分子内胺/硼烷受阻路易斯对与氧气的选择性氧化。
Selective Oxidation of an Active Intramolecular Amine/Borane Frustrated Lewis Pair with Dioxygen.
机构信息
Organisch-Chemisches Institut, Westfälische Wilhelms-Universität Münster , Corrensstrasse 40, 48149 Münster, Germany.
Mulliken Center for Theoretical Chemistry, Institut für Physikalische und Theoretische Chemie, Universität Bonn , Beringstrasse 4, 53115 Bonn, Germany.
出版信息
J Am Chem Soc. 2016 Apr 6;138(13):4302-5. doi: 10.1021/jacs.6b00325. Epub 2016 Mar 23.
Oxidation reactions are rarely encountered in frustrated Lewis pair (FLP) chemistry. We describe the selective reaction of an amine/borane FLP with molecular oxygen. The trimethylene-bridged amine/borane frustrated Lewis pair was prepared by hydroboration of N-allyl-tetramethylpiperidine with Piers' borane [HB(C6F5)2]. The intramolecular N/B system undergoes a variety of typical FLP reactions. It is a very active hydrogen splitting reagent at ambient conditions. Its reaction with dioxygen takes place rapidly at ambient conditions to give a tetrahydroisoxazolium/borate salt. A possible pathway of its formation is proposed and supported by DFT calculations.
氧化反应在受阻路易斯对（FLP）化学中很少见。我们描述了胺/硼烷 FLP 与分子氧的选择性反应。三亚甲基桥接的胺/硼烷受阻路易斯对是通过 N-烯丙基-四甲基哌啶与 Piers' 硼烷[HB(C6F5)2]的硼氢化反应制备的。分子内的 N/B 体系经历了各种典型的 FLP 反应。它在环境条件下是一种非常活跃的氢分裂试剂。它与氧气的反应在环境条件下迅速进行，生成四氢异噁唑鎓/硼酸盐盐。提出了一种可能的形成途径，并通过 DFT 计算得到了支持。
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