The highly enantioselective organocatalytic synthesis of dihydropyran spirocyclic compounds bearing di- and trifluoromethyl groups by aldol cyclization reaction via trienamine using cyclic 2,5-dienones and different di- and trifluoromethylketones is described. Using a bifunctional aminothiourea catalyst, trifluoromethyl-functionalized dihydropyran spirocyclic products were obtained with good yields and enantioselectivities. Subsequent transformation with H and Pd/C has allowed the synthesis of the tetrahydropyran structure with three stereocenters. The plausible reaction mechanism was investigated by computational methods.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1021/acs.joc.4c01839 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Catalytic Asymmetric Total Synthesis of (+)-Chamaecydin and (+)-Isochamaecydin and their Stereoisomers.
Angew Chem Int Ed Engl
January 2025
Changchun Institute of Applied Chemistry Chinese Academy of Sciences: Chang Chun Institute of Applied Chemistry Chinese Academy of Sciences, Jilin Province Key Lab of Green Chemistry and Process, CHINA.
A modular approach was developed for the first catalytic asymmetric total syntheses of naturally occurring C30 terpene quinone methides and their non-natural stereoisomers, which feature the presence of an unprecedented spiro[4.4]nonane-containing 6-6-6-5-5-3 hexacyclic skeleton. Resting on a chiral phosphinamide-catalyzed enantioselective reduction of 2,2-disubstituted cyclohexane-1,3-dione, a concise route for the synthesis of enantioenriched 6-6 bicyclic fragment was developed.
View Article and Find Full Text PDFIntramolecular Cascade Cyclization of Cyclobutanone: Asymmetric Construction of Cyclobutanone Fused Oxa-Spirocycles.
Org Lett
January 2025
Department of Chemistry, Indian Institute of Science Education and Research (IISER) Bhopal, Bhopal By-pass Road, Bhauri, Bhopal 462066, India.
The successful implementation of a cascade reaction involving a cyclobutyl unit has posed a significant challenge in achieving ring-retentive functionalization because of the ring's sacrificial tendency. Herein, we have accomplished a cinchona-derived squaramide-catalyzed cascade reaction sequence, encompassing the desymmetrization of cyclobutanone, followed by an aldol reaction and, subsequently, a 1,4-addition step. This overall process offers a viable strategy to access architecturally fascinating oxa-spirocycles fused with cyclobutanone motifs in good yields with high optical purity.
View Article and Find Full Text PDFPromoted formation of pyrazines by targeted precursor addition to improve aroma of thermally processed methionine-glucose Amadori compound.
Food Chem
February 2025
Department of Food Science, Rutgers University, 65 Dudley Road, New Brunswick, NJ 08901, USA. Electronic address:
The methionine/glucose (Met/Glc) and methionine/glucose-derived Amadori rearrangement product (MG-ARP) models were established to analyze their differences in flavor profiles and aroma potentiality. The principal component analysis revealed the advantage of MG-ARP in the formation of low temperature-induced processing flavor. MG-ARP exhibited superior potential in the rapid formation and high intensity of processed flavor than the Met/Glc except for the inefficiency in pyrazine production.
View Article and Find Full Text PDFTen-Step Total Synthesis of (±)-Phaeocaulisin A Enabled by Cyclopropanol Ring-Opening Carbonylation.
J Am Chem Soc
November 2024
Department of Chemistry, Emory University, Atlanta, Georgia 30322, United States.
We report an efficient total synthesis of (±)-phaeocaulisin A, a guaianolide sesquiterpene natural product possessing a complex tetracyclic skeleton embedded with an oxaspirolactone and a fused bicyclic lactone, four oxygen-containing stereocenters, and an 8-oxabicyclo[3.2.1]octane core.
View Article and Find Full Text PDFConcise Synthesis of Norzoanthamine Enabled by a Set of Photochemical Transformations.
J Am Chem Soc
November 2024
School of Pharmacy, Fudan University, Shanghai, China, 201203.
Norzoanthamine is a structurally complex polycyclic natural product that expresses a broad range of biological activities, rendering facile access to it and its analogs of considerable importance in drug discovery and development. However, strategies for efficient access to this class of marine alkaloids remain lacking. Here, we report a strategy, characterized by three key photochemical reactions, that we used to synthesize norzoanthamine in 16 steps.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!