Stepwise Introduction of Different Substituents to α-Chloro-ω-hydrooligosilanes: Convenient Synthesis of Unsymmetrically Substituted Oligosilanes

Abstract

A series of unsymmetrically substituted oligosilanes were synthesized via stepwise introduction of different substituents to α-chloro-ω-hydrooligosilanes. The reactions of α-chloro-ω-hydrooligosilanes with organolithium or Grignard reagents gave hydrooligosilanes having various alkyl, alkenyl, alkynyl and aryl groups. Thus-obtained hydrooligosilanes were converted into alkoxyoligosilanes by ruthenium-catalyzed dehydrogenative alkoxylation with alcohols.

Oligosilanes as Silyl Radical Precursors through Oxidative Si−Si Bond Cleavage Using Redox Catalysis

“…[1a, 3] Considering material properties, installation of additional functionalities to the oligosilane backbone is of importance. In this regard, oligosilanyl halides [3,4] and oligosilanyl hydrides [3] have been identified as substrates for modification of oligosilanes through reductive couplings, [1a] Lewis acid-catalyzed transformations, [5] radical processes [6] or transition metal-catalyzed reactions (Scheme 1 a). [7] However, these methods show limited applicability due to their relatively harsh conditions that lead to competing SiÀSi bond cleavage.…”

Coordination Chemistry of Silicon

“…The review article by Ohshita and coworkers comprehensively outlines works related to the utilization of disilanylene polymers to modify the TiO 2 surface and their applications in dye-sensitized solar cells [19]. Kanno, Kyushin, and coworkers describe new straightforward synthetic methods for unsymmetrically substituted oligosilanes with various functional groups [20]. Reactions with organolithium or Grignard reagents and ruthenium-catalyzed alkoxylations were employed for the substitution of each functional group.…”