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

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.

Alkenyl-Functionalized Open-Cage Silsesquioxanes (RSiMe2O)3R′7Si7O9: A Novel Class of Building Nanoblocks

“…Analogue influence of the t -Bu and (CH 3 ) 2 OSi(CH 3 ) 3 groups on forming the product of monohydrosilylation of 1,3-diynes was previously observed. 69 , 70 …”

Hydroelementation of diynes

“…Depending on the type of the catalyst, reagents, their concentration, ratio, and process conditions, silylated 1,3-enynes, 1,3dienes, or allenes can be formed, frequently as a complex mixture of products (up to nine different compounds can potentially be formed). 62,73,74,156,164 Many papers describe the hydrosilylation of monoalkynes, 14,41,48,49,51 but the addition of the Si-H bond to 1,3-diynes is much more demanding and limited only to a few papers. The hydrosilylation of 1,3-diynes occurs mainly in the presence of noble metal complexes (Rh, Pt, Pd, Ru).…”

“…Our recent papers focused on the hydrosilylation of 1,3-diynes with silanes or silsesquioxanes in the presence of commercially available platinum complexes give the first detailed research which discusses the influence of several parameters on the hydrosilylation selectivity. 73,74,165 In a report by Perry et al the synthesis of conjugated polymers from 1,3-diynes and bis(silylhydrides) were described. The products were obtained via hydrosilylation reactions in the presence of Karstedt's catalyst 194.…”

“…[63][64][65][66][67][68][69][70][71] Working on the hydroboration and hydrosilylation of various unsaturated compounds and especially on the reactivity of conjugated 1,3-diynes in these processes, we have found that literature information is often scattered, with no detailed procedures or much discussion on the process optimisation or methodology. [72][73][74][75][76][77][78][79][80][81][82][83][84][85][86][87] Therefore, we have decided to build a comprehensive and critical compendium focused on this subject, which will systemise the existing knowledge on the hydroelementation of diynes in relation to the formation of different products. We will also show the possible applications of the obtained products in the synthesis of fine chemicals and materials.…”

Formation of Bifunctional Octasilsesquioxanes via Silylative Coupling and Cross-Metathesis Reaction

“…The simple functionalization of the inorganic core, as well as of the organic moieties attached to it, allows one to create various structures and to control the properties of the obtained materials. Among the highly valuable synthetic procedures for the functionalization of silsesquioxanes (SQs), we can list Heck coupling [ 3 , 4 , 5 ], Sonogashira coupling [ 6 ], hydrosilylation [ 7 , 8 , 9 , 10 , 11 , 12 , 13 , 14 , 15 ], cross-metathesis (CM) [ 16 , 17 , 18 , 19 ], silylative coupling (SC) [ 20 ], O -silylation [ 21 , 22 ] and Friedel–Crafts [ 23 ]. They are all dependent on the type of the functional group attached to the Si–O–Si (SiHC=CH 2 , SiH SiOH).…”