Synthetic organic chemistry has been markedly affected by the booming of gold catalysis over the past decade. The renaissance of this coinage metal allowed unprecedented transformations to be realized in a highly selective manner and rendered “old chemistry” more accessible from a practical point of view. Particularly, organic compounds containing C–C multiple bonds benefited from the high carbophilicity of gold species, that opened access to a great chemical diversity through direct and selective π-electrophilic activations. Nowadays, the complexity of naturally occurring compounds based on functionalized aromatic frameworks continues to inspire and influence developments in synthetic chemistry. Furthermore, the ubiquitous presence of arene-based systems in pharmaceuticals, agrochemicals, and functional organic materials warrants the growing demand for mild, selective and sustainable synthetic routes to their preparation. In this context, although the peculiar aptitude of gold salts/complexes for interaction with aromatic compounds (auration process) has long been known, the direct catalytic gold decoration of arenes, has risen to prominence only recently. Here, the extensive use of electrophilic activation of C–C multiple bonds by gold species deserves a prominent mention, and the great strides made in the field over the last few years are described in this tutorial review.

The direct functionalization of aromatic compounds, via Friedel–Crafts alkylation reactions with alcohols, is one of the cornerstones in organic chemistry. The present emerging area deals with the recent advances in the use of π-activated alcohols in the catalytic and stereoselective construction of benzylic stereocenters.