Iodonium salts as efficient iodine(iii)-based noncovalent organocatalysts for Knorr-type reactions

Abstract

Hypervalent iodine(III)-derivatives display higher catalytic activity than other aliphatic and aromatic iodine(I)– or bromine(I)-containing substrates for a Knorr-type reaction of N-acetyl hydrazides with acetyl acetone to give N-acyl pyrazoles. The highest activity was observed for dibenziodolium triflate, for which 10 mol% resulted in the generation of N-acyl pyrazole from acyl hydrazide and acetyl acetone typically at 50 °C for 3.5–6 h with up to 99% isolated yields. ¹H NMR titration data and DFT calculations indicate that the catalytic activity of the iodine(III) is caused by the binding with a ketone.