This review describes unexpected dynamical behaviors of rearranging carbocations and the modern computational methods used to elucidate these aspects of reaction mechanisms. Unique potential energy surface topologies associated with these rearrangements have been discovered in recent years that are not only of fundamental interest, but also provide insight into the way Nature manipulates chemical space to accomplish specific chemical transformations. Cautions for analyzing both experimental and theoretical data on carbocation rearrangements are included throughout.
Download full-text PDF |
Source |
|---|---|
| http://www.ncbi.nlm.nih.gov/pmc/articles/PMC4902080 | PMC |
| http://dx.doi.org/10.3762/bjoc.12.41 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Engineering terpene synthases and their substrates for the biocatalytic production of terpene natural products and analogues.
Chem Commun (Camb)
January 2025
School of Chemistry, Cardiff University, Main Building, Park Place, CF10 3AT, Cardiff, UK.
Terpene synthases produce a wide number of hydrocarbon skeletons by controlling intramolecular rearrangements of allylic pyrophosphate subtrates reactive carbocation intermediates. Here we review recent research focused on engineering terpene synthases and modifying their substrates to rationally manipulate terpene catalyisis. Molecular dynamic simulations and solid state X-ray crystallography are powerful techniques to identify substrate binding modes, key active site residues for substrate folding, and the location of active site water.
View Article and Find Full Text PDFAliphatic Amines Unlocked for Selective Transformations through Diazotization.
Angew Chem Int Ed Engl
December 2024
Institute of Organic Chemistry Polish Academy of Sciences, Kasprzaka 44/52, 01-224, Warsaw, Poland.
While aromatic diazonium salts are important reagents in organic synthesis, 'Diazonium ions generated from ordinary aliphatic primary amines are usually useless for preparative purposes, since they lead to a mixture of products giving not only substitution by any nucleophile present, but also elimination and rearrangements if the substrate permits.' In this work, we report that this statement is no longer valid, and it is now possible to control diazotization of aliphatic amines by utilizing isopentyl nitrite in HFIP. This transformation enabled electrophilic aromatic substitution with these highly abundant and commercially available alkyl reagents, as well as transforming them into building blocks typically employed in organic synthesis.
View Article and Find Full Text PDFMechanistic Investigation of the Pseudo-Halogen Effect in Enantioselective Aminocatalyzed [6 + 4] and [10 + 6] Cycloadditions: Enabling Unique Favorskii-Like Rearrangements.
J Am Chem Soc
December 2024
Department of Chemistry, Aarhus University, DK-8000 Aarhus C, Denmark.
A mechanistic investigation into the novel combination of the -halogen effect with enantioselective aminocatalysis unravels the mechanistic intricacies of [6 + 4] and [10 + 6] higher-order cycloadditions and the succeeding new Favorskii-like rearrangements. By introducing the OTf-group into the tropone framework, it can serve both as an activator for the cycloaddition and as a proficient leaving group within the corresponding cycloadduct, thus enabling unprecedented ring-contracting Favorskii-like rearrangements. Integrating the -OTf group creates an electron-deficient 6π-component leveraging the -halogen effect by enhancing the polarization and introducing new strategic interaction points.
View Article and Find Full Text PDFBioinspired Total Synthesis of Natural Products.
Acc Chem Res
December 2024
State Key Laboratory of Natural and Biomimetic Drugs, School of Pharmaceutical Sciences, and Chemical Biology Center, Peking University, 38 Xueyuan Road, Beijing 100191, China.
Article Synopsis
- The text discusses the challenges in total synthesis of natural products, focusing on improving efficiency and allowing for diverse syntheses.
- It highlights the use of bioinspired synthesis, especially late-stage skeletal diversification, as an effective strategy to achieve these goals.
- The authors summarize their research efforts, including key methods that mimic natural biosynthetic reactions to create complex molecules efficiently, showcasing successful syntheses of various natural products.
The crystal structure of Grindelia robusta 7,13-copalyl diphosphate synthase reveals active site features controlling catalytic specificity.
J Biol Chem
December 2024
Department of Plant Biology, University of California-Davis, Davis, California, USA. Electronic address:
Diterpenoid natural products serve critical functions in plant development and ecological adaptation and many diterpenoids have economic value as bioproducts. The family of class II diterpene synthases catalyzes the committed reactions in diterpenoid biosynthesis, converting a common geranylgeranyl diphosphate precursor into different bicyclic prenyl diphosphate scaffolds. Enzymatic rearrangement and modification of these precursors generate the diversity of bioactive diterpenoids.
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!