Selectivity-Controllable Aromatic Alkane Oxidation

Oxidation is a very widely used and important organic chemical reaction.The proportion of chemical products obtained through the oxidation process is the largest.The oxidation reaction which is difficult to selectivity control,in different conditions,using different oxidants,can get different degree of oxidation products or mixtures,and oxidation products are thermodynamically unstable intermediates,the reaction selectivity and controllability is always a challenging problem.Our group has been committed to the research on free radical inturruped reactions,the important issue in the research is by the change of the reaction conditions to produce a series of free radical reactions through selectivity and controllability interruped the carbon free radical.In this paper,based on the synergistic effects of N-hydroxyphthalimide and tert-butyl nitrite,makes the aromatic alkanes produce aryl alkane carbon radicals,for one hand the use of free radical cross coupling can selectivity controllable get single and double ammonia oxidation products,on the other hand the use of free radical oxidation with oxygen can get single and double oxidation products.The research content of this paper mainly includes the following two parts:1.Using the synergistic effect of N-hydroxyphthalimide and tert-butyl nitrite,tert-butyl nitrite as nitric oxide source,selective and deeply controllable ammoxidized the arylalkane to mononitrile and dinitrile products.In this reaction,the versatility of aralkane substrates is good,which can all get very high yields.The chiral materials can also be well achieved conversion to mononitrile and dinitrile,and ee values can be well preserved.We also have achieved the gram-level synthesis of the anti-depressant citalopram from large-scale industrial materials m-xylene.2.Using the synergistic effect of N-hydroxyphthalimide and tert-butyl nitrite,oxygen as oxygen source,selective and deeply controllable ammoxidized the arylalkane to monoketone and diketone products.In this reaction,the versatility of aralkane substrates is good,which can all get very high yields.The chiral materials can also be well achieved conversion to monoketone and diketone,and ee values can be well preserved.We also have achieved the gram-level synthesis of the diazepam drug lenperone.