Synthesis of Silicon-Functionalized (Silylmethyl)silanes and 伪,蠅-Dichlorocarbosilanes Using the TMOP (2,4,6-Trimethoxyphenyl) Protecting Group: (TMOP)Me2SiCH2Cl and (TMOP)2<

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• 作者：Nadine Laskowski ; Eva-Maria Reis ; Lisa K枚tzner ; Johannes A. Baus ; Christian Burschka ; Reinhold Tacke
• 刊名：Organometallics
• 出版年：2013
• 出版时间：June 10, 2013
• 年：2013
• 卷：32
• 期：11
• 页码：3269-3278
• 全文大小：408K
• 年卷期：v.32,no.11(June 10, 2013)
• ISSN：1520-6041

文摘

In this study, the synthetic potential of the 2,4,6-trimethoxyphenyl (TMOP)-substituted (chloromethyl)silanes (TMOP)Me₂SiCH₂Cl (1) and (TMOP)₂MeSiCH₂Cl (2) for the preparation of Si-functionalized (silylmethyl)silanes and 伪,蠅-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)₂MeSiCH₂MgCl, and (TMOP)₂MeSiCH₂Li, 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).