Activation of O₂ by Organosilicon Reagents Yields Quantitative Amounts of H₂O₂ or (Me₃Si)₂O₂ for Efficient O‐Transfer Reactions

Abstract

Abstract Molecular oxygen is kinetically inert and rarely used as a primary oxidant for low temperature selective oxygenation reactions. Here, we show that O 2 is converted into H 2 O 2 in almost quantitative yields (98 %) at ambient temperature and atmospheric pressure in the presence of bis(trimethylsilyl)‐1,4‐cyclohexadiene 1 . Similarly, the reaction of O 2 with dihydro‐bis(trimethylsilyl) viologen 2 and pyrazine 3 yields bis(trimethylsilyl) peroxide (BTSP) in excellent yields (up to 99 %) at low temperature. Both processes demonstrate that readily available organosilicon reagents enable chemistry typically observed with mono‐oxygenase co‐enzymes, such as FADH 2 and FMNH 2 , in biological systems, or at higher pressure via the industrial anthraquinone process. This efficient synthesis of H 2 O 2 and BTSP directly from O 2 is particularly attractive for the preparation of the corresponding O‐17 and O‐18 labeled reagents without the need of large excess amounts of O 2 . These are showcased in O‐atom transfer reactions to various organic or inorganic substrates, in a two‐step one‐pot process, making the rapid and on‐demand synthesis of large libraries of O‐labeled compounds readily possible.