The asymmetric Mannich reaction ranks among the most potent enantioselective and diastereoselective C-C-bond forming reactions. In recent years, organocatalysed versions of asymmetric Mannich processes have been increasingly reported and used in a rapidly growing number of applications. This tutorial review provides an overview of the recent history of the asymmetric organocatalysed Mannich reaction, including scope and limitations, and application of different catalyst systems.
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http://dx.doi.org/10.1039/b713885g | DOI Listing |
J Org Chem
January 2025
Key Laboratory of Medicinal Molecule Science & Pharmaceutical Engineering, School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 100081, China.
A concise and efficient asymmetric Mannich/hemiketalization/retro-Henry cascade reaction between -hydroxy-α-aminosulfones and α-nitroketones was developed by utilizing a cinchona-derived bifunctional squaramide catalyst. This methodology provided access to β-nitro-substituted amino compounds with up to 95% yield and >99% ee. The practicality was demonstrated by scale-up and diverse derivatizations, including the synthesis of imidazolidinone and amino acid analogs.
View Article and Find Full Text PDFAcc Chem Res
January 2025
Chongqing Key Laboratory of Natural Product Synthesis and Drug Research, Innovative Drug Research Center, School of Pharmaceutical Sciences, Chongqing University, Chongqing 401331, China.
ConspectusThe Mannich reaction, involving the nucleophilic addition of an enol(ate) intermediate to an imine or iminium ion, is one of the most widely used synthetic methods for the synthesis of β-amino carbonyl compounds. Nevertheless, the homo-Mannich reaction, which utilizes a homoenolate intermediate as the nucleophilic partner and provides straightforward access to the valuable γ-amino carbonyl compounds, remains underexplored. This can be largely attributed to the difficulties in generation and manipulation of the homoenolate species, despite various homoenolate equivalents that have been developed.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
State Key Laboratory of Bioactive Molecules and Druggability Assessment, Jinan University, Guangzhou, 510632, China.
Secupyritines A-C are unique polycyclic Securinega alkaloids isolated from medicinal plant Flueggea suffruticosa. They feature a distinctive 6/6/6/5/6 fused pentacyclic ring system with a highly strained 2-oxa-6-aza[4.4.
View Article and Find Full Text PDFNat Commun
December 2024
Key Laboratory of Phytochemistry and Natural Medicines, Kunming Institute of Botany, Chinese Academy of Sciences, Kunming, China.
The functionalized polycycle with densely contiguous tertiary stereocenters is a formidable challenge in synthesizing the parvistemoline family of Stemona alkaloids. We herein report their catalytic, asymmetric total syntheses in 13-14 steps from commercially available 2-(methoxycarbonyl)-pyrrole, featuring the development and deployment of an Ir/Pd-synergistically-catalyzed allylation of α-non-substituted keto esters with secondary aryl-substituted alcohols, stereodivergently accessible to four stereoisomers. Using chiral Pd-enolate and Ir π-allyl complex under neutral conditions, no epimerization occurs.
View Article and Find Full Text PDFBiopolymers
January 2025
Department of Chemistry, Faculty of Engineering and Science, Bursa Technical University, Bursa, Turkey.
Cellulose is one of the most abundant biopolymers in nature. Despite being the subject of research in various fields, it is not as famous as chitosan in catalyst design. Herein, a novel thiourea-functionalized cellulose (CTU-6) was synthesized as a robust hydrogen bonding catalyst with the degree of substitution (DS) of 0.
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