Alkyl enol ethers (AEE) are versatile synthetic intermediates with a unique reactivity pattern. This review article summarizes the synthesis of AEE as well as its reactivity and how enol ether undergoes intermolecular reactions for various bond formation, leading to the construction of several useful organic molecules. The synthetic applications of alkyl enol ethers towards intermolecular bond-forming reactions include metal-catalyzed reactions, cycloaddition and heterocycle formation as well as rwactions in the field of natural products synthesis. The achievement of these impressive transformations prove the countless synthetic potential of AEE. The main objective of this review is to bring attentiveness among synthetic chemists to show how AEE extensively can be used to react with both electrophiles as well as nucleophiles, thereby behaving as an ambiphilic reactant. We trust that the unique reactivity pattern of alkyl enol ethers and the fundamental mechanistic idea can attract chemists in AEE chemistry. Exclusively, intermolecular reactions of AEE with other functionalized moieties have not been reviewed to the best of our knowledge.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1002/asia.202100277 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Chemoenzymatic Formation of Oxa-Terpenoids by Sesqui- and Diterpene Synthase-Mediated Biotransformations with 9-Oxy-FPP Ether Derivatives.
Biochemistry
January 2025
Institute of Organic Chemistry, Leibniz University Hannover, Schneiderberg 1B, Hannover 30167, Germany.
Farnesyl pyrophosphate derivatives bearing an additional oxygen atom at position 5 proved to be very suitable for expanding the substrate promiscuity of sesquiterpene synthases (STSs) and the formation of new oxygenated terpenoids. Insertion of an oxygen atom in position 9, however, caused larger restraints that led to restricted acceptance by STSs. In order to reduce some of the proposed restrictions, two FPP-ether derivatives with altered substitution pattern around the terminal olefinic double bond were designed.
View Article and Find Full Text PDFVisible light-mediated formal alkylation and [4+1]-cycloaddition strategies of silyl enol ethers with aryldiazoacetates.
Chem Commun (Camb)
January 2025
Universidade Estadual de Campinas, Instituto de Química, CEP 13083-862, Campinas, SP, Brazil.
A reaction sequence of visible light-mediated cyclopropanation/acid-promoted ring-opening is described for the formal alkylation of silyl enol ethers with aryldiazoacetates. Under the same conditions, the Danishefsky's diene can react with aryldiazoacetates to afford [4+1]-cycloaddition adducts. Key mechanistic aspects are proposed based on experimental evidence and DFT calculations.
View Article and Find Full Text PDFN Dissociation vs Reversible 1,2-Methyl Migration in PCP Cobalt(I) Complexes in the Stereoselective Isomerization () of Allyl Ethers.
JACS Au
November 2024
Schulich Faculty of Chemistry and the Resnick Sustainability Center for Catalysis, Technion - Israel Institute of Technology, Technion City, Haifa 3200008, Israel.
With growing efforts pushing toward sustainable catalysis, using earth-abundant metals has become increasingly important. Here, we present the first examples of cobalt PCP pincer complexes that demonstrate dual stereoselectivity for allyl ether isomerization. While the cationic cobalt complex [((PCP)Co)-μ-N][BAr ] () mainly favors the -isomer of the enol ether, the corresponding methyl complex [(PCP)CoMe] () mostly gives the -isomer.
View Article and Find Full Text PDFOxy-pyridinium Ylides Mediated 1,4-Pyridyl/Aryl Translocation.
Org Lett
November 2024
Jiangsu Key Laboratory of Advanced Catalytic Materials & Technology, School of Petrochemical Engineering, Changzhou University, Changzhou, Jiangsu 213164, People's Republic of China.
Molecular rearrangement via carbene transfer is a powerful tool to access molecular diversity. Herein, we describe an efficient approach to selective pyridyl/aryl relocation via a rhodium-catalyzed aminoarylation of diazo compounds, providing a promising strategy to access -pyridyl N-alkylated pyridone scaffolds in a single operation. This reaction features the novel reactivity of oxy-pyridinium ylide, rhodium-associated five-membered transition state, and 1,4-pyridyl/aryl relocation.
View Article and Find Full Text PDFUltrasound-Assisted Remote Benzylic C(sp)-H Alkylation of -Fluoroamides with Enol Silanes.
J Org Chem
November 2024
State Key Laboratory and Institute of Elemento-Organic Chemistry, National Engineering Research Center of Pesticide, Nankai University; College of Chemistry, Nankai University, Weijin Road 94#, Nankai District, Tianjin 300071, China.
We have developed an ultrasound-assisted remote benzylic C(sp)-H alkylation of -fluorobenzamides with enol silanes; a series of β-aryl substituted propiophenones was generated in good to high yields. This reaction represents a C(sp)-C(sp) coupling and features simplicity, high efficiency, and wide substrate scope in a multiple-step sequential process, which involves N-F homolysis, 1,5-hydrogen atom transfer, benzylic radical addition, oxidation by copper(II) salt, and removal of the trimethylsilyl group. Also, DFT theoretical calculations and Marcus theory were employed to consolidate the proposed reaction mechanism.
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!