Complementary Cooperative Catalytic Systems in the Aerobic Oxidation of a Wide Range of Si−H‐Reagents to Si−OH‐Products: From Monomers to Oligomers and Polymers

Abstract

The article presents an in-depth study of the applicability of cooperative [M]-/Organo-catalytic systems in aerobic SiÀ Hfunctionalization. A thorough kinetic study allowed us to identify two "complementary" catalytic systems based on earthabundant [M]-catalysts and inexpensive commercially available organic catalysts. The first system, Co(OAc) 2 /N-hydroxysuccinimide, made it possible to oxidize a SiÀ H-group to a SiÀ OHgroup in a wide range of monomers, including previously unknown ones, that dramatically differ in their reactivity. However, this system failed in the case of oligomeric and polymeric substrates. This problem was solved by application of the Cu(OAc) 2 /N-hydroxyphthalimide system. A wide potential for gram-scale (50-100 g) preparation of SiÀ OH-containing products with molecular architectures of different complexity was revealed using the established "substrate-reactivity-catalytic system" relationship. In particular, previously unknown types of dumbbell-shaped and graft polymers were synthesized using alkoxysilanols.

Oxidation of Hydrosilanes to Silanols by Peracetic Acid

“…In addition to transition metals supported on carbon, other heterogeneous catalysts employed to synthesize silanes include gold polyoxometalates and titanium zeolites . Other oxidations have been reported via organocatalysis, , cooperative catalyst systems, organic photoredox, electrochemical synthesis, and enzymatic catalysis . Reviews focused on silanol structure and general synthesis as well as transition-metal-catalyzed oxidation of hydrosilanes have been published and contain a more comprehensive overview of the literature.…”

Siloxane-containing derivatives of benzoic acid: chemical transformation of the carboxyl group

“…Further, over the past 10–20 years, there have been a number of works on their synthesis and application. 16 Thus, polymers based on p -carboxy-phenylsiloxanes were obtained, HOFs and MOFs. 16 However, with regard to the chemical transformation of the carboxyl group of p -carboxy-phenylsiloxanes into the corresponding amides, esters, thioesters, etc.…”

“…16 Thus, polymers based on p -carboxy-phenylsiloxanes were obtained, HOFs and MOFs. 16 However, with regard to the chemical transformation of the carboxyl group of p -carboxy-phenylsiloxanes into the corresponding amides, esters, thioesters, etc. , there are practically no data in the literature.…”