Organic Selenium Participates In The Reaction Of Carbon-oxygen Bond Formation

The C-O bond is a very important fragment in drug intermediates.Formation of C-O bond by alkoxylation of the sp3 C-X bond has a very large application in the pharmaceutical industry.In addition,construction of C-O bond via direct activation of C-H bond will greatly reduce the synthesis steps and production costs for pharmaceutical industry.Thus,we investigated the a-C-H and a-C-X alkoxylation of carbonyl group of a-bromo-aryl-ethanone derivatives.We also investigated the direct ?-C-H(sp3)functionalization of aryl-ethanone derivatives and ?-C-H(sp3)functionalization of propiophenone.This thesis include the following three parts:1.The effects of organoselenium catalysts with different electrical properties and steric hindrance on alkoxylation of carbonyl group of a-bromo-aryl-ethanone derivatives were studied under aerobic conditions.In addition,we explored the effects of a series of different combinations of organoselenium catalysts and copper reagents on alkoxylation of carbonyl group of a-bromo-aryl-ethanone derivatives.2.The activation of a-C-H bond of aryl-ethanone derivatives was studied.It is a great challenge for the direct activation of a-position of carbonyl group of the unsubstituted aryl ketone derivatives.Finally,we developed an highly efficient method for the construction of C-O bond via a-C-H functionalization of carbonyl group of aryl-ethanone derivatives in the presence of oxygen and catalytic amount of additives after exploring a series of different combinations of organoselenium catalysts and copper reagents.3.The direct ?-C-H(sp3)functionalization of propiophenone was investigated.The activation of ?-C-H bond of the carbonyl group is more difficult to be achieved than the activation of a-C-H bond of the carbonyl group.We finally developed an approach to the direct?-alkoxylation of ketones with alcohol by screening several organoselenium catalysts,oxidants and additives in detail.