Palladium catalysis aminocarbonylation

Aside from alkoxycarbonylations, hydroxycarbonylations in the presence of water to yield allenic carboxylic acids [15] (93, Y = OH) and aminocarbonylations in the presence of amines to give the analogous amides [139] (93, Y = NRR ) have also been carried out, respectively (Scheme 7.13). These products of structure 102 can also be obtained if using the propargylamines 101 with R1 = Ph or R3 Z H as starting materials (Scheme 7.15) [140]. Additionally, hydroxycarbonylations, also termed carboxyla-tions, are successful without palladium catalysis by reaction of propargyl halides and carbon monoxide in the presence of nickel(II) cyanide under phase-transfer conditions [141, 142]. 

The potential of palladium-catalyzed aminochlorination reactions of alkenes dates back to their isolation as side products in aminocarbonylation reactions under copper(II)dichloride cocatalysis [47d]. These reactions were later developed further using copper(II) salts as co-oxidants or reoxidants, respectively, and concomitantly as halide sources. For example, Chemler showed that various aminohalogenation reactions proceed under palladium catalysis in the presence of potassium carbonate as base in moderate to excellent yields in the presence of an excess of the copper oxidant [80]. Both five- and six-membered rings 115 and 116 were formed under these conditions from allyl anilines 114 (Scheme 16.28). Among other examples... 

The aminocarbonylation of phenols with carbon monoxide and ammonia has been achieved using palladium catalysis. After in situ conversion of the phenols to the corresponding nonaflates, oxidative addition to the palladium gives an aryl palladium complex which undergoes carbon monoxide insertion. Nucleophilic attack of ammonia results in the formation of the benzamide. ... 

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... 

Carbamoylsilane also led to the CO-free aminocarbonylation of alkenyl halides through catalysis by palladium complexes [54]. 

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