Copper Catalyzed Borylation of Alkynes: An Experimental Mechanistic Study.

The copper catalyzed hydroboration of alkynes with B2pin2 was studied by in detail studies of individual relevant steps along the catalytic pathway. A number of reaction steps were retraced by in situ NMR spectroscopy as well as central intermediates and side-products were isolated and comprehensively characterized. A copper boryl complex is central to the catalytic process by inserting the terminal alkyne substrate into the B-Cu bond. The selectivity of this step - depending on the NHC auxiliary ligand - determines the α/β selectivity observed in the product. The latter complex is protonated by the auxiliary alcohol reagent resulting in hydroboration product formation and formation of a Cu alkoxido complex. Reaction of the latter with B2pin2 results in the regeneration of the central copper boryl complex. This alcoholysis step depends on the acidity of the alcohol, in particular on the relative acidity of the alcohol vs. the alkyne substrate. A number of side reactions leading to the hydrogenation product of the alkyne substrate and a bis hydroborated product were identified and studied in some detail. It is concluded that the performance of a particular catalytic system depends crucially on the relative acidities of the reagents and generalizations may be difficult.