3-Hydroxy-4-pentenyl amines

As stated above, aliphatic amines are potent ligands for electrophilic transition metals and are efficient catalyst poisons in attempted alkene animation reactions. However, tosylation of the basic amino group greatly reduces its complexing ability, yet does not compromise its ability to nucleophilically attack complexed alkenes. Thus, a variety of alkenic tosamides efficiently cyclized under palladium(II) catalysis producing N-tosylenamines in excellent yield (equations 17 and 18).32 Again, this alkene amination proceeded through an unstable a-alkylpalladium(II) species, which could be intercepted by carbon monoxide, to result in an overall aminocarbonylation of alkenes. With ureas of 3-hydroxy-4-pentenyl-amines (Scheme 7), this palladium-catalyzed process was quite efficient but it was somewhat less so with... 

For example (Scheme 13.44), treatment of y-hydroxy olefins with a catalytic amount of PdCl2—(CH3CN)2 and a stoichiometric amount of CUCI2 in methanol under CO leads to intramolecular alkoxylation/carboalkoxylation sequence and formation of substituted tetrahydrofurans 61 [80-83]. Similarly, 4-pentenyl carbamates undergo palladium-catalyzed intramolecular amination/carboalkoxylation to form substituted pyrrolidine derivatives 62 [84,85]. 

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