Study On Iodooxygenation Of Alkenes Involved In Molecular Iodine

The simultaneous introduction of two different functional groups to the olefin carbon-carbon double bond by one-step method is an important reaction process in organic synthesis.The direct bifunctionalization of olefins without metal participation has received more and more attention because of its advantages of simple operation and low cost,which greatly enriches the application of olefins in organic synthesis.Based on literature review and previous work,this dissertation further focuses on the1,2-difunctionalization of olefins,and develops a substrate controlled regioselective olefin Iodooxygenation method with no metal catalyst.And a preliminary study was conducted on the derivatization reaction of the product.This thesis mainly includes the following contents:In this part,the recent progress in the research of alkene bifunctional reactions are reviewed.The content is introduced according to the free radical reaction mechanism and the iodine reaction mechanism.We have developed a I₂/TBHP-mediated N-hydroxylamine involved olefin1,2-iodooxygenation reaction.When N-hydroxybenzotriazole is used as an N-hydroxyamine substrate,aryl olefins,alkyl olefins,and cycloolefins generate the correspondingβ-iodobifunctionalized product,while 2-vinyl pyridine and acrylate are generated correspondingα-iodobifunctionalized products.The regioselective addition of iodine oxygen groups to olefins is achieved through the regulation of olefinic substrates,when N-hydroxy-7-azobenzotriazole was used as a substrate,the regioselective addition of iodine oxygen groups to olefins can be achieved by adjusting the reaction temperature.Through the investigation of the mechanism,it was found that the regioselectivity of this reaction depends on the free radical reaction and the iodine reaction mechanism.Based on the above research,preliminary derivatization of the reaction products was studied.A class ofβ-iodo-N-alkoxybenzotriazoles was developed as a raw material,and a molecule of HI was removed to form N-alkenyloxybenzotriazoles under the action of base.The Iodooxygenation products of various olefins give the target N-alkenyloxybenzotriazole product in moderate to excellent yield.