A cobalt-catalyzed method for the hydrogermylation of alkynes is reported, providing a selective and accessible route to ()-β-vinyl(trialkyl)germanes from terminal alkynes and HGeBu. As shown in multiple examples, the developed method demonstrates a broad functional group tolerance an practical utility for late-stage hydrogermylation of natural products. The method is compatible with alkynes bearing both aryl and alkyl substituents, providing unrivaled selectivity for previously challenging 1° alkyl-substituted alkynes. Moreover, the catalyst used in this method, Co(CO), is a cheap and commercially available reagent. Conducted mechanistic studies supported the -addition of BuGeH to an alkyne π-complex.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1021/acs.orglett.1c00928 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
From Pseudocyclic to Macrocyclic Ionophores: Strategies toward the Synthesis of Cyclic Monensin Derivatives.
J Org Chem
January 2025
Department of Medical Chemistry, Faculty of Chemistry, Adam Mickiewicz University, Uniwersytetu Poznańskiego 8, 61-614 Poznań, Poland.
There has been a long search for a simple preparation of new cyclic analogues of ionophore antibiotics. We report a simple and general synthesis of three new cyclic derivatives of polyether ionophore, monensin A (MON). The application of the Huisgen 1,3-dipolar cycloaddition of azides and terminal alkynes to macrocyclization results in a concise, synthetic route to monensin lacton or lactam in only 4 steps.
View Article and Find Full Text PDFDiscovery, Characterization, and Anti-XOD Activity of Calcium Metallophore from .
Org Lett
January 2025
School of Pharmacy, Guizhou University of Traditional Chinese Medicine, Guiyang 550025, China.
In this work, coixalkyne A (), a natural polynuclear calcium complex with a novel cross-shaped molecular architecture, was isolated from L. along with the undescribed analogue coixalkyne B (). Their structures were identified by means of NMR spectroscopy, ECD calculations, and single-crystal X-ray diffraction.
View Article and Find Full Text PDFMo(0) carbonyl complexes bearing the bis(3,5-dimethylpyrazole) ligand: catalysis of the regioselective [2 + 2 + 2] cycloaddition of terminal alkynes to synthesize 1,3,5-isomers.
Dalton Trans
January 2025
Department of Chemistry, Indian Institute of Technology Kharagpur, Kharagpur, 721302 India.
The reaction between 1,3-bis(3,5-dimethylpyrazolylmethyl)hexahydropyrimidine L and Mo(CO) in CHCN at 130 °C afforded a binuclear Mo(0) complex 1 containing a new macrocycle formed upon C-N bond cleavage in L in good yield. Conversely, a clean reaction takes place between L and [Mo(CO)(COD)] in THF at 60 °C to give a new metalloligand complex [Mo(CO)(κ-,-L)] 2 containing a spectator pyrazole arm in 83% yield. Their structures were determined by X-ray diffraction methods, and a plausible mechanism is proposed for the C-N bond cleavage leading to complex 1.
View Article and Find Full Text PDFMetal-organic frameworks generated from oligomeric ligands with functionalized tethers.
Chem Sci
December 2024
Department of Chemistry and Biochemistry, University of California, San Diego La Jolla California 92093 USA
Metal-organic frameworks (MOFs) can be prepared from oligomeric organic ligands to prepare materials referred to as oligoMOFs. Studies of oligoMOFs are relatively limited, with most existing reports focused on fundamental structure-property relationships. In this report, functional groups, such as terminal alkynes and pyridine groups, are installed on the tether between 1,4-benzene dicarboxylic acid (Hbdc) groups of the dimer ligands.
View Article and Find Full Text PDFRecycling e-waste into gold-loaded covalent organic framework catalysts for terminal alkyne carboxylation.
Nat Commun
December 2024
Department of Food Science, College of Agricultural and Life Sciences, Cornell University, Stocking Hall, Ithaca, NY, USA.
The rising demand for gold requires innovative methods for its recovery from e-waste. Here we present the synthesis of two tetrazine-based vinyl-linked covalent organic frameworks: TTF-COF and TPE-COF that adsorb gold ions and nanoparticles and catalyze the carboxylation of terminal alkynes. These covalent organic frameworks have low band gaps and high photocurrent responses.
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!