Study On The AIBN-catalyzed Oxidative Cleavage Of Gem-Disubstituted Alkenes And Copper-Catalyzed Cross-Coupling Reaction Of AllyI Boron Ester With Halogenated Alkanes

Oxidative cleavage of olefins to the carbonyl compounds is an important transformation in organic synthesis. However, methods reported in literatures always suffer from several drawbacks, such as over-stoichiometric amounts of oxidants, toxic metals and too much byproduct. Recently, methods catalyzed by the non-metallic catalyst with O2 as oxidant have been reported by the Jiao group, which opened up a new horizon in this area. The development of another approach for the aerobic oxygenation of olefins is still urgently required. Herein, we have developed an economical and environmental method for the oxidative cleavage of C=C bond. AIBN was employed as the catalyst and oxygen was employed as the oxidant to promote the oxidation reaction. This method afforded convenient access to a variety of ketones from the olefins. Moreover, a relatively good selectivity for the oxidation of geminal diaryl ethylene was represented in our developed system. Moreover, we also investigated the Large-scale experiment and mechanism, expanding the application value and theoretical value.Cross-coupling reactions of organometallic reagents with electrophiles are among the most useful C-C bond-forming reactions in organic synthesis. The introduction of allyl group into the oraganic molecular is particular important. Although considerable progress has been made in allyl-alkyl coupling reactions, However, allyl Grignard reagent all are all inevitable in the previous reports, which always suffers from such drawbacks as moisture-sensitive and manipulation difficulty. Therefore, finding a gentle and convenient allylation method still remains a challenge. Allylboronic acid pinacol ester [allylB(pin)], as a stable and commercially available organicboron reagent, has drawn considerable attention and great advances has been achieved in recent years. Until now the catalysis of such transformations by copper has not been reported. Based on such thoughts, we reported copper-catalyzed coupling reaction of allylB(pin) with primary, secondary and tertiary halogenated alkanes for the first time. This method provides an effective method for the synthesis of a series of substituted olefins. What’s more, we also deeply investigated the selectivity and proposed a relatively reasonable mechanism based on the literatures and verification experiment.