Oxidative phenol-arene and phenol-phenol cross-coupling using periodic acid
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Abstract Chemoselective cross-coupling of phenol derivatives is valuable for generating products that retain halides. Here we discuss recent developments in selective cross-couplings of chloroaryl phenol derivatives, with a particular focus on reactions of chloroaryl tosylates. The first example of a C–O-selective Ni-catalyzed Suzuki–Miyaura coupling of chloroaryl tosylates is discussed in detail. 1 Introduction 2 Density Functional Theory Studies on Oxidative Addition at Nickel(0) 3 Stoichiometric Oxidative Addition Studies 4 Development of a Tosylate-Selective Suzuki Coupling 5 Conclusion and Outlookmore » « less
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Although copper‐catalyzed organic transformations are prevalent, insights into the interactions of phenols with simple copper(II) salts are not well understood. In contrast, inspired by the oxygenase‐type modifications of the phenolic substrates, the reactions of substituted phenols with metastable copper–oxygen intermediates are well documented. The present report sheds light on the reactions of substituted phenols with benchtop stable CuCl2salt and the role of a common base like triethylamine. Moreover, the reactions of substituted phenols with CuCl2in the presence of weakly coordinating tripodalN‐nitrosated ligandL3NOhave been illustrated, while a closely related tripodal copper(II) complexL3HCuCl2(2) of the corresponding non‐nitrosated ligandL3Hdoes not react with the phenolic substrates. Phenol reactions with CuCl2in the presence of theL3NOligand enable in depth mechanistic investigation, thereby illustrating a bimolecular rate law with ΔH‡= 15.13 kcal mol−1, ΔS‡ = −9.6 eu, and kinetic isotope effectk2(ArOH)/k2(ArOD) in the range of 1.35–1.43. Thus, these findings suggest that simple copper(II) salts like CuCl2are capable of facilitating a proton‐coupled electron transfer (PCET) pathway.more » « less
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Catalytic hydrodeoxygenation (HDO) of phenolics is a necessary step for upgrading bio-oils to transportation fuels. Bimetallic catalysts offer the potential of increased activities and selectivities for desired products. Adding non-metallic elements, such as phosphorous, allows for charge distribution between the metal and nonmetal atoms, which improves Lewis acid character of catalytic surfaces. This work utilizes experimental and density functional theory (DFT) based calculations to identify potential C–O bond cleavage pathways and product selectivities for HDO reactions on FeMoP, RuMoP, and NiMoP catalysts. Our work demonstrates that FeMoP catalyst favors direct deoxygenation pathway due to a lower activation energy barrier for C–O bond cleavage whereas RuMoP and NiMoP catalysts promote ring hydrogenation first, followed by the cleavage of C–O bond. The Bader charge analysis indicates that for these catalytic systems Mo δ+ site bears a large positive charge which acts as a Lewis acid site for HDO reactions. Overall, we find that trends in the experimental product selectivities are in good agreement with that predicted with DFT calculations.more » « less
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