Synthesis of Silicon-Functionalized (Silylmethyl)silanes and α,ω-Dichlorocarbosilanes Using the TMOP (2,4,6-Trimethoxyphenyl) Protecting Group: (TMOP)Me2SiCH2Cl and (TMOP)2MeSiCH2Cl as Reagents To Introduce the ClMe2SiCH2, MeOMe2SiCH2, or Cl2MeSiCH2 Group by Nucleophilic Substitution at Silicon

In this study, the synthetic potential of the 2,4,6-trimethoxyphenyl (TMOP)-substituted (chloromethyl)silanes (TMOP)Me2SiCH2Cl (1) and (TMOP)(2)MeSiCH2Cl (2) for the preparation of Si-functionalized (silylmethyl)silanes and alpha,omega-dichlorocarbosilanes (with skeletons consisting of alternate carbon and silicon atoms) was investigated. Compounds 1 and 2 were used as reagents to introduce the ClMe2SiCH2, MeOMe2SiCH2, or Cl2MeSiCH2 group by nucleophilic substitution at silicon. The three-step synthetic method involves the (i) transformation of 1 and 2 into (TMOP)Me2SiCH2MgCl, (TMOP)Me2SiCH2Li, (TMOP)(2)MeSiCH2MgCl, and (TMOP)(2)MeSiCH2Li, respectively, (ii) reaction of these nucleophiles with chloro- or methoxysilanes, and (iii) subsequent selective cleavage of the TMOP protecting group with HCl/Et2O or MeOH/[CF3COOH]. Using this method, the following compounds were prepared: ClMe2SiCH2SiMe3 (3), ClMe2SiCH2SiMe2Cl (4), ClMe2SiCH2SiMeCl2 (5), ClMe2SiCH2SiCl3 (6), ClMe2SiCH2Si(OMe)(3) (7), MeOMe2SiCH2Si(OMe)(3) (8), Cl2MeSiCH2SiMe3 (9), Me2Si(CH2SiMe2Cl)(2) (10), and Me2Si(CH2SiMe2CH2SiMe2Cl)(2) (11).