Peroxygenase‐Catalysed Selective Oxidation of Silanes to Silanols

Abstract

A peroxygenase-catalysed hydroxylation of organosilanes is reported. The recombinant peroxygenase from Agrocybe aegerita (AaeUPO) enabled efficient conversion of a broad range of silane starting materials in attractive productivities (up to 300 mM h À 1 ), catalyst performance (up to 84 s À 1 and more than 120 000 catalytic turnovers). Molecular modelling of the enzyme-substrate interaction puts a basis for the mechanistic understanding of AaeUPO selectivity.

Rhodium-Catalyzed Hydrolytic Cleavage of the Silicon–Carbon Bond of Silacyclobutanes to Access Silanols

“…13 In general, there are two primary approaches for introducing the Si−OH group into organosilicon compounds (Figure 1): (1) through the hydrolysis of Si−Cl, Si−OR, or Si−NR 2 in the presence of an acid or base catalyst 14 and (2) via oxidation or hydrolysis of Si−H (Figure 1b). 15 However, these methods often lead to side reactions, such as further condensation of the desired Si−OH groups or the formation of complex mixtures of siloxanes that are challenging to separate. 13b Consequently, despite the considerable potential of Si−H or Si−X bond hydroxylation for silanol synthesis, achieving a clean synthesis of silanols without side reactions remains a limited but highly desirable goal.…”