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 Si−H‐functionalization. A thorough kinetic study allowed us to identify two “complementary” catalytic systems based on earth‐abundant [M]‐catalysts and inexpensive commercially available organic catalysts. The first system, Co(OAc) 2 /N‐hydroxysuccinimide, made it possible to oxidize a Si−H‐group to a Si−OH‐group 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 Si−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.