The regulation of regioselectivity is an objective often pursued by organic chemists, and the comprehension of its mechanisms is crucial for devising efficient synthetic pathways. In this report, we conducted theoretical calculations to explore the regioselectivity regulatory mechanisms of two palladium-catalyzed cyclization reactions. In these cyclization reactions, manipulating the structural differences in the reaction substrates leads to the formation of distinct products. A detailed reaction mechanism and reactivity profile for this reaction were revealed. Furthermore, a π-π stacking assisted regioselectivity regulatory mechanism was proven by distortion-interaction energy analysis and noncovalent interaction calculations. The calculated results presented herein provide a theoretical guide for further experimental investigations of regioselectivity regulation.
Download full-text PDF |
Source |
|---|---|
| http://www.ncbi.nlm.nih.gov/pmc/articles/PMC11615657 | PMC |
| http://dx.doi.org/10.1039/d4ra06552b | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Cobalt-Catalyzed Enantioselective Reductive Coupling of Imines and Internal Alkynes.
Angew Chem Int Ed Engl
January 2025
IISER Kolkata: Indian Institute of Science Education and Research Kolkata, Department of Chemical Sciences, Mohanpur, 741246, Nadia, INDIA.
Chiral allyl amines are important structural components in natural products, pharmaceuticals, and chiral catalysts. Herein, we report a cobalt-catalyzed enantioselective reductive coupling of imines with internal alkynes to synthesize chiral allyl amines. The reaction is catalyzed by a cobalt complex derived from commercially available bisphosphine ligand utilizing zinc as the electron donor.
View Article and Find Full Text PDF[1+5] Cyclization of Indoline-Derived Azadienes with 1,3,5-Triazinanes: An Efficient Protocol for the Synthesis of Indoline-Spiro-Hexahydropyrimidines.
Chemistry
January 2025
Zhengzhou University, School of Pharmaceutical Sciences, 100 Science Avenue, 450001, Zhengzhou, CHINA.
An unprecedented formal [1+5] cyclization of indoline-derived azadienes with 1,3,5-triazinanes has been realized, providing a facile access to biologically important indoline-spiro-hexahydropyrimidines with good to excellent yields (up to 99% yield). Different from previous reports, this is the first study that indoline-derived azadienes could participate in cyclizations as one-atom synthons. This methodology is also distinguished by not involving any additive or catalyst, readily available starting materials, wide range of substrate applicability, operational simplicity and simultaneously reassembling two C-N and two C-C bonds in one-step reaction.
View Article and Find Full Text PDFUltrastable Imidazole-linked Porous Organic Cages for Ammonia Capture and Detection.
Angew Chem Int Ed Engl
January 2025
Chinese Academy of Sciences Fujian Institute of Research on the Structure of Matter, State Key Laboratory of Structural Chemistry, 350108, Fuzhou, CHINA.
Here, we report the facile synthesis of imidazole-linked porous organic cages (IPOCs) via an in-situ cyclization reaction protocol. Specifically, three IPOCs with [2+4] lantern-like structures and one with a [3+6] triangular prism structure were successfully prepared through condensation reactions between tetraformyl-functionalized calix[4]arene and bis(o-phenylenediamine) monomers in a single pot. Notably, these IPOCs exhibit high porosity, with Brunauer-Emmett-Teller (BET) specific surface areas reaching up to 1162 m2 g-1.
View Article and Find Full Text PDFVisible-light-induced radical-cascade alkylation/cyclization of acrylamides: access to 3,3-dialkylated oxindoles.
Org Biomol Chem
January 2025
School of Chemical Engineering, Zhengzhou University, Zhengzhou 450001, China.
A visible-light-induced deoxygenative alkylation/cyclization of acrylamides with alcohols activated by CS has been developed by using xanthate salts as alkyl radical precursors in the presence of tricyclohexylphosphine. It proceeds through a tandem radical addition/cyclization process, and this protocol provides a reliable and practical approach to building the skeleton of 3,3-disubstituted oxindoles in moderate to good yields. Notable features of this reaction include readily available starting reagents, broad substrate scope and mild reaction conditions.
View Article and Find Full Text PDFOne Step Synthesis of 4,6,8-Trimethoxyazulenes - a General Building Block for 2-Functionalized Azulenes.
Chemistry
January 2025
Ruprecht Karls Universitat Heidelberg, Organisch-Chemisches Institut, Im Neuenheimer Feld 270, 69120, Heidelberg, GERMANY.
Here we present a simple gold-catalyzed one-pot reaction of easily available diarylbutadiynes, with trimethoxybenzene as solvent and reactant to synthesize 4,6,8-trimethoxyazulenes. The methoxy substituents, which render the azulene very electron-rich, enable a change of azulenes typical regioselectivity for electrophilic substitutions, which enables facile electrophilic 2-substitution with iodine, bromine, chlorine, selenium or sulfur. Especially the 2-haloazulenes which can usually only be obtained through lengthy multistep syntheses are valuable building blocks for the synthesis of 2-substituted azulene derivatives.
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!