We disclose here practical strategies toward the synthesis of morpholines and Claisen rearrangement products based on the divergent reactivity of a common halonium intermediate. These reactions employ widely available alkenes in a Lewis acid-catalyzed halo-etherification process that can then transform them into the desired products with exceptional regioselectivity for both activated and unactivated olefins. Our mechanistic probe reveals an interesting regiochemical kinetic resolution process.
Download full-text PDF |
Source |
|---|---|
| http://www.ncbi.nlm.nih.gov/pmc/articles/PMC9205334 | PMC |
| http://dx.doi.org/10.1021/acs.joc.1c02804 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
DFT Investigation of the Stereoselectivity of the Lewis-Acid-Catalyzed Diels-Alder Reaction between 2,5-Dimethylfuran and Acrolein.
ACS Omega
January 2025
Laboratory of Theoretical Chemistry, Theoretical and Structural Physical Chemistry Unit, Namur Institute of Structured Matter (NISM), University of Namur, rue de Bruxelles, 61, B-5000 Namur, Belgium.
Density functional theory (DFT) has been enacted to study the Diels-Alder reaction between 2,5-dimethylfuran (2,5-DMF), a direct product of biomass transformation, and acrolein and to analyze its thermodynamics, kinetics, and mechanism when catalyzed by a Lewis acid (LA), in comparison to the uncatalyzed reaction. The uncatalyzed reaction occurs via a typical one-step asynchronous process, corresponding to a normal electron demand (NED) mechanism, where acrolein is an electrophile whereas 2,5-DMF is a nucleophile. The small endo selectivity in solvents of low dielectric constants is replaced by a small exo selectivity in solvents with larger dielectric constants, such as DMSO.
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 PDFLewis acid-catalyzed [2π+2σ] cycloaddition of dihydropyridines with bicyclobutanes.
Chem Commun (Camb)
January 2025
Organisch-Chemisches Institut, Universität Münster, Corrensstraße 40, 48149 Münster, Germany.
Herein we report a simple BF-catalyzed cycloaddition of dihydropyridines with bicyclobutanes for the expedient synthesis of novel three-dimensional azacycle-fused bicyclo[2.1.1]hexane scaffolds.
View Article and Find Full Text PDFDiverse Synthesis of Arene-Fused [n.1.1]-Bridged Molecules via Catalytic Cycloaddition and Rearrangement Reactions.
Angew Chem Int Ed Engl
December 2024
Frontier Institute of Science and Technology, Xi'an Jiaotong University, Xi'an, Shaanxi, 710054, China.
Although great advancement has been made in synthesis of 3D bridged bicyclic[n.1.1]-bioisosteres, facile construction of 2D/3D merged molecules incorporating bridged rings, as novel chemical space in drug discovery, remains a significant challenge.
View Article and Find Full Text PDFElectrogenerated Lewis Acid-Catalyzed Claisen Rearrangement of Allyl Aryl Ethers.
Org Lett
December 2024
Division of Applied Chemistry, Graduate School of Environmental, Life, Natural Science and Technology, Okayama University, 3-1-1 Tsushima-naka, Kita-ku, Okayama 700-8530, Japan.
Catalysts for Claisen rearrangement have been intensively studied to overcome the need for high temperature. However, previous studies have encountered challenges, such as the need for heating, a long reaction time, and/or the need for equivalent amounts of catalyst. In this study, we introduce an effective electrogenerated boron-based Lewis acid catalyst for the aromatic Claisen rearrangement, which proceeds in a few minutes at ambient temperature.
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!