7287-82-3Relevant articles and documents
Origin of the detrimental effect of lithium halides on an enantioselective nucleophilic alkylation of aldehydes
Pate, Franck,Duguet, Nicolas,Oulyadi, Hassan,Harrison-Marchand, Anne,Fressigne, Catherine,Valnot, Jean-Yves,Lasne, Marie-Claire,Maddaluno, Jacques
, p. 6982 - 6991 (2007)
(Chemical Equation Presented) The effect of lithium halides on the enantioselectivity of the addition of methyllithium on o-tolualdehyde, in the presence of chiral lithium amides derived from chiral 3-aminopyrrolidines (3APLi), has been investigated. The enantiomeric excess of the resulting 1-o-tolylethanol was found to drop upon addition of significant amounts of LiCl, introduced before the aldehyde. The competitive affinity between the lithium amide, the methyllithium, and the lithium halides in THF was examined by multinuclear NMR spectroscopy and DFT calculations. The results showed that the original mixed aggregate of the chiral lithium amide and methyllithium is rapidly, totally, and irreversibly replaced by a similar 1:1 complex involving one lithium chloride or bromide and one lithium amide. While the MeLi/LiX substitution occurs with some degree of epimerization at the nitrogen for the endo-MeLi:3APLi complex, it is mostly stereospecific for the exo-type arrangements of the aggregate. The thermodynamic preference for mixed aggregates between 3APLi and LiX was confirmed by static DFT calculations: the data show that the LiCl and LiBr aggregates are more stable than their MeLi counterparts by more than 10 kcal·mol-1 provided THF is explicitly taken into account. These results suggest that a sequestration of the source of chirality by the lithium halides is at the origin of the detrimental effect of these additives on the ee of the model reaction.
Cinchona-Alkaloid-Derived NNP Ligand for Iridium-Catalyzed Asymmetric Hydrogenation of Ketones
Zhang, Lin,Zhang, Ling,Chen, Qian,Li, Linlin,Jiang, Jian,Sun, Hao,Zhao, Chong,Yang, Yuanyong,Li, Chun
supporting information, p. 415 - 419 (2022/01/12)
Most ligands applied for asymmetric hydrogenation are synthesized via multistep reactions with expensive chemical reagents. Herein, a series of novel and easily accessed cinchona-alkaloid-based NNP ligands have been developed in two steps. By combining [Ir(COD)Cl]2, 39 ketones including aromatic, heteroaryl, and alkyl ketones have been hydrogenated, all affording valuable chiral alcohols with 96.0-99.9% ee. A plausible reaction mechanism was discussed by NMR, HRMS, and DFT, and an activating model involving trihydride was verified.
C3 The symmetry contains a chiral ligand H3L of an amide bond. Preparation method and application
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Paragraph 0092-0099, (2021/09/08)
The invention discloses C. 3 Chiral ligand H with symmetric amide bond3 L Relates to the technical field of material chemistry and chiral chemistry. The invention further provides the chiral ligand H. 3 L Preparation method and application thereof. The present invention has the advantage that the chiral ligand H of the present invention is a chiral ligand. 3 The L has a higher C. 3 The symmetric and flexible amide group enables coordination of the lanthanide metal ions with high coordination number and high oxygen affinity to be assembled into a novel structure-structure lanthanide metal chiral porous coordination cage. Moreover, the abundant chiral amide groups and amino acid residues on the ligand framework can be directly introduced into the synthesized lanthanide metal chiral porous coordination cage, thereby being beneficial to generating multiple chiral recognition sites and unique chiral microenvironments which mimic the biological enzyme binding pocket and further realize the purpose of high enantioselectivity separation of a series of chiral small molecule compounds.
Dynamic Kinetic Resolution of Alcohols by Enantioselective Silylation Enabled by Two Orthogonal Transition-Metal Catalysts
Oestreich, Martin,Seliger, Jan
, p. 247 - 251 (2020/10/29)
A nonenzymatic dynamic kinetic resolution of acyclic and cyclic benzylic alcohols is reported. The approach merges rapid transition-metal-catalyzed alcohol racemization and enantioselective Cu-H-catalyzed dehydrogenative Si-O coupling of alcohols and hydrosilanes. The catalytic processes are orthogonal, and the racemization catalyst does not promote any background reactions such as the racemization of the silyl ether and its unselective formation. Often-used ruthenium half-sandwich complexes are not suitable but a bifunctional ruthenium pincer complex perfectly fulfills this purpose. By this, enantioselective silylation of racemic alcohol mixtures is achieved in high yields and with good levels of enantioselection.
