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Modular POP Ligands in Rhodium‐Mediated Asymmetric Hydrogenation: A Comparative Catalysis Study
Author(s) -
NúñezRico José L.,
Etayo Pablo,
FernándezPérez Héctor,
VidalFerran Anton
Publication year - 2012
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.201200477
Subject(s) - chemistry , rhodium , enantioselective synthesis , ligand (biochemistry) , reactivity (psychology) , catalysis , medicinal chemistry , acetophenone , steric effects , cationic polymerization , enol , alcohol , substrate (aquarium) , organic chemistry , stereochemistry , medicine , biochemistry , geology , oceanography , receptor , alternative medicine , pathology
Highly efficient and enantioselective hydrogenation reactions for α‐(acylamino)acrylates, itaconic acid derivatives and analogues, α‐substituted enol ester derivatives, and α‐arylenamides (25 substrates) catalyzed by chiral cationic rhodium complexes of a set of POP ligands have been developed. The catalytic systems derived from these POP ligands provided a straightforward access to enantiomerically enriched α‐amino acid, carboxylic acid, amine, and alcohol derivatives that are valuable chiral building blocks. Excellent efficiencies (full conversion in all cases) and extremely high enantiomeric excesses (94–99% ee ) were achieved for a wide range of α‐substituted enol ester derivatives, regardless of the substitution pattern. The R‐oxy group of the ligand (methoxy or triphenylmethoxy) strongly influences the enantioselectivity and catalytic activity. Greater steric bulk around the metal centre correlated to greater (or similar) enantioselectivity, but also to slower hydrogenation. Furthermore, the hydrogenation rates observed with the four model substrates follow the same trend, independently of the R‐oxy group of the ligand: methyl 2‐acetamidoacrylate>dimethyl itaconate>1‐phenylvinyl acetate> N ‐(1‐phenylvinyl)acetamide. A substrate‐to‐catalyst ratio (S/C) of up to 10,000:1 was sufficient for total hydrogenation of a model substrate of intermediate reactivity (dimethyl itaconate), and did not imply any loss in conversion or enantioselectivity.