The diazo group has untapped utility in chemical biology. The tolerance of stabilized diazo groups to cellular metabolism is comparable to that of azido groups. However, chemoselectivity has been elusive, as both groups undergo 1,3-dipolar cycloadditions with strained alkynes. Removing strain and tuning dipolarophile electronics yields diazo group selective 1,3-dipolar cycloadditions that can be performed in the presence of an azido group. For example, diazoacetamide but not its azido congener react with dehydroalanine residues, as in the natural product nisin.
Download full-text PDF |
Source |
|---|---|
| http://www.ncbi.nlm.nih.gov/pmc/articles/PMC5141246 | PMC |
| http://dx.doi.org/10.1021/acs.orglett.6b00278 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Scalable synthesis of (±)-gregatin A a 1,3-dipolar cycloaddition strategy.
Org Biomol Chem
January 2025
State Key Laboratory and Institute of Elemento-Organic Chemistry, Frontiers Science Center for New Organic Matter, College of Chemistry, Nankai University, Tianjin 300071, China.
A 6-step gram-scale synthesis of the fungal polyketide (±)-gregatin A is described. The synthetic route features an intermolecular 1,3-dipolar cycloaddition, a Mo-mediated disconnection of the isoxazole skeleton, and an acid-mediated deprotection/enamine hydrolysis and hemiketalization cascade.
View Article and Find Full Text PDFSynthesis of Nonplanar Push-Pull Chromophores with Various Heterocyclic Moieties via [2 + 2] Cycloaddition-Retroelectrocyclization Reaction.
J Org Chem
January 2025
Department of Materials Science and Engineering, Institute of Science Tokyo, 2-12-1 Ookayama, Meguro-ku, Tokyo 152-8552, Japan.
A series of 1,1,4,4-tetracyanobuta-1,3-diene (TCBD) derivatives with various heterocyclic moieties, including pyridine, carbazole, indole, and benzothiadiazole, was newly synthesized through a [2 + 2] cycloaddition-retroelectrocyclization reaction. Symmetric electron-rich 1,3-butadiynes with end-capped heterocyclic substituents were reacted with tetracyanoethylene (TCNE), yielding the target TCBD products in 60-80% yields under ambient or mild heating conditions. The thermal stability and optical and electrochemical properties of both 1,3-butadiyne precursors and the corresponding TCBD derivatives were investigated by using thermogravimetric analysis (TGA), UV-vis spectroscopy, and cyclic voltammetry (CV).
View Article and Find Full Text PDFSc-Catalyzed Asymmetric [2 + 2] Annulation of 2-Alkynylnaphthols with Dienes to Access Cyclobutene Frameworks.
Org Lett
January 2025
State Key Laboratory of Southwestern Chinese Medicine Resources, School of Pharmacy, Chengdu University of Traditional Chinese Medicine, Chengdu 611137, P. R. China.
Herein, we introduce a scandium-catalyzed synthetic strategy that provides access to a diverse and functionalized array of cyclobutene frameworks adorned with a quaternary carbon center. This approach broadens the synthetic repertoire of 2-alkynylnaphthols with alkenes, offering a versatile platform for the construction of complex molecular architectures. The asymmetric catalytic [2 + 2] cycloaddition reaction demonstrates a wide substrate scope and an impressive functional group tolerance, yielding products with high efficiency, up to 97% yield, and excellent enantiomeric excess of up to 97%.
View Article and Find Full Text PDFEnantiospecific Synthesis of Tetrahydroindolizines from Spiro-cyclopropanecarboxylated Sugars.
J Org Chem
January 2025
School of Chemistry, University of Hyderabad, C. R. Rao Road, Gachibowli, Hyderabad 500 046, India.
A facile two-step enantiospecific synthesis of 5,6,7,8-tetrahydroindolizine scaffolds has been developed via TMSOTf-promoted [3 + 2] cycloaddition between carbohydrate-derived spirocyclic donor-acceptor cyclopropanecarboxlates and alkyl/aryl nitriles followed by an intramolecular Mitsunobu reaction of the resulting chiral 2/5-(4-hydroxybutyl)pyrrole derivatives.
View Article and Find Full Text PDFUnveiling the Reaction Mechanism of Diels-Alder Cycloadditions between 2,5-Dimethylfuran and Ethylene Derivatives Using Topological Tools.
Chemphyschem
January 2025
University of Namur, Department of Chemistry, Rue de Bruxelles, 61, 5000, Namur, BELGIUM.
The [4+2] Diels-Alder cycloaddition reaction between 2,5-DMF (1) and ethylene derivatives (2a-h) activated by electron-withdrawing groups has been studied at the density functional theory levels using a panoply of tools to unravel the reaction mechanisms. From the analysis of the reactivity indices, 2a-h behave as electrophiles while 1 as nucleophile, and the activation of the double bond of ethylene increases its electrophilicity, which is accompanied by an enhancement of the polarity of the reaction. The activation Gibbs free energy decreases linearly as a function of this increase of polarity, as estimated by the electrophilicity difference between the reactants.
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!