We report synthetic methodology that permits access to two oxacyclic strained intermediates, the 4,5-benzofuranyne and the 3,4-oxacyclohexyne. In situ trapping of these intermediates affords an array of heterocyclic scaffolds by the formation of one or more new C-C or C-heteroatom bonds. Experimentally determined regioselectivities were consistent with predictions made using the distortion/interaction model and were also found to be greater compared to selectivities seen in the case of trapping experiments of the corresponding N-containing intermediates. These studies demonstrate the synthetic versatility of oxacyclic arynes and alkynes for the synthesis of functionalized heterocycles, while further expanding the scope of the distortion/interaction model. Moreover, these efforts underscore the value of harnessing strained heterocyclic intermediates as a unique approach to building polycyclic heteroatom-containing frameworks.
Download full-text PDF |
Source |
|---|---|
| http://www.ncbi.nlm.nih.gov/pmc/articles/PMC7036139 | PMC |
| http://dx.doi.org/10.1021/jacs.6b01986 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Density Functional Theory Rationalization of the Mechanism, Selectivity, and Role of Substituents in Au(I)-Catalyzed Synthesis of Pyrazolines and Dihydropyridines.
J Org Chem
December 2024
College of Chemistry and Chemical Engineering, Shaanxi University of Science and Technology, Xi'an 710021, P. R. China.
Article Synopsis
- - A study investigated how gold catalysts affect the synthesis of pyrazolines and dihydropyridines from imines and methyl phenylpropiolate, focusing on three different imines with unique substituents.
- - The research found that the type of nitrogen substituent influences the reaction path: NHCOMe leads to outward ring opening and pyrazoline products, while aromatic substituents prompt inward ring opening and dihydropyridine products.
- - The configuration of dihydropyridine is determined by the substituent on the aromatic ring, with electron-donating groups causing direct formation of 1,4-dihydropyridine and electron-withdrawing groups leading to 1,2-dihyd
Insights into the Synergistic Interplay of Ligand and Base Effects in Palladium-Catalyzed Enantioselectivity Hydrofunctionalization of Dienes.
Inorg Chem
November 2024
Jilin Provincial Key Laboratory of Organic Functional Molecular Design & Synthesis. Faculty of Chemistry, Northeast Normal University, Changchun 130024, China.
Transition-metal-catalyzed enantioselective C-O bond constructions via hydrofunctionalization involving the use of O-based nucleophiles are an important topic in synthetic chemistry. Herein, density functional theory calculations were conducted to unveil the mechanism and enantioselectivity of Pd-catalyzed asymmetric hydrofunctionalization of conjugated dienes. We found that the base-assisted 4,3-activation model of the ligand-to-ligand hydrogen transfer (LLHT) mechanism is the most preferred one among all the cases, which could be ascribed to the favorable C-H···O interactions and the electrostatic interactions.
View Article and Find Full Text PDFThe role of linkers and frustrated lewis pairs catalysts in the formation of zwitterionic 1,2-anti-addition product with non-conjugated terminal diacetylenes: A computational study.
J Mol Graph Model
December 2024
Computation and Simulation Unit (Analytical & Environmental Science Division and Centralized Instrument Facility), CSIR-Central Salt & Marine Chemicals Research Institute, Bhavnagar, Gujarat, India, 364 002; Academy of Scientific and Innovative Research (AcSIR), Ghaziabad, 201002, India. Electronic address:
This study presents a computational investigation into the mechanistic pathway and the linker units involved in forming the zwitterionic 1,2-anti-addition product of non-conjugated diacetylenes, di(propargyl)ether (DPE), di(prop-2yn-1yl)sulfane (DPS) and 1,6-Heptadiyne (HD) catalyzed by the inter-molecular phosphine/borane frustrated Lewis pairs (FLPs), i.e., PPh[CH(CF)](P-CF)/[B(CF)]([B]) and P(o-tolyl)(P-tol)/[B(CF)]([B]).
View Article and Find Full Text PDFDiels-Alder Reaction Mechanisms of La@C and Gd@C Studied Using Density Functional Theory.
Chemistry
November 2024
Institute of Chemical Research of Catalonia (ICIQ-CERCA), The Barcelona Institute of Science and Technology, Avgda. Països Catalans, 16, Tarragona, 43007, Spain.
Encapsulation of transition metals represents a crucial method for modifying the electronic structure and regulating the reactivity of fullerene, thereby expanding its applications. Herein, we present calculations with density functional theory methods to investigate the mechanisms of the Diels-Alder (DA) reactions of cyclopentadiene and La@C or Gd@C as well as their tricationic derivatives. Our findings indicate that the encapsulation of La and Gd into the C cage is thermodynamically favorable.
View Article and Find Full Text PDFComputational Exploration on Coupling Formic Acid Production with Propylene Synthesis via Catalytic Transfer Hydrogenation: The Role of beyond Reverse Water Gas Shift Reaction.
J Org Chem
September 2024
Department of Chemistry, Visva-Bharati University, Santiniketan, Bolpur 731235, India.
CO-assisted propane dehydrogenation (CO-ODHP) is emerging as an alternative route to the direct dehydrogenation of propane. Previous studies on CO-ODHP have shown that the role of CO is to shift the reaction equilibrium toward the product side by consuming the produced H molecules via reverse water gas shift (RWGS) reaction. Since the ultimate fate of CO is to get reduced, we herein propose another pathway of CO reduction in the realm of CO-ODHP─CO hydrogenation to formic acid (FA).
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!