Synthesis of chiral hydantoin derivatives by homogeneous Pd-catalyzed asymmetric hydrogenation

Synthesis of Chiral Hydantoins and Thiazolidinediones viaIridium‐Catalyzed Asymmetric Hydrogenation

“…In 2017, Wang and co‐workers reported the synthesis of chiral hydantoin derivatives via a Pd‐catalyzed asymmetric hydrogenation reaction, delivering the products with poor to good enantioselectivities (only two products were obtained in 88% and 90% ee values, respectively), and most of the products were obtained in 45%—65% ee values (Scheme 1a). [ 4 ] To the best of our knowledge, the catalytic asymmetric synthesis of chiral thiazolidinediones has never been reported. Therefore, developing efficient method for the preparation of those chiral compounds is highly desirable.…”

Organocatalytic cascade nucleophilic/aza-Michael addition reactions: metal-free catalytic strategy for the synthesis of hydantoins

“…10 Classical synthetic pathways, including the Bucherer–Bergs, 11 the Biltz, 12 and the Urech 13 or Read reactions, 14 show wide application in hydantoin synthesis. Alternatively, a variety of catalytic examples such as Pd-, Cu- or TBAB-catalyzed functionalization of hydantoin nucleus, 15 Cu-catalyzed C–H α-amination of esters with diaziridinones, 16 transition-metal catalyzed intermolecular [2 + 2 + 1] cycloaddition reactions, 17 Pd-catalyzed oxidative carbonylation of α-amino amides, 18 Ag-catalyzed α-amination and α-arylation of silyl ketene acetals, 19 and Ir- or Pd-catalyzed asymmetric hydrogenation of arylidene-hydantoins, 20 have been reported over the years (Scheme 2a). Although significant achievements have been demonstrated, the metal-free catalytic strategies remain rare (Scheme 2b).…”

Chiral Recognition of Hydantoin Derivatives Enabled by Tetraaza Macrocyclic Chiral Solvating Agents Using 1H NMR Spectroscopy

“…Nevertheless, recognition of chiral cyclic substrates has rarely been investigated by 1 H NMR spectroscopy . This is surprising, given the fact that enantiomerically pure cyclic products, including several chiral hydantoin derivatives, have been used to treat many human diseases, due to their powerful physiological and pharmacological activities . In this paper, we offer a significant solution to the challenging chiral recognition of hydantoin derivatives, as five-membered N,N-heterocyclic compounds, with the discovery of a panel of remarkable tetraaza macrocyclic chiral solvating agents (TAMCSAs) that enable the determination of enantiomeric purity by means of 1 H NMR spectroscopy.…”