The treatment of PdCl with KCO and HCOH in dioxane gives black precipitates, which are an effective catalyst for the semireduction of alkynes to alkenes using formic acid as a reductant. Even 0.05 mol % Pd promoted the reduction reaction of tolane in high yield with high selectivity.
Download full-text PDF |
Source |
---|---|
http://dx.doi.org/10.1021/acs.joc.8b02169 | DOI Listing |
Angew Chem Int Ed Engl
September 2024
Organic and Inorganic Chemistry Department, University of Oviedo, Avenida Julián Clavería 8, 33006, Oviedo, Spain.
The direct synthesis of alkenes from alkynes usually requires the use of transition-metal catalysts. Unfortunately, efficient biocatalytic alternatives for this transformation have yet to be discovered. Herein, the selective bioreduction of electron-deficient alkynes to alkenes catalysed by ene-reductases (EREDs) is described.
View Article and Find Full Text PDFSmall
August 2024
School of Chemistry and Material Sciences, Hangzhou Institute of Advanced Study, University of Chinese Academy of Sciences, 1 Sub-lane Xiangshan, Hangzhou, 310024, China.
Selective semi-hydrogenation of alkynes is a significant reaction for preparing functionalized alkenes. Electrochemical semi-hydrogenation presents a sustainable alternative to the traditional thermal process. In this research, affordable copper acetylacetonate is employed as a catalyst precursor for the electrocatalytic hydrogenation of alkynes, using MeOH as the hydrogen source in an undivided cell.
View Article and Find Full Text PDFJ Org Chem
December 2023
Instituto de Química, Departamento de Química Orgânica, Universidade Federal do Rio Grande do Sul (UFRGS), P.O. Box 15003, 91501-970 Porto Alegre, RS, Brazil.
In this work, we present the CS/KOH system as a practical and efficient reductive medium for obtaining ()-alkenes from alkynes through a highly stereoselective semireduction reaction. This cost-effective system enabled successful semireduction reactions of diverse alkynes using water as a hydrogen source, yielding moderate to excellent yields. The versatility of this protocol is further demonstrated through the synthesis of relevant compounds such as pinosylvin and resveratrol precursors, along with the notable anticancer agent DMU-212.
View Article and Find Full Text PDFJ Am Chem Soc
October 2023
Max-Planck-Institut für Kohlenforschung, 45470 Mülheim/Ruhr, Germany.
In conceptual terms, the first total synthesis of the cytotoxic marine natural product njaoamine C differs from all known approaches toward related alkaloids of the manzamine superfamily in that both macrocyclic rings enveloping the diazatricyclic core are concomitantly formed; this goal was reached by double ring closing alkyne metathesis (dRCAM). The success of this maneuver does not merely reflect a favorable preorientation of the four alkyne chains that need to be concatenated in the proper pairwise manner but is also the outcome of dynamic covalent chemistry involving error correction by the chosen "canopy" molybdenum alkylidyne catalyst. The end game downstream of dRCAM capitalizes on the striking chemoselectivity of palladium-catalyzed hydrostannation, which selects for (hetero)arylalkynes even in the presence of sterically much more accessible dialkylalkynes or alkenes; for this preference, the method complements the classical repertoire of hydrometalation and semireduction reactions.
View Article and Find Full Text PDFChemistry
October 2023
Institut de Chimie et Biochimie Moléculaires et Supramoléculaires (ICBMS, UMR 5246 du CNRS), Univ Lyon, Université Lyon 1, 1 rue Victor Grignard, 69100, Villeurbanne, France.
We report a selectivity-switchable nickel hydride-catalyzed methodology that enables the stereocontrolled semi-reduction of internal alkynes to E- or Z-alkenes under very mild conditions. The proposed transfer semi-hydrogenation process involves the use of a dual nickel/photoredox catalytic system and triethylamine, not only as a sacrificial reductant, but also as a source of hydrogen atoms. Mechanistic studies revealed a pathway involving photo-induced generation of nickel hydride, syn-hydronickelation of alkyne, and alkenylnickel isomerization as key steps.
View Article and Find Full Text PDFEnter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!