Selective Oxidation Of Alcohols Catalyzed By TEMPO Built-in Conjugated Microporous Polymers

The oxidation of alcohols is one of the most important reactions in organic synthesis.And 2,2,6,6-tetramethylpiperidine-1-oxyl?TEMPO?as an organic small molecular oxidant,it is used more and more widely in the field of alcohol oxidation reaction.When TEMPO is used as oxidant,the reaction has the advantages of good selectivity,high conversion rate and mild reaction conditions.However,TEMPO is relatively expensive,and it is difficult to separate from the product.Thus,thesupported TEMPO for its recycling in the oxidant of alcohols is of great significance.Organic porous polymers have great potential applications in the field of optoelectronic devices,adsorption and separation of materials,energy and heterogeneous catalysis.The possibility of designing novel catalyst system by an appropriate combination of polymers/TEMPOsystem on a suitable support which enable efficient recycling of system has been described.We focused on the catalytic oxidation of alcohols by TPE-TEMPO-CMP and DCT-TEMPO-CMP.Simple alcohols using TPE-TEMPO-CMPwasreadily oxidized to the corresponding aldehyde or ketones in yields of 99%under the Anelli catalytic system.And the yield of simple alcoholsusingDCT-TEMPO-CMP can also readily reach 99%under the NaNO₂/O₂ catalytic system.Moreover,alcohols containing unsaturated groups couldbe converted into their corresponding aldehydes or ketonesin high yields.The two kinds of catalysts were reused for more than 10 times,which showed excellent stability.