Multifunctional Organocatalysts ‐ Singly‐Linked and Macrocyclic Bisphosphoric Acids for Asymmetric Phase‐Transfer and Brønsted‐Acid Catalysis

The linking of phosphoric acids via covalent or mechanical bonds has proven to be a successful strategy for the design of novel organocatalysts. Here, we present the first systematic investigation of singly‐linked and macrocyclic bisphosphoric acids, including their synthesis and their application in phase‐transfer and Brønsted acid catalysis. We found that the novel bisphosphoric acids show dramatically increased enantioselectivities in comparison to their monophosphoric acid analogues. However, the nature, length and number of linkers has a profound influence on the enantioselectivities. In the asymmetric dearomative fluorination via phase‐transfer catalysis, bisphosphoric acids with a single, rigid bisalkyne‐linker give the best results with moderate to good enantiomeric excesses. In contrast, bisphosphoric acids with flexible linkers give excellent enantioselectivities in the transfer‐hydrogenation of quinolines via cooperative Brønsted acid catalysis. In the latter case, sufficiently long linkers are needed for high stereoselectivities, as found experimentally and supported by DFT calculations.