RESUMO
An organocatalytic strategy for the direct carboxylation of terminal alkynes with CO2 has been developed. The combined use of a bifunctional organocatalyst and Cs2CO3 resulted in a robust catalytic system for the preparation of a range of propiolic acid derivatives in high yields with broad substrate scope using CO2 at atmospheric pressure under mild temperatures (60 °C). This work has demonstrated that this organocatalytic method offers a competitive alternative to metal catalysis for the carboxylation of terminal alkynes and CO2. In addition, this protocol was suitable for the three-component carboxylation of terminal alkynes, alkyl halides, and CO2.
RESUMO
The method of UV/Visible absorption spectroscopy for olefin catalytic system was introduced in this paper, whose testing condition was much closer to the polymerization conditions. The actions of olefin polymerization catalyst (dbm)2 ZrCl2 with cocatalyst AlEt2 Cl (or MAO) were investigated by UV/visible absorption spectroscopy at atmosphere temperature. It was shown that the UV/Visible main absorption band of the zirconocenium, which can be related to the ligand to metal charge transfer bands (LMCT), varies greatly upon incremental addition of AlEt2 Cl or MAO. For the low molar ratios of Al/Zr in the catalytic system, there was the substitution of an electron withdrawing chlorine atom by a donating alkyl group. Then a hypsochromic shift of the initial catalyst absorption band, corresponding to the monomethylation of the catalyst, was observed in each catalytic system (dbm)2 ZrCl2/AlEt2 Cl (or (dbm)2 ZrCl2/MAO). On the contrary, further addition of AlEt2 Cl (or MAO) was accompanied by a continuous bathochromic shift of the maximal wavelength, which corresponding to the formation of more dissociated ionic active species. Then, there would be a coordination of monomer to the ionic active species.
