Highly Selective Palladium-Catalyzed Intramolecular Aminonitroxylation of Alkenes

Abstract

A palladium-catalyzed intramolecular oxidative aminonitroxylation of unactivated alkenes, in which AgNO₃ functioned as a mild nitrate reagent in the presence of PhI(OAc)₂, has been developed. Mechanistic studies suggest that this selective aminonitroxylation reaction likely resulted from a new oxidant PhI(ONO₂)₂ generated in situ from AgNO₃ and PhI(OAc)₂.

Key words

palladium - alkenes - difunctionalization - silver - aminonitroxylation

References and Notes

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8

The same stereochemical behavior has been reported.^4a,b,5b,6

10

The alternative path a in Scheme  [²] is less likely, but cannot be excluded at this moment. This is because the differen-tiation of cis- and trans-aminopalladation is very difficult.

12

The organic layer contained no Ag ion, which was demon-strated by addition of Bu₄NCl - no AgCl precipitated from the organic layer.