Synthesis of bulky tris{[}(dimethyl(alkyl/aryl)silyl)methyl]stannanes as radical based reducing agents

The synthesis of novel bulky tris{[}dimethyl(ethyl/benzyl/p-tolyl/alpha-naphthyl)silylmethyl]stannane s (1-4) is described. Alkylation of SnCl(4) with Me(2)(ethyl/p-tolyl)SiCH(2)MgBr (10-11) gave mainly the triorganotin chlorides {[}(Me(2)(ethyl/p-tolyl)SiCH(2))](3)SnCl 14 and 15, which were isolated by silica gel chromatography. Reduction of 14 and 15 with LiAlH(4) in THF gave the corresponding triorganotin hydrides 1 and 2, respectively. {[}Me(2)(benzyl/alpha-naphthyl)SiCH(2)](3)SnCl 16 and 17, generated by the alkylation of SnCl(4) with Me(2)(benzyl/alpha-naphthyl) SiCH(2)MgBr 12 and 13, were inseparable from the minor product {[}Me(2)(benzyl/alpha-naphthyl)SiCH(2)](2)SnCl(2) 18 and 19, respectively. Treatment of the mixtures of 16/18 and 17/19 with NaOH furnished the corresponding mixtures of stannoxanes, from which the hexakisdistannoxanes {[}Me(2)(benzyl/alpha-naphthyl)SiCH(2)](6)Sn(2)O 20 and 22 were isolated from the minor dialkyltin oxide derivatives {[}Me(2)(benzyl/alpha-naphthyl)SiCH(2)](2)SnO in good yields. Reduction of 20 and 22 with BH(3) in THF gave {[}Me(2)(benzyl/alpha-naphthyl)SiCH(2)](3)SnH (3 and 4), respectively in good yields. (1)H, (13)C, (119)Sn, (29)Si NMR characteristics of the newly synthesized compounds are included. (C) 2011 Elsevier B. V. All rights reserved.