Silanetriols as Powerful Starting Materials for Selective Condensation to Bulky POSS Cages

硅烷三醇作为选择性缩合生成大体积POSS笼状化合物的强效起始原料

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Abstract

Controlled condensation reactions of tertiary silanetriols CH(3)(CH(2)) (n) (CH(3))(2)CSi(OH)(3) (1b-f; n = 1-5) in the presence of trifluoroacetic acid and the hydrolysis of CH(3)(CH(2))(6)(CH(3))(2)CSiCl(3) (3) lead to the selective formation of the corresponding disiloxane tetrols [CH(3)(CH(2)) (n) (CH(3))(2)CSi(OH)(2)](2)O (2b-g; n = 1-6) in good yields. The TBAF-driven condensation reactions of the silanetriols CH(3)(CH(2)) (n) (CH(3))(2)CSi(OH)(3) (1a-c; n = 0-2) as well as of the disiloxane-1,1,3,3-tetrol 2d (n = 3) yield in the selective formation of the first T(8) cages bearing tertiary carbon substituents, CH(3)(CH(2)) (n) (CH(3))(2)C (4a-d; n = 0-3), which was not possible via the condensation of their alkoxysilane counterparts so far. The resulting compounds 2b-g and 4a-d have been characterized by multinuclear NMR, MS, and single-crystal X-ray diffraction.

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