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.

An update on chiral phosphoric acid organocatalyzed stereoselective reactions

“…[1][2][3][4][5][6] On the other hand, catalysts that completely transfer a proton to the substrate are Chiral Phosphoric Acids (CPAs), N-triflyl phosphoramides, chiral disulfonimides, and imidodiphosphate-type Brønsted acids. [7][8][9][10][11] Since the first report in 2004, chiral phosphoric acids have been establishing new trends with robust synthetic protocols and are undoubtedly the reference in Brønsted acid-type organocatalysis. 12,13 This kind of catalyst has a well-defined chiral environment around the active site and represents a powerful instrument for asymmetric transformations.…”

“…[37][38][39][40] Also it excludes other CPA derivatives, such as N-triflyl phosphoramides, chiral disulfonimides, and imidodiphosphate-type Brønsted acids recently reviewed elsewhere. [8][9][10][11] Eddy I. Jiménez Eddy Ivanhoe Jiménez received his PhD from Universidad Nacional Autónoma de México (UNAM), focusing on the area of asymmetric organocatalysis under the mentorship of Prof. Marcos Hernández-Rodríguez. As a research assistant at the Institute of Chemistry, UNAM, he worked for eight months synthesizing polyaromatic compounds.…”

“…1–6 On the other hand, catalysts that completely transfer a proton to the substrate are Chiral Phosphoric Acids (CPAs), N -triflyl phosphoramides, chiral disulfonimides, and imidodiphosphate-type Brønsted acids. 7–11…”

“…37–40 Also it excludes other CPA derivatives, such as N -triflyl phosphoramides, chiral disulfonimides, and imidodiphosphate-type Brønsted acids recently reviewed elsewhere. 8–11…”

Enantioselective Synthesis of Chiral Cyclobutenes Enabled by Brønsted Acid-Catalyzed Isomerization of BCBs

“…Nonetheless, BCBs have been scarcely involved in asymmetric transformations, and the enantiocontrol for the isomerization process of BCBs to cyclobutenes, to the best of our knowledge, has been never challenged. The pioneering findings incorporating our understanding in organocatalysis inspired us to conquer this transformation with a chiral Brønsted acid (CBA) . The decisive factor of the present scenario belongs to the selection of suitable BCB substrates and a CBA catalyst.…”