Study On The α-phosphoryloxylation Of Ketones With Hypervalent Iodion Reagent

Chapter one, the latest application of the hypervalent iodion regent,(diacetoxyiodo)benzene (DIB) in organic synthesis has been reviewed，andin which the recent development of catalytic organic reaction withhypervalent iodion reagents is included.Chapter two, study on the-phosphoryloxylation of ketones. Ketophosphates are important strategic precursors in a variety of synthesis;however, the method for preparation of them has been rather limited. Inorder to develop some simple, mild and efficient methods to prepare moreketol phosphates, we have investigated the-phosphoryloxylation ofketones using of organic hypervalent iodine reagents due to their chemicalproperties and reactivity are similar to those of Hg (II), Tl (III) and Pb (IV), but without the toxic and environmental problems of these heavy metalcongeners. With these new methods for-phosphoryloxylation of ketone,the keto phosphates have been prepared in moderate to good yields.In the first part of chapter two, it is introduced an efficient one-potα-phosphoryloxylation of ketones. When ketones are treated with(diacetoxyiodo)benzene and phosphates in CH2Cl2at room temperature, the-phosphoryloxylaction of ketones is easily be carried out, providing theketol phosphates in good yields. In the second part, theα-phosphoryloxylation of ketones under catalytic hypervalent iodion regentis investigated. Under the optimum reaction conditions, a veriety of ketonesare treated with2equivalents of phosphates and m-CPBA in the presenceof0.1equivalent of (diacetoxyiodo)benzene as catalyst in acetonitrile atroom temperature for24hours, the keto phosphates are prepared inmoderate to good yields. In the last part, the new improvement for theα-phosphoryloxylation of ketones under microwave irradiation is reported,which greatly increases the rate of reaction, and the reaction time isshortened to1minute.