Activation of O2 by Organosilicon Reagents Yields Quantitative Amounts of H2O2 or (Me3Si)2O2 for Efficient O‐Transfer Reactions
Activation of O2 by Organosilicon Reagents Yields Quantitative Amounts of H2O2 or (Me3Si)2O2 for Efficient O‐Transfer Reactions
复制标题
通过有机硅试剂活化 O2，产生定量的 H2O2 或 (Me3Si)2O2，用于有效的 O 转移反应
DOI：
10.1002/hlca.201800156
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发表时间：
2018
影响因子：
1.8
通讯作者：
Christophe Coperet
中科院分区：
文献类型：
--
作者：
Keishi Yamamoto;Shinji Tanaka;Hiromu Hosoya;Hayato Tsurugi;Kazushi Mashima;Christophe Coperet
分子氧是动力学惰性的，很少用作低温选择性氧化反应的主要氧化剂。在这里，我们表明，在环境温度和大气压下，在双（三甲基硅烷基）-1，4-环己二烯1的存在下，O2几乎以定量产率（98%）转化为H2 O2。类似地，O2与二氢-双（三甲基硅基）紫精2和吡嗪3的反应在低温下以优异的产率（高达99%）产生双（三甲基硅基）过氧化物（BTSP）。这两种工艺都证明，易于获得的有机硅试剂能够在生物系统中或在较高压力下实现通常与单加氧酶辅酶（如FADH 2和FMNH 2）一起观察到的化学反应，从而可用于工业蒽醌工艺。这种直接从O2高效合成H2 O2和BTSP的方法对于制备相应的O-17和O-18标记试剂特别有吸引力，而无需大量过量的O2。这些在O-原子转移反应中展示到各种有机或无机底物中，在两步一锅法中，使快速和按需合成O-标记化合物的大型库成为可能。
Molecular oxygen is kinetically inert and rarely used as a primary oxidant for low temperature selective oxygenation reactions. Here, we show that O2is converted into H2O2in almost quantitative yields (98 %) at ambient temperature and atmospheric pressure in the presence of bis(trimethylsilyl)‐1,4‐cyclohexadiene1. Similarly, the reaction of O2with dihydro‐bis(trimethylsilyl) viologen2and pyrazine3yields 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 FADH2and FMNH2, in biological systems, or at higher pressureviathe industrial anthraquinone process. This efficient synthesis of H2O2and BTSP directly from O2is particularly attractive for the preparation of the corresponding O‐17 and O‐18 labeled reagents without the need of large excess amounts of O2. 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.