Synthesis of Functional 3‐Buten‐1‐ynes and 1,3‐Butadienes with Silsesquioxane Moiety <i>via</i> Hydrosilylation of 1,3‐Diynes

Abstract

Abstract Highly effective procedures for the addition of one or two molecules of 1‐dimethylsiloxy‐3,5,7,9,11,13,15‐heptaisobutylpentacyclo‐[9.5.1.1 3,9 .1 5,15 .1 7,13 ]octasiloxane ((HSiMe 2 O)( i ‐Bu) 7 Si 8 O 12 , ( 1 )) to the symmetrically 1,4‐disubstituted 1,3‐diynes have been successfully developed for the first time. As a result, novel silsesquioxanes bearing substituents such as CH 3 , t ‐Bu, (CH 3 ) 2 OSi(CH 3 ) 3 , C 6 H 5 , C 6 H 4 Br‐4, C 6 H 4 (BO 2 C 2 (CH 3 ) 4 )‐4, OH, COOCH 3 , and morpholino were obtained and characterized by 1 H, 13 C, 29 Si NMR and mass spectrometry. Detailed optimization of reaction conditions was performed with a wide range of temperatures, in the presence of various types of catalysts and ratios of reagents, to obtain complex information about the process selectivity and develop efficient methods for synthesizing targeted compounds. It was found that precisely optimized approaches provided 3‐buten‐1‐ynes or 1,3‐butadienes with high yields, without decomposition of other reactive functionalities presented in the molecule structure. Due to the presence of reactive functional groups, the resulting compounds constituted a new silsesquioxane family characterized by unique structures and potential applications.