Self-Assembly of Bidentate Ligands for Combinatorial Homogeneous Catalysis:  Asymmetric Rhodium-Catalyzed Hydrogenation

Abstract

The first chiral ligand library based on self-assembly through complementary hydrogen-bonding was realized. From a 10 x 4 ligand library, catalysts that show excellent activity and enantioselectivity for the asymmetric rhodium-catalyzed hydrogenation have been identified.

Trans-chelating diphosphines, the elusive ligands!

“…In the last few years, a fascinating new strategy emerged which makes use of supramolecular interactions for the construction of cis-chelating diphosphines [185][186][187][188][189][190][191][192][193][194][195][196][197][198][199][200]. The challenging synthesis of trans-chelating diphosphines has also been approached with this methodology.…”

Self‐Assembled Bidentate Ligands for the Nickel‐Catalyzed Hydrocyanation of Alkenes

“…[18][19][20][21][22] Heterodimeric selfassembled bidentate ligands bearing chiral information were recently applied successfully to rhodium-catalyzed asymmetric hydrogenation. [16] …”

Combinatorial Transition‐Metal Catalysis: Mixing Monodentate Ligands to Control Enantio‐, Diastereo‐, and Regioselectivity

“…[123] Subsequently, it was applied in enantioselective Rh-catalyzed olefin hydrogenation. [124] In this case the two substituents at the P atom bound to the heterocycles are not two aryl groups, but the binol moiety leading to the respective phosphonites 115 and 116, which dimerize spontaneously. The respective Rh complex, which constitutes the heterocombination, leads to high enantioselectivity (> 90 % ee).…”