Study On Allylic And Benzylic Oxidative Transformation

Among numerous organic conversion reactions,oxidation reaction is a very important one.Oxidation process can convert cheap and easily available hydrocarbons into other structural units or fine chemical products.Therefore,Oxidation reaction has a wide range of applications in both industrial production and daily life.For example,in the traditional industry,a large amount of energy can be obtained by the oxidation process of fossil fuels such as coal,oil,and natural gas.However,oxidation reactions tend to be more complex and difficult to control than other organic reactions.Due to the high bond dissociation energies(BDES),common carbon-hydrogen bonds have good thermal stability and chemical stability,which makes them relatively inert in chemical reactions.Therefore,the selective oxidation of compounds under mild conditions has always been a hotspot and difficulty for chemists.However,the allyl position and the benzylic carbon-hydrogen bond have ?-? superconjugation in the molecule,and the stability of the intermediate is enhanced,so the bond energy of the carbon-hydrogen bond is lowered and the reactivity is improved.This opens up the possibility of selective oxidation of allylic and benzylic sites.In order to adapt to the inherent requirements of green chemistry development and environmental sustainability,our research team has been working on environmentally friendly,mild and inexpensive oxidation methods.In particular,there is a strong research interest in the oxidative reaction of allylic sites and benzylic sites.Based on the original work of the laboratory,this paper has carried out three aspects of work based on the allylic position and the benzylic oxidation strategy:1.The ?,?-dehydrogenation reaction of aldehydes and ketones is based on the development of Pd-tBuONO in the laboratory to catalyze the anti-Markov Wacker oxidation of olefins.By understanding the enol intermediates in the mechanism,the?,?-dehydrogenation reaction of aldehydes with palladium catalyzed by oxygen as an oxidant was realized.Moreover,in the expansion of this work,the ?,?-dehydrogenation reaction of ketone compounds under the same catalytic system was realized.2.In the expansion of the ?,?-dehydrogenation reaction of carbonyl compounds,we have developed a new method for the preparation of non-metal catalyzed alkali-promoted ?,?-unsaturated amide compounds based on the development of amides in the alpha position oxidation work.3.We have developed CuSO4 catalyzed isocyanide and benzyl anion redox cascade cyclization with toluene derivatives and isonitriles as substrates.The synthesis of terpenoids was successfully achieved by the coupling of C-C and C-N bonds.