An efficient, transition-metal-free method to synthesize pyrazolone thioethers as well as 2-aryl and 3-aryl benzofuran thioethers by employing aryl sulfonyl chlorides as sulfenylation reagents in the presence of triphenylphosphine was developed. Potassium iodide was found to facilitate the transformation for the first time by generating more reactive sulfenyl iodide in situ from sulfenyl chloride.
A new method for the synthesis of di- and trisubstituted pyrroles via copper-catalyzed cyclization of ethyl allenoates with activated isocyanides has been developed. In contrast to related annulation reactions previously reported, this new process features a skeletal rearrangement in which the aryl sulfonyl moiety, which functions as the electron-withdrawing group in the α-carbon of the isocyanide, was found to migrate to the γ-carbon of the starting allenoate in the final product for the first time.
A convenient approach for the synthesis of β-substituted α,β-unsaturated carbonyl porphyrin compounds via base-catalyzed aldol reaction was developed. By this method, a series of β-substituted α,β-unsaturated carbonyl porphyrin compounds were constructed using β-porphyrin formaldehyde and ketones with moderate to excellent yields under mild reaction conditions, especially solvent-free, and good functional group tolerance. Furthermore, this process was successfully applied to the reactions of different metal porphyrin which have been reported to have poor reaction effects with good yields.
The first total synthesis of I3,II8-biapigenin and ridiculuflavone A was achieved via Sonogashira and rhodium-catalyzed oxidative coupling as the key steps.
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