Aldol reaction is one of the most important methods for the formation of carbon-carbon bonds. Because of its significance and usefulness, asymmetric versions of this reaction have been realized with different approaches in the past. Over the last decade, the area of organocatalysis has made significant progresses. As one of most studied reactions in organocatalyses, organocatalyzed aldol reaction has emerged as a powerful tool for the synthesis of a large number of useful products in optically enriched forms. In this review, we summarize our efforts on the development of novel organocatalyzed aldol reactions for the enantioselective synthesis of biological active molecules. Literatures closely related to our studies are also covered.
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http://dx.doi.org/10.1055/s-0030-1260029 | DOI Listing |
RSC Adv
June 2024
Centro de Ciências Naturais e Humanas, Universidade Federal do ABC 09210-580 Santo André Brazil
Proline, along with its derivatives, has been employed as an efficient organocatalyst for aldol reactions, with the ability to promote the creation of stereoselective C-C bonds. Even though the Houk-List transition state model is able to explain the stereoselectivity observed when proline is used as a catalyst, few studies investigate the role of microheterogeneous media in modulating the reaction outcome. In this work, molecular dynamics and electronic structure calculations were used to investigate the aldol reaction in the condensed phase.
View Article and Find Full Text PDFOrg Lett
June 2024
Sichuan Research Center for Drug Precision Industrial Technology, West China School of Pharmacy, Sichuan University, Chengdu 610041, China.
We have successfully accomplished a catalytic asymmetric total synthesis of entecavir, a first-line antihepatitis B virus medication. The pivotal aspect of our strategy lies in the utilization of a Pd-catalyzed enyne borylative cyclization reaction, enabling the construction of a highly substituted cyclopentene scaffold with exceptional stereoselectivity. Additionally, we efficiently accessed the crucial 1,3-diol enyne system early in our synthetic route through a diarylprolinol organocatalyzed enantioselective cross-aldol reaction and Re-catalyzed allylic alcohol relocation.
View Article and Find Full Text PDFChem Commun (Camb)
May 2024
School of Environment, State Key Laboratory of Antiviral Drugs, Pingyuan Laboratory, Key Laboratory of Green Chemical Media and Reactions, Ministry of Education, School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang, Henan 453007, China.
Thioglycoside bond formation an asymmetric sulfa-Michael/aldol reaction of ()-β-nucleobase acrylketones and 1,4-dithiane-2,5-diol has been achieved with a cinchona alkaloid-derived bifunctional squaramide chiral catalyst. Diverse purine, benzimidazole, and imidazole substrates are well tolerated and generate 4'-thionucleoside derivatives containing three contiguous stereogenic centers with excellent results (30 examples, up to 97% yield, >20 : 1 dr and up to 99% ee). Moreover, the novel strategy provides an efficient and convenient synthetic route to construct chiral 4'-thionucleosides.
View Article and Find Full Text PDFOrg Lett
February 2024
School of Chemistry, The Bio21 Institute, The University of Melbourne, Melbourne, Victoria 3010, Australia.
The first total synthesis of myxobacteria metabolite icumazole A () is reported. Key steps in the route include an organocatalyzed asymmetric self-aldol reaction followed by an acetate aldol reaction to form the stereotriad present in the oxazole moiety, an intramolecular Diels-Alder reaction to form the isochromanone, and an acetylide addition and selective methylation. The final steps involved a high-yielding modified Cadiot-Chodkiewicz coupling and stereoselective reduction to secure the -diene and afford .
View Article and Find Full Text PDFOrg Biomol Chem
December 2023
Department of Chemistry, Institute of Science, Banaras Hindu University, Varanasi 221 005, India.
A novel, simple and metal-free tandem approach for synthesizing α-substituted ()-α,β-unsaturated aldehyde derivatives through acid-catalyzed epoxide rearrangement and organocatalyzed aldol condensation processes has been described. This transformation has a broad substrate scope under mild conditions, including epoxides and aldehydes containing diverse functional groups, resulting in moderate to high yields of the desired products. Eventually, large-scale reactions and the synthesis of some bioactive molecules are used to demonstrate the potential applicability of the developed method.
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