(P,C)-cyclometalated Au(III) complexes have shown remarkable ability to catalyze the intermolecular hydroarylation of alkynes. Evidence of an outer-sphere mechanism has been provided in a previous study and is confirmed here by analysing the experimental data and DFT calculations. In this work, we propose evaluation of critical energies of dissociation of Au(III) complexes with different substrates energy-resolved mass spectrometry (ERMS) experiments and kinetic modelling. The kinetic model is based on a multi-collisional approach. On the one hand, the classification confirms the mechanism previously proposed; on the other hand, it supports the collisional model and its application to particularly fragile adducts.
Download full-text PDF |
Source |
---|---|
http://dx.doi.org/10.1039/d3dt02393a | DOI Listing |
J Org Chem
November 2024
CICA, Centro Interdisciplinar de Química e Bioloxía and Departamento de Química, Universidade da Coruña, 15071 A Coruña, Spain.
Pyrroles, privileged structural motifs in drug and material science, have been synthesized by indium(III)-catalyzed intramolecular cyclization of homopropargyl azides. This methodology exhibits a broad substrate scope, providing substituted pyrroles and bispyrroles in good yields. Furthermore, an atom-economical sequential method for the synthesis of benzo[]indoles has been discovered from azido-diynes using InCl as catalyst.
View Article and Find Full Text PDFOrg Biomol Chem
October 2024
College of Tobacco Science, Henan Agricultural University, Zhengzhou, 450046, China.
Transition-metal-catalyzed selective hydroarylation of alkynes represents a state-of-the-art approach in organic chemistry. Herein, we report the reaction of symmetrical 1,3-diynes and arylboronic acids, with Pd(OAc) as the catalyst and PCy as the ligand, affording functionalized enynes in good to excellent yields. Its efficiency is demonstrated by its good functional group tolerance and broad substrate scope.
View Article and Find Full Text PDFChem Commun (Camb)
September 2024
Chemical Sciences and Technology Division, CSIR-National Institute for Interdisciplinary Science and Technology (CSIR-NIIST), Thiruvananthapuram 695019, Kerala, India.
The visible light-promoted -alkenylation of phenols and naphthols with terminal alkynes is achieved using 2,4,6-tris(4-fluorophenyl)pyrylium tetrafluoroborate (T(-F)PPT) as a photocatalyst at room temperature without the need of any external ligand or additive. Apart from its excellent functional group tolerance, the protocol described herein represents an appealing alternative strategy to classical transition-metal catalysed hydroarylation reactions. Mechanistic investigations revealed that the reaction involves a radical pathway.
View Article and Find Full Text PDFJ Org Chem
June 2024
College of Chemistry, Jilin University, Changchun 130012, Jilin, P. R. China.
Herein, we report a reaction protocol for the construction of benzo[]carbazole and dibenzo[,]carbazole frameworks. The detailed gold catalytic reaction conditions developed for the challenging intermolecular carbon nucleophilic addition to internal alkynes are realized, giving the desired alkyne hydroarylation products in good yields. The resulting trisubstituted alkenes are able to undergo photomediated cyclization, furnishing the desired carbazole molecules with excellent yields and high efficiency.
View Article and Find Full Text PDFChem Commun (Camb)
May 2024
School of Chemistry, MOE Key Laboratory for Nonequilibrium Synthesis and Modulation of Condensed Matter, Xi'an Key Laboratory of Sustainable Energy Materials Chemistry, Xi'an Jiaotong University (XJTU), Xi'an, 710049, China.
A gold(I)-catalyzed protecting-group-free benzannulation approach to functionalized NH-carbazoles was accomplished the hydroarylation of alkynes with 2-alkenylindoles. A broad spectrum of terminal and internal alkynes and 2-alkenylindoles successfully participated in this annulation reaction. The protocol efficiently enabled the formation of substituted NH-carbazoles with moderate to specific regioselectivities.
View Article and Find Full Text PDFEnter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!