Perfluoroalkylsulfonyl Fluoride-induced Acylation Or Enol Esterification Of Carboxylic Acid With 1,3-Dicarbonyls And Phosphorylation Of Alcohols With Diphenylphosphine Oxide

Perfluoroalkanosulfonyl fluoride(R_fSO₂F,for example n-C₄F₉SO₂ F and n-C₈F₁₇SO₂F)is a type of excellent hydroxyl-activating reagent.Over the past ten years,our research group has been devoted to exploring the application of R_fSO₂ F in organic synthesis.Research results showed that R_fSO₂ F can not only activate the hydroxyl group of alcohols resulting in the construction of C-F,C-O,C-S and C-N bonds,but also can serve as an excellent condensing reagent to activate carboxylic acids to induce esterification,amidation and anhydridization.The reaction of R_fSO₂ F with ketoximes resulted in the smooth Beckmann rearrangement providing the corresponding amides as products;when it was subjected to the reaction with aldoximes,nitriles formed as elimination products.These results show that R_fSO₂ F will gradually serve as an important reagent in organic synthesis.Therefore,to further study the application of R_fSO₂ F in organic synthesis is highly in demands.This Master degree thesis was composed of the following two parts.In part one,acylation or enol esterification of carboxylic acids with 1,3-diketones induced by R_fSO₂ F was investigated,and the corresponding tricarbonyls or enol esters were formed in 45-65% yields.The effects of solvents,reaction temperature,bases,ratio of substrate to reagents and reaction time on yields were evaluated.A possible mechanism was put forward to interpret the reaction phenomina.Our developed method has the following advantages: mild reaction conditions,simple work-up procedure and high selectivity.An alternative method for the preparation of tricarbonyls or enol esters was provided.In part two,the Atherton-Todd-type phosphorylation reaction of alcohols with diphenylphosphine oxide induced by R_fSO₂ F was investigated,and the corresponding diphenylphosphinate esters were formed in 52-78% yields.The effects of solvents,reaction temperature,bases,ratio of substrate to reagents and reaction time on yields were evaluated.A possible mechanism was put forward to interpret the reaction phenomina.Our developed method has the following advantages: mild and metal-free reaction conditions and the use of non-toxic and stable R_fSO₂ F.An alternate method for the preparation of diphenylphosphinate esters was thus provided.