has been studied by means of DFT calculations.

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