A general class of well-defined, air-stable, and readily available Pd(II)-NHC precatalysts (NHC = N-heterocyclic carbene) for Suzuki and Buchwald-Hartwig cross-coupling of amides (transamidation) and esters by selective N-C/O-C cleavage is reported. Since these precatalysts are highly active and the easiest to synthesize, the study clearly suggests that [Pd(NHC)(acac)Cl] should be routinely included during the development of new cross-coupling methods. An assay for in situ screening of NHC salts in this cross-coupling manifold is presented.
Download full-text PDF |
Source |
---|---|
http://dx.doi.org/10.1021/acs.orglett.9b01053 | DOI Listing |
J Am Chem Soc
January 2025
State Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan University, Shanghai 200438, China.
In traditional atom transfer radical polymerization (ATRP), oxygen must be meticulously eliminated due to its propensity to quench radical species and halt the polymerization process. Additionally, oxygen oxidizes the lower-valent Cu catalyst, compromising its ability to activate alkyl halides and propagate polymerization. In this study, we present an oxygen-driven ATRP utilizing alkylborane compounds, a method that not only circumvents the need for stringent oxygen removal but also exploits oxygen as an essential cofactor to promote polymerization.
View Article and Find Full Text PDFTransition metal-catalyzed alkyne metathesis has become a useful tool in synthetic chemistry. Well-defined alkyne metathesis catalysts comprise alkylidyne complexes of tungsten, molybdenum and rhenium. Non-d Re(v) alkylidyne catalysts exhibit advantages such as remarkable tolerance to air and moisture as well as excellent functional group compatibility.
View Article and Find Full Text PDFJ Am Chem Soc
October 2024
Department of Chemistry, Carnegie Mellon University, 4400 Fifth Avenue, Pittsburgh, Pennsylvania 15213, United States.
In atom transfer radical polymerization (ATRP), dormant alkyl halides are intermittently activated to form growing radicals in the presence of a Cu/L/X-Cu/L (activator/deactivator) catalytic system. Recently developed very active copper complexes could decrease the catalyst concentration to ppm level. However, unavoidable radical termination results in irreversible oxidation of the activator to the deactivator species, leading to limited monomer conversions.
View Article and Find Full Text PDFACS Catal
September 2024
Department of Chemistry, Center of Excellence in Polymer Chemistry (CPEC), University of Houston, 3589 Cullen Boulevard, Houston, Texas 77004, United States.
Design of catalysts for Ni-catalyzed olefin polymerization predominantly focuses on ligand design rather than the activation process when attempting to achieve a broader scope of polyolefin micro- and macrostructures. Air-stable alkyl-or aryl-functionalized Ni precatalysts were designed which eliminate the need of in situ alkylating processes and are activated solely by halide abstraction to generate the cationic complex for olefin polymerization. These complexes represent an emerging class of olefin polymerization catalysts, enabling the study of various cocatalysts forming either inner- or outer-sphere ion pairs.
View Article and Find Full Text PDFJ Org Chem
June 2024
Department of Chemistry and Chemical Biology, Indian Institute of Technology (Indian School of Mines), Dhanbad 826004, India.
An air-stable, robust, and well-defined copper(II)-7-azaindole--oxide-based catalyst [Cu(7-AINO)] (abbreviated as Cu(II)-7-AINO) has been demonstrated as an efficient catalyst for various Ullmann-type coupling reactions. This easily prepared and cost-effective catalyst facilitates the arylation and heteroarylation of diverse -, -, and -nucleophiles, including azoles, aminoazoles, (hetero)arylthiols, and phenols. Notably, they also exhibit substantial compatibility with a wide range of functional groups.
View Article and Find Full Text PDFEnter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!