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Practical Preparation Methods for Highly Active Azaadamantane-Nitroxyl-Radical-Type Oxidation Catalysts

  作者 SHIBUYA MASATOSHI; SASANO YUSUKE; TOMIZAWA MASAKI; HAMADA TOSHIMASA; KOZAWA MASAMI; NAGAHAMA NORIAKI; IWABUCHI YOSHIHARU  
  选自 期刊  Synthesis;  卷期  2011年-21;  页码  3418-3425  
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[摘要]We have recently disclosed that a less hindered class of nitroxyl radicals, i.e., 2-azaadamantan-N-oxyl (AZADO), 1-Me-AZADO, and 9-azabicyclo[3.3.1]nonan-N-oxyl (ABNO), exhibit marked catalytic activity for the oxidation of alcohols with the aid of environmentally friendly oxidants, offering a green and sustainable option for current alcohol oxidation. Encouraged by their outstanding catalytic performance, we envisioned the development of scalable routes to these radicals that could be extended to the commercialization of these radicals for benchtop use as well as for industrial use as optional reagents that complement TEMPO, the flagship compound of stable nitroxyl radicals. We herein describe short and reproducible preparation methods for AZADO and 1-Me-AZADO, featuring an efficient construction of the 2-azaadamantane skeleton.

 
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