Using N-heterocyclic carbene (NHC) ligands several well-defined and monomeric Cu(I) complexes (NHC)Cu(X) can be prepared and isolated (X = alkyl, aryl, amido, alkoxide, aryloxide or sulfido). Using Cu(I) alkoxide or methyl complexes as catalyst precursors, efficient intramolecular hydroalkoxylation of alkynes to form 5- or 6-membered rings with exocyclic olefin groups has been observed. Conversion of alkynyl amines has also been observed. Combined experimental and computational mechanistic studies for reactions of alkynyl alcohols are consistent with a reaction pathway that involves the formation of Cu(I) alkoxide followed by alkyne coordination and insertion into the Cu-alkoxide bond. Intermolecular protonolysis with a second equivalent of alkynyl alcohol completes the catalytic cycle. The details of mechanistic studies will be presented.

Catalytic intramolecular alkyne hydroalkoxylation and hydroamination: Cu(I) catalysts supported by N-heterocyclic carbene ligands

244th National Meeting (2012)

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