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Uronic acids are carbohydrates carrying a terminal carboxylic acid and have a unique reactivity in stereoselective glycosylation reactions. Herein, the competing intramolecular stabilization of uronic acid cations by the C‐5 carboxylic acid or the C‐4 acetyl group was studied with infrared ion spectroscopy (IRIS). IRIS reveals that a mixture of bridged ions is formed, in which the mixture is driven towards the C‐1,C‐5 dioxolanium ion when the C‐5,C‐2‐relationship is cis, and towards the formation of the C‐1,C‐4 dioxepanium ion when this relation is trans. Isomer‐population analysis and interconversion barrier computations show that the two bridged structures are not in dynamic equilibrium and that their ratio parallels the density functional theory computed stability of the structures. These studies reveal how the intrinsic interplay of the different functional groups influences the formation of the different regioisomeric products. [ABSTRACT FROM AUTHOR]

N‐Acyliminium ions are highly reactive intermediates that are important for creating CC‐bonds adjacent to nitrogen atoms. Here we report the characterization of cyclic N‐acyliminium ions in the gas phase, generated by collision induced dissociation tandem mass spectrometry followed by infrared ion spectroscopy using the FELIX infrared free electron laser. Comparison of DFT calculated spectra with the experimentally observed IR spectra provided valuable insights in the conformations of the N‐acyliminium ions. [ABSTRACT FROM AUTHOR]

Cover Feature: Breslow Intermediates (Amino Enols) and Their Keto Tautomers: First Gas-Phase Characterization by IR Ion Spectroscopy (Chem. Eur. J. 8/2021) Keywords: Breslow intermediate; density functional calculations; IR spectroscopy; mass spectrometry; umpolung EN Breslow intermediate density functional calculations IR spectroscopy mass spectrometry umpolung 2552 2552 1 02/08/21 20210205 NES 210205 B Breslow Intermediates b are of pivotal importance for chemical and biological Umpolung reactions catalyzed by N-heterocyclic carbenes (NHCs). The enol-ketone tautomerism of a number of NHC-aldehyde combinations, crucial for their chemical reactivity, have been determined in the gas-phase and interpreted by DFT calculations. [Extracted from the article]

Breslow intermediates (BIs) are the crucial nucleophilic amino enol intermediates formed from electrophilic aldehydes in the course of N‐heterocyclic carbene (NHC)‐catalyzed umpolung reactions. Both in organocatalytic and enzymatic umpolung, the question whether the Breslow intermediate exists as the nucleophilic enol or in the form of its electrophilic keto tautomer is of utmost importance for its reactivity and function. Herein, the preparation of charge‐tagged Breslow intermediates/keto tautomers derived from three different types of NHCs (imidazolidin‐2‐ylidenes, 1,2,4‐triazolin‐5‐ylidenes, thiazolin‐2‐ylidenes) and aldehydes is reported. An ammonium charge tag is introduced through the aldehyde unit or the NHC. ESI‐MS IR ion spectroscopy allowed the unambiguous conclusion that in the gas phase, the imidazolidin‐2‐ylidene‐derived BI indeed exists as a diamino enol, while both 1,2,4‐triazolin‐5‐ylidenes and thiazolin‐2‐ylidenes give the keto tautomer. This result coincides with the tautomeric states observed for the BIs in solution (NMR) and in the crystalline state (XRD), and is in line with our earlier calculations on the energetics of BI keto–enol equilibria. [ABSTRACT FROM AUTHOR]

The product of a revealed transformation—NHC‐ethynyl coupling—was observed as a catalyst transformation pathway in the Sonogashira cross‐coupling, catalyzed by Pd/NHC complexes. The 2‐ethynylated azolium salt was isolated in individual form and fully characterized, including X‐ray analysis. A number of possible intermediates of this transformation with common formulae (NHC)nPd(C2Ph) (n=1,2) were observed and subjected to collision‐induced dissociation (CID) and infrared multiphoton dissociation (IRMPD) experiments to elucidate their structure. Measured bond dissociation energies (BDEs) and IRMPD spectra were in an excellent agreement with quantum calculations for coupling product π‐complexes with Pd0. Molecular dynamics simulations confirmed the observed multiple CID fragmentation pathways. An unconventional methodology to study catalyst evolution suggests the reported transformation to be considered in the development of new catalytic systems for alkyne functionalization reactions. [ABSTRACT FROM AUTHOR]

B Understanding dynamic interplay b between the molecular and ionic forms of metal/N-heterocyclic carbene (M/NHC) complexes is the key to develop efficient catalysts with N-heterocyclic carbene ligands. B Understanding dynamic interplay b between the molecular and ionic forms of metal/N-heterocyclic carbene (M/NHC) complexes is the key to develop efficient catalysts with N-heterocyclic carbene ligands. Carbene ligands, dynamic catalysis, electrospray ionization, mass spectrometry, Mizoroki-Heck reaction. [Extracted from the article]

N‐Heterocyclic carbene (NHC) ligands are ubiquitously utilized in catalysis. A common catalyst design model assumes strong M–NHC binding in this metal–ligand framework. In contrast to this common assumption, we demonstrate here that lability and controlled cleavage of the M−NHC bond (rather than its stabilization) could be more important for high‐performance catalysis at low catalyst concentrations. The present study reveals a dynamic stabilization mechanism with labile metal–NHC binding and [PdX3]−[NHC‐R]+ ion pair formation. Access to reactive anionic palladium intermediates formed by dissociation of the NHC ligands and plausible stabilization of the molecular catalyst in solution by interaction with the [NHC‐R]+ azolium ion is of particular importance for an efficient and recyclable catalyst. These ionic Pd/NHC complexes allowed for the first time the recycling of the complex in a well‐defined form with isolation at each cycle. Computational investigation of the reaction mechanism confirms a facile formation of NHC‐free anionic Pd in polar media through either Ph–NHC coupling or reversible H–NHC coupling. The present study formulates novel ideas for M/NHC catalyst design. [ABSTRACT FROM AUTHOR]