Asymmetric epoxidation of α-substituted acroleins with hydrogen peroxide has been catalyzed by diphenylprolinol diphenylmethylsilyl ether to afford α-substituted-β,β-unsubstituted-α,β-epoxy aldehyde with excellent enantioselectivity and the generation of a chiral quaternary carbon center. The method was applied to a short synthesis of (R)-methyl palmoxirate.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1021/ol102269s | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Chiral Bis-8-Aryl-isoquinoline Bis-alkylamine Iron Catalysts for Asymmetric Oxidation Reactions.
Org Lett
January 2025
Department of Chemistry, Ben-Gurion University of the Negev, Beer-Sheva 8410501, Israel.
A novel class of bis-8-aryl-isoquinoline () bis-alkylamine iron complexes, Fe()(OTf) and Fe()(OTf) ( = dipyrrolidinyl or = ,'-dimethylcyclohexyl-diamine), for asymmetric oxidation reactions is reported. The scalable divergent synthesis of 8-aryl-3-formylisoquinolines (), the key intermediates in preparing these ligands, enables precise structural and electronic tuning around the metal center. The enantioselective epoxidation and hydroxy carbonylation of conjugated alkenes, mediated by the Fe() catalyst with HO as the oxidant, demonstrates the potential of these redox Fe[N] catalysts in inducing face selection in oxygen transfer transformations.
View Article and Find Full Text PDFPeroxycarbenium-Mediated Asymmetric Synthesis of 1,2-Dioxanes and 1,2-Dioxolanes.
J Am Chem Soc
January 2025
BioCIS, Faculté de Pharmacie, Université Paris-Saclay, CNRS, Orsay 91400, France.
The endoperoxide scaffold is found in numerous natural products and synthetic substances of pharmaceutical interest. The main challenge to their synthetic access remains the preparation of chiral compounds due to the weakness of the peroxide bond, which limits the scope of available or applicable methods. Here, we demonstrate how peroxycarbenium species can be trapped by silylated nucleophiles with high enantioselectivities and diastereoselectivities when applicable, using a chiral imidophosphorimidate (IDPi) as a catalyst.
View Article and Find Full Text PDFHighly Position- and Enantioselective Catalytic Epoxidation of Polyolefins Mediated by a Chiral Mn Complex, Including a One-Step Conversion of Squalene to the ()-2,3-Epoxide, a Precursor of Natural Steroids and Terpenoids.
J Am Chem Soc
January 2025
Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts 02138, United States.
Reported herein is the synthesis of a novel chiral dicarboxylic ligand for Mn(II) and the application of the Mn complex to the highly enantio- and position-selective epoxidation of C═C under mild conditions, even with polyolefinic substrates. A stereomechanistic basis for asymmetric induction is suggested.
View Article and Find Full Text PDFBioinspired concise synthesis of caged Sesquiterpenoids Artatrovirenols A and B.
Nat Commun
January 2025
State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou, 730000, Gansu, PR China.
Artatrovirenols A and B are two newly isolated sesquiterpenoids with a complex caged framework. We report herein a concise synthesis of artatrovirenols A and B in 9 and 8 steps, respectively. The complex caged tetracycle is rapidly constructed from a known planar guaiane-type precursor through a bioinspired intramolecular [4 + 2] cyclization to firstly access artatrovirenol B, which is further transformed into artatrovirenol A through a biomimetic epoxidation-mediated lactonization reaction.
View Article and Find Full Text PDFCurrent-Regulated Selective Nickel-Catalyzed Electroreductive Cross-Electrophile Carbonylation to β/γ-Hydroxy Ketones.
Angew Chem Int Ed Engl
December 2024
School of Chemical Engineering and Technology, Xi'an Jiaotong University, Xi An Shi, Xi'an 710049, P. R. China.
The nickel catalyzed multi-component cross-electrophile carbonylation which emerges as a powerful and efficient method for constructing diverse ketones has attracted increasing attention of organic chemists. However, the selectivity of this reaction poses a significant challenge. In this work, we have developed a current-regulated selective nickel-catalyzed electroreductive cross-electrophile carbonylation, which offers a direct convergent synthesis of β/γ-hydroxy ketones, which represent pivotal structural motifs found in numerous natural products, bioactive molecules, pharmaceutical compounds, and essential building blocks.
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!