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Origins of unique gold-catalysed chemo- and site-selective C-H functionalization of phenols with diazo compounds.

ABSTRACT: In past decade, gold revealed more and more unique properties in carbene chemistry. It was disclosed in our recent communication (J. Am. Chem. Soc. 2014, 136, 6904) that gold carbenes have unprecedented chemo- and site-selectivity and ligand effect toward the functionalization of C-H bonds in phenols. In this full article, we report a comprehensively combined theoretical and experimental study on the mechanism of the insertion of gold carbenes into C-H and O-H bonds in phenol. It significantly revealed that the ligands have an important effect on C-H insertion and the reaction proceeds through a pathway involving the formation of an enolate-like intermediate. Moreover, two water molecules serving as a proton shuttle are believed to be the key issue for achieving chemoselective C-H functionalization, which is strongly supported by the DFT calculations and control experiments. It is the first time that a clear explanation is given about the prominent catalysis of gold carbenes toward C-H functionalization based on a theoretical and experimental study.

SUBMITTER: Liu Y

PROVIDER: S-EPMC5968449 | biostudies-literature | 2016 Mar

REPOSITORIES: biostudies-literature

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Origins of unique gold-catalysed chemo- and site-selective C-H functionalization of phenols with diazo compounds.

Liu Yuan Y Yu Zhunzhun Z Zhang John Zenghui JZ Liu Lu L Xia Fei F Zhang Junliang J

Chemical science 20151127 3

In past decade, gold revealed more and more unique properties in carbene chemistry. It was disclosed in our recent communication (<i>J. Am. Chem. Soc.</i> 2014, <b>136</b>, 6904) that gold carbenes have unprecedented chemo- and site-selectivity and ligand effect toward the functionalization of C-H bonds in phenols. In this full article, we report a comprehensively combined theoretical and experimental study on the mechanism of the insertion of gold carbenes into C-H and O-H bonds in phenol. It s ...[more]

PMID: 29899922

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Project description:Despite their wide use in academia as metal-carbene precursors, diazo compounds are often avoided in industry owing to concerns over their instability, exothermic decomposition, and potential explosive behavior. The stability of sulfonyl azides and other diazo transfer reagents is relatively well understood, but there is little reliable data available for diazo compounds. This work first collates available sensitivity and thermal analysis data for diazo transfer reagents and diazo compounds to act as an accessible reference resource. Thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and accelerating rate calorimetry (ARC) data for the model donor/acceptor diazo compound ethyl (phenyl)diazoacetate are presented. We also present a rigorous DSC dataset with 43 other diazo compounds, enabling direct comparison to other energetic materials to provide a clear reference work to the academic and industrial chemistry communities. Interestingly, there is a wide range of onset temperatures (T onset) for this series of compounds, which varied between 75 and 160 °C. The thermal stability variation depends on the electronic effect of substituents and the amount of charge delocalization. A statistical model is demonstrated to predict the thermal stability of differently substituted phenyl diazoacetates. A maximum recommended process temperature (T D24) to avoid decomposition is estimated for selected diazo compounds. The average enthalpy of decomposition (ΔH D) for diazo compounds without other energetic functional groups is -102 kJ mol-1. Several diazo transfer reagents are analyzed using the same DSC protocol and found to have higher thermal stability, which is in general agreement with the reported values. For sulfonyl azide reagents, an average ΔH D of -201 kJ mol-1 is observed. High-quality thermal data from ARC experiments shows the initiation of decomposition for ethyl (phenyl)diazoacetate to be 60 °C, compared to that of 100 °C for the common diazo transfer reagent p-acetamidobenzenesulfonyl azide (p-ABSA). The Yoshida correlation is applied to DSC data for each diazo compound to provide an indication of both their impact sensitivity (IS) and explosivity. As a neat substance, none of the diazo compounds tested are predicted to be explosive, but many (particularly donor/acceptor diazo compounds) are predicted to be impact-sensitive. It is therefore recommended that manipulation, agitation, and other processing of neat diazo compounds are conducted with due care to avoid impacts, particularly in large quantities. The full dataset is presented to inform chemists of the nature and magnitude of hazards when using diazo compounds and diazo transfer reagents. Given the demonstrated potential for rapid heat generation and gas evolution, adequate temperature control and cautious addition of reagents that begin a reaction are strongly recommended when conducting reactions with diazo compounds.

Dataset Information

Origins of unique gold-catalysed chemo- and site-selective C-H functionalization of phenols with diazo compounds.

Publications

Origins of unique gold-catalysed chemo- and site-selective C-H functionalization of phenols with diazo compounds.

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