Epoxides, vinyl reaction with nitrogen nucleophiles

In the presence of a palladium catalyst, allyl epoxides (113) react with nitrogen nucleophiles at the al-kenic carbon atom remote from the oxirane ring to give 1,4-adducts (114)." In the absence of a palladium catalyst, azide ion attacks the oxirane ring affording 1,2-adducts (115 Scheme 52 and Table 2)." Vinyl epoxide (116) gave 1,2- and 1,4-azido alcohol in a ratio of 1 1.5 irrespective of the reaction system. " Intramolecular cyclization of vinyl epoxide (117) in the presence of a palladium catalyst afforded isoquinuclidine (118 Scheme 52). ... 

A Pd-mediated reaction of a vinyl epoxide with an isocyanate offers synthetically useful transformation (Scheme 4). A diastereoselective vicinal hydroxyamination is established, which involves trapping an initial zwitterion with an isocyanate and subsequent nucleophilic attack of a nitrogen anion on a rr-allylpalladium intermediate (Scheme 4)... 

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