The development of large scale synthesis of enantiopure and thermally stable (R)- and (S)-BINOL molecules constitutes a key milestone in the field of asymmetric catalysis. Particularly, a great variety of chiral binaphthyl-based phosphorus compounds, herein represented by phosphite and phosphine classes, have earned considerable relevance due to their versatility as ligands in enantioselective metal-catalysed reactions, allowing the preparation of optically active products with the desired enantiopurity. This review highlights the most relevant concepts and accounts regarding general synthetic procedures for binaphthyl-based mono- and bidentate phosphites and phosphines. Furthermore, the search for environmentally benign chemical catalytic processes compelled us to also give special attention to the functionalisation of binaphthyl-based phosphorus ligands for use in alternative reaction media. When available, a critical selection of their applications in catalysis is briefly assessed.

New and highly active mononuclear phosphite gold(I) catalysts are described. Turn-over numbers up to 37 000 for the furan–yne reaction and up to 28 000 000 for the two-fold hydroalkoxylation of alkynes are reported.

Catalytic carbon dioxide transformation to low valence carbon molecules such as carbon monoxide, formic acid, methanol and methane is a sustainable way to produce fuels and chemicals. Molecular catalysts can be designed to selectively transform CO₂at mild conditions, but a solvent medium is required. Instead, the molecular catalysts can be immobilized on solid supports to facilitate the continuous flow procedure and the separation of the products to recycle the catalytic systems for a more sustainable process. Photosensitive supports may also favor the light‐absorbing steps and electron transfer processes. In this article, the recent results obtained in the photocatalytic CO₂‐reduction using catalytic systems formed by molecular compounds anchored on solids are reviewed.