Imidodiphosphorimidates ( IDPis ): Catalyst Motifs with Unprecedented Reactivity and Selectivity

Abstract The conceptually designed imidodiphosphorimidates (IDPis) have emerged as one of the most potent classes of chiral acid catalysts. They are characterized by enzyme‐like, highly confined active site and high acidity, which underlie their wide‐reaching applications as Brønsted acid catalysts and as precatalysts for silylium Lewis acids. Many carbon‐carbon and carbon‐heteroatom bond formation reactions that were deemed intractable could now be attained with spectacular reactivity and selectivity. Substrates that are small, unbiased and/or possess insufficient reactivity such as simple alkenes could now be engaged. The high structural confinement is particularly invaluable to control stereo‐ and chemoselectivity. The well‐defined steric environment offers unique opportunity to control high‐energy but structurally unbiased cation intermediates such as the norbonyl cations. Beyond practical appeals such as good scalability as well as ease and modularity of preparation, the extremely low pre‐catalyst loadings required to achieve high turnover and stereoselectivity have also come to define a new frontier in organocatalysis.