Synthesis of functional derivatives of stereoregular organocyclosilsesquioxanes by thiol-ene addition

Well-defined cyclic silanol derivatives

“…84 Recently, they demonstrated that the vinyl groups of previously developed all-cis-tetravinylcyclotetrasiloxanes (52 and 69) can be easily modified by thiol-ene addition. 85 (c) Bond extension of all-cis-T 4 . All-cis-T 4 with different functional groups attached to opposite sides of the ring skeleton can be functionalized selectively on each face through typical organic transformations like hydrosilylation, C-C coupling reaction, Piers-Rubinsztajn and thiol-ene reaction, allowing the synthesis of a wide range of Janus-type cyclotetrasiloxanes.…”

“…The behavior at the water/air interface of compound 132 shows its high potential of utilization as an agent for hydrophobic surface treatment (Table 10). 85…”

The Use of the Thiol-Ene Addition Click Reaction in the Chemistry of Organosilicon Compounds: An Alternative or a Supplement to the Classical Hydrosilylation?

“…These compounds are synthesized from polyhedral metallosiloxanes and cannot be obtained by the classical organosilicon chemistry reactions. The possibility of modifying all-cis-tetravinyl-tetrakis(trimethylsiloxy)cyclotetrasiloxane and cis-tetravinyl-tetrakis(dimethylvinylsiloxy)cyclotetrasiloxane with various polar fragments by the hydrothiolation reaction was shown [ 96 ]. In particular, an amphiphilic “Janus” cycle was obtained (see Figure 22 ); compounds of this class are very much in demand in supramolecular chemistry because of their ability to undergo self-organization under various conditions.…”

Thiolated Janus Silsesquioxane Tetrapod: New Precursors for Functional Materials

“…Janus T4 tetrapods, i.e., with different o functions on opposite faces, are thus obtained by the condensation of a comme available chlorosilane on a T4 tetrasilanolate [11]. Using this functionalization approach, several functional Janus tetrapod silses anes have now been reported, together with details of their synthesis in some cases ( 2) [11,23,24,[37][38][39][40][41][42][43][44][45][46][47][48][49][50][51]. To the best of our knowledge, these T4 compounds have all bee tionalized on the silanol/silanolate face of the precursor molecule via condensatio tions with commercially available chlorosilanes, to yield a Janus tetrapod silsesqu However, post-functionalization can be realized either on the Si-O-SiMe2R face, ma hydrosilylation [37][38][39][41][42][43]50,51] or by the Piers-Rubinsztajn reaction [23,24]; or Si-C face using a wide range of standard reactions including Suzuki [44], Sonog [11,45] and Heck coupling reactions [11,45,47], etc.…”

“…Herein, we report the development of a new bifunctional Janus T4 tetrapod, in the orthogonal silsesquioxane and organic faces are independently functionalized ( Using this functionalization approach, several functional Janus tetrapod silsesquioxanes have now been reported, together with details of their synthesis in some cases (Figure 2) [11,23,24,[37][38][39][40][41][42][43][44][45][46][47][48][49][50][51]. To the best of our knowledge, these T 4 compounds have all been functionalized on the silanol/silanolate face of the precursor molecule via condensation reactions with commercially available chlorosilanes, to yield a Janus tetrapod silsesquioxane.…”