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Activation of O 2 by Organosilicon Reagents Yields Quantitative Amounts of H 2 O 2 or (Me 3 Si) 2 O 2 for Efficient O‐Transfer Reactions
Author(s) -
Yamamoto Keishi,
Tanaka Shinji,
Hosoya Hiromu,
Tsurugi Hayato,
Mashima Kazushi,
Copéret Christophe
Publication year - 2018
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.201800156
Subject(s) - chemistry , organosilicon , reagent , trimethylsilyl , pyrazine , peroxide , organic chemistry
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.