Phosphites, reaction with hexafluoroacetone

In the reaction of iso< anato-phosphites with hexafluoroacetone, attack on oxygen gives the intermediate (53), which on cyclization and further... 

Studies on the synthesis of cage-like phosphoranes based on casade reactions of trivalent phosphorus derivatives with unsaturated activated compounds has continued. For example, reactions of phosphites bearing dioxaphosphorinane (1), dioxaphospholane (2) and catechol derivatives (3) with hexafluoroacetone, chloral, mesoxalic and trifluoropyruvic acid esters have been performed to produce a series of novel carcass -type pentacoordinated phosphoranes with high regio- and stereoselectivity. Hence, upon treatment of hexafluoroacetone (4) with phosphites (1) and (2), pen-taoxophosphoranes (5) and (6) were formed (Scheme 1). 

Hexafluoroacetone azine accepts nucleophiles (ROH, RSH, R NH) in positions 1 and 2 to yield hydrazones [27] Phosphites give open-chain products via a skeletal rearrangement [22] Radical addition reactions are also reported [22] Treatment of tnfluoropyruvates with tosylhydrazine and phosphorus oxychlo-ride-pyndme yields tnfluoromethyl-substituted diazo compounds [24] (equation 3)... 

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