Recently we have discovered a regioselective acylation of cyclometalated platinum complexes in which the cyclometalated platinum complex (2a, X = NH, R = H, Figure 1) was selectively acylated by reacting with acetic anhydride in acetic acid. It was further discovered that the acylated complex (3a, X = NH, R = H) could also be directly prepared in a cascade intramolecular cycloplatination-acylation reaction by reacting the organic ligand (1a, X = NH, R = H) with potassium tetrachloroplatinate in a mixture of acetic acid and acetic anhydride. In this presentation, we will report the scope and limitations of this newly discovered reaction. First, optimization of the reaction conditions indicated that a number of other solvents such as acetonitrile, benzonitrile, 1,2-dichloroethane, and chlorobenzene could be used in the acylation reaction. The reaction showed great tolerance to various linker groups (X = O, S, CH2, etc.), as well as many electron donating/withdrawing groups (R). The full results of acylation experiments with a library of substrates will be reported. The use of other electrophiles, such as benzoyl chloride, benzyl bromide, allyl bromide, methyl iodide, and crotonyl chloride, will also be reported. Mechanistic implications will be discussed from these experimental results.

Scope, limitations, and mechanistic aspects of a regioselective acylation of cycloplatinated complexes

249th National Meeting (2015)

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