Inverting the Diastereoselectivity of the Mukaiyama–Michael Addition with Graphite-Based Catalysts

Abstract

Here, we show that graphite-based catalysts, mainly graphite oxide (GO) and exfoliated GO, are effective recyclable catalysts for a relevant stereoselective Mukaiyama–Michael addition, outperforming currently available catalysts. Moreover, the graphite-based catalysts described here invert the diastereoselectivity relative to that observed with known catalysts, with the unprecedented large prevalence of the anti diastereoisomer. This inverted diastereoselectivity is increased when the catalyst concentration is reduced and after catalyst recycling. Density functional theory calculations suggest that the selectivity is determined by two types of supramolecular interactions operating between the catalyst and the substrates at the diastereoselectivity-determining transition state, specifically, the π-stacking of β-nitrostyrene with graphite and the van der Waals interaction between the SiMe3 group of the silyl ether and the graphite.