An iron-based catalytic system was developed for the cross-coupling of 1-bromoalkynes with terminal alkynes to selectively generate unsymmetrical 1,3-butadiynes in water under air. It was found that a combination of 1-bromoalkynes derived from less acidic terminal alkynes with more acidic counterparts would greatly enhance yields and selectivity for unsymmetrical 1,3butadiynes. The reaction was also applicable for the synthesis of unsymmetrical 1,3,5-hexatriynes through coupling of 1-bromoalkynes and trimethylsilyl-protected 1,3-butadiynes in a one-pot manner.
The association of a commercially-available iron (III) chloride hexahydrate (FeCl3∙6H2O) with cationic 2,2′-bipyridyl in water was proven to be an operationally simple and reusable catalytic system for the highly-selective reduction of nitroarenes to anilines. This procedure was conducted under air using 1–2 mol% of catalyst in the presence of nitroarenes and 4 equiv of hydrazine monohydrate (H2NNH2∙H2O) in neat water at 100 °C for 12 h, and provided high to excellent yields of aniline derivatives. After separation of the aqueous catalytic system from the organic product, the residual aqueous solution could be applied for subsequent reuse, without any catalyst retreatment or regeneration, for several runs with only a slight decrease in activity, proving this process eco-friendly.
The combination of commercially available FeCl3·6H2O with a water-soluble cationic 2,2′-bipyridyl catalytic system was found to enable the direct conjugate addition of aryl iodides onto activated alkenes, such as an α,β-unsaturated ester and a ketone, in a weakly acidic aqueous solution. This operationally simple protocol was carried out at 80 °C under air atmosphere in a potassium acetate-buffered aqueous solution for 12 h in the presence of Zn dust as a reductant to provide the desired 1,4-adducts in good yields.
Isoflavones were synthesized from the reaction of 3-bromochromone derivatives and aryltributylstannanes via Stille coupling catalyzed by a water-soluble and reusable PdCl 2 (NH 3) 2 /2,2 0-cationic bipyridyl system in aqueous solution. For prototype 3-bromochromone, the coupling reaction was performed at 80 C for 24 hr with 2.5 mol% catalyst in water in the presence of tetrabutylammonium fluoride. After the reaction, the aqueous solution could be reused for several runs, indicating that its activity was only slightly decreased. For substituted 3-bromochromones, the addition of NaHCO 3 and a higher reaction temperature (120 C) were required to gain satisfactory outcomes. In addition, naturally occurring products, such as daidzein, could be obtained by this protocol via a one-pot reaction.
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