Fragmentation and rearrangement of Breslow intermediates: branches to both radical and ionic pathways
Literature Information
Ming-Hsiu Hsieh, Jen-Shiang K. Yu
Breslow intermediates are the key species in N-heterocyclic carbene-catalyzed reactions to promote the C–C bond formation. As the fragmentation and rearrangement of Breslow intermediates terminate the catalytic cycle of N-heterocyclic carbene, two mechanisms under debate have been proposed in terms of the radical channel and the ionic route. Theoretical calculations demonstrate herein that ionic and radical characteristics can coexist, depending on the protonation state of the hydroxyl group in Breslow intermediates: radicals are merely generated in the enol system, while both ionic and radical species exist in the enolate system with a lower barrier. Complete pathways for thiamin analogue and N-allyl benzothiazole Breslow intermediates are exclusively constructed considering experimental conditions. The growing population of the enolate under higher pH values rationalizes the increased rate of the fragmentation of thiamin. The fragmentation products of thiamin, namely pyrimidine and ketone, are the thermodynamic products, while the tertiary alcohol is both the kinetic and thermodynamic product for N-allyl benzothiazole Breslow intermediate via a Claisen-like rearrangement. Other NHCs used to synthesize tertiary alcohols could form the enolate due to the base, followed by the production of stable radicals and recombination to form tertiary alcohols. It is concluded that specific protonation states and chemical structures of NHCs account for the distinct mechanisms.
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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.










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