| Abstract
| - P-Nitrosophosphates, such as 9, react as N−O heterodienophiles with 1,3-dienes to form highlyfunctionalized cycloadducts that can be directly transformed into allylic phosphoramidates. The insitu periodate oxidation of the unstable N-hydroxyphosphoramidate precursors provides an efficientpreparation of these new reactive intermediates. P-Nitrosophosphate (9) regioselectively reacts with1-methoxy-1,3-butadiene to provide cycloadduct 16. P-Nitrosophosphate (9) also reacts with 9,10-dimethylanthracene to give cycloadduct 17, which undergoes retro Diels−Alder dissociation to re-form 9. In the absence of a 1,3-diene, the decomposition of 17 produces nitrous oxide, evidence fornitroxyl, the one-electron-reduced form of nitric oxide. An asymmetric P-nitrosophosphate reactedwith 1,3-cyclohexadiene to form a mixture of diastereomeric cycloadducts (19 and 20) in a 1.6:1ratio. These results identify P-nitrosophosphates as new species that react similarly to acyl nitrosocompounds, making them useful synthetic intermediates and potential nitroxyl delivery agents.
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