Total Synthesis of (−)‐Perezoperezone through an Intermolecular [5+2] Homodimerization of Hydroxy <i>p</i>‐Quinone

Coupling sites of nitrogen dopants and intrinsic carbon defects (N/DC) in metal‐free carbon are highly active toward electrocatalytic oxygen reduction reaction (ORR), and yet they are hard to be effectively constructed. Here, a novel synthesis strategy for fabrication of N/DC‐enriched metal‐free carbon from precursors containing metal‐nitrogen moieties (M‐Nx) is reported. During pyrolysis of the precursors, the M‐Nx is in situ converted to endogenous metal oxides (MOx) via a halide‐mediated “bait and switch” mechanism to realize a domain‐confined etching of the carbon matrix around the nitrogen dopants, forming abundant N/DC coupling sites in the final carbon products. The optimized N/DC‐enriched carbon exhibits an outstanding ORR activity and stability with a half‐wave potential of 0.903 V (versus RHE) in 0.1 m KOH solution, outperforming most of the reported metal‐free carbon catalysts. Experimental investigations and theoretical calculations demonstrate an improved electron‐donating ability and optimized binding energies of the N/DC coupling sites toward the ORR intermediates, which are primarily responsible for such an excellent ORR activity. This domain‐confined endogenous MOx etching strategy is also widely applicable to different M‐Nx‐containing precursors as well as different halide mediators, which opens up new possibilities to fabricate metal/nonmetal doped carbon materials enriched with various coupling sites of desired synergistic properties.

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Domain‐Confined Etching Strategy to Regulate Defective Sites in Carbon for High‐Efficiency Electrocatalytic Oxygen Reduction

Liu

Huang

et al. 2022

Adv Funct Materials

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Organocatalytic One‐Pot Synthesis of Pseudo‐Terpenoids

et al. 2022

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Structurally complex cedrane scaffolds were synthesized in very good yields with high chemo-and diastereoselectivities in a sequential one-pot manner. A combination of intermolecular olefination, intramolecular Michael and Michael reactions or intermolecular olefination, intramolecular Michael and aldol reactions were used as the key steps from the readily available hydroxy-p-quinone butanals and phosphoranes with catalytic amounts of quinine at ambient temperatures for a few hours. This is a unique one-pot combination of coupling and annulation routes for the green synthesis of a library of tricyclic pseudo-terpenoids (cedrane scaffolds) with high selectivity and yields. Organocatalytic ring isomerization was highlighted through transforming one ring into another one by retrocyclization. We have discussed thoroughly mechanistic aspects of these tandem coupling/annulation and ring isomerization reactions based on control experiments and X-ray crystal structure analysis.

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Total Synthesis of (−)‐Perezoperezone through an Intermolecular [5+2] Homodimerization of Hydroxy p‐Quinone

Cited by 2 publications

References 74 publications

Domain‐Confined Etching Strategy to Regulate Defective Sites in Carbon for High‐Efficiency Electrocatalytic Oxygen Reduction

Domain‐Confined Etching Strategy to Regulate Defective Sites in Carbon for High‐Efficiency Electrocatalytic Oxygen Reduction

Organocatalytic One‐Pot Synthesis of Pseudo‐Terpenoids

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