Natural Cinchona Alkaloids (natural + cinchona_alkaloid)

Distribution by Scientific Domains


Selected Abstracts


Back to Natural Cinchona Alkaloids: Highly Enantioselective Michael Addition of Malononitrile to Enones

ADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 18 2009
Alessio Russo
Abstract An efficient and convenient highly enantioselective Michael addition of malononitrile to enones has been developed by using quinine as the organocatalyst. The adducts were isolated in excellent yield and high asymmetric induction (up to 95% ee). An easy route to difficultly accessible ester derivatives has been also disclosed. [source]


Bifunctional Catalysis by Natural Cinchona Alkaloids: A Mechanism Explained

CHEMISTRY - A EUROPEAN JOURNAL, Issue 32 2009
Clotilde
Abstract The use of bifunctional chiral catalysts, which are able to simultaneously bind and activate two reacting partners, currently represents an efficient and reliable strategy for the stereoselective preparation of valuable chiral compounds. Cinchona alkaloids such as quinine and quinidine, simple organic molecules generously provided by Nature, were the first compounds to be proposed to operate through a cooperative catalysis. To date, a full mechanistic characterization of the dual catalysis mode of cinchona alkaloids has proven a challenging objective, due to the transient, non-covalent nature of the involved catalyst,substrate interactions. Here, we propose a mechanistic rationale on how natural cinchona alkaloids act as efficient bifunctional catalysts by using a broad range of computational methods, including classical molecular dynamics, a mixed quantum mechanical/molecular mechanics (QM/MM) approach, and correlated ab-initio calculations. We also unravel the origin of enantio- and diastereoselectivity, which is due to a specific network of hydrogen bonds that stabilize the transition state of the rate-determining step. The results are validated by experimental evidence. [source]


Efficient iridium and rhodium-catalyzed asymmetric transfer hydrogenation using 9-amino(9-deoxy) cinchona alkaloids as chiral ligands

APPLIED ORGANOMETALLIC CHEMISTRY, Issue 5 2006
Wei He
Abstract 9-Amino (9-deoxy) cinchona alkaloids, derived from natural cinchona alkaloids, were applied in asymmetric transfer hydrogenation in both iridium and rhodium catalytic systems using i -propanol as the hydrogen source. A series of aromatic ketones was examined, and good to excellent conversions and enantioselectivities were observed. The best results were achieved using 9-amino(9-deoxy) epicinchonine 2a as the ligand and [Ir(COD)Cl]2 as the metal precursor, and for the isobutylphenone, the conversion and enantioselectivity were obtained in 90 and 97% e.e. respectively. Copyright © 2006 John Wiley & Sons, Ltd. [source]


Bifunctional Catalysis by Natural Cinchona Alkaloids: A Mechanism Explained

CHEMISTRY - A EUROPEAN JOURNAL, Issue 32 2009
Clotilde
Abstract The use of bifunctional chiral catalysts, which are able to simultaneously bind and activate two reacting partners, currently represents an efficient and reliable strategy for the stereoselective preparation of valuable chiral compounds. Cinchona alkaloids such as quinine and quinidine, simple organic molecules generously provided by Nature, were the first compounds to be proposed to operate through a cooperative catalysis. To date, a full mechanistic characterization of the dual catalysis mode of cinchona alkaloids has proven a challenging objective, due to the transient, non-covalent nature of the involved catalyst,substrate interactions. Here, we propose a mechanistic rationale on how natural cinchona alkaloids act as efficient bifunctional catalysts by using a broad range of computational methods, including classical molecular dynamics, a mixed quantum mechanical/molecular mechanics (QM/MM) approach, and correlated ab-initio calculations. We also unravel the origin of enantio- and diastereoselectivity, which is due to a specific network of hydrogen bonds that stabilize the transition state of the rate-determining step. The results are validated by experimental evidence. [source]