Zinc amide catalyzed, regioselective allenylation and propargylation of ketones with allenyl boronate is reported. Tertiary allenyl and homopropargyl alcohols were obtained, respectively, in high selectivities, from the same starting materials, simply by changing the reaction conditions. The substrate scope was wide. Mechanistic studies suggest that the reactions are controlled under kinetic and thermodynamic conditions.
Facile formation of allylzinc species from allylboronate and zinc amide was discovered. The boron-to-zinc exchange process occurred smoothly to afford the corresponding allylzinc amides, which were successfully employed in catalytic allylation reactions with electrophiles. Asymmetric catalysis using a chiral zinc amide is also reported.
The efficient catalytic allylation of ketones, imines, and hydrazones with allylboronates using a catalytic amount of zinc amide is reported. In this reaction, the boron-to-zinc exchange process occurred smoothly to afford the corresponding allylzinc amides, and the desired allylation reactions proceeded in high efficiency (~0.1 mol%). A mechanistic study revealed that transmetalation was a rate-determining step in the catalytic cycle, and also that the amide ligand on the zinc center played a key role in preparing reactive allylzinc species. Catalytic asymmetric allylations were also investigated, and high enantioselectivities were obtained using chiral di-
Al-containing mesoporous molecular sieves(Al-MCM-41) were synthesized at ambient temperature. The structures of samples were characterized by XRD, N2-adsorption/desorption isotherms and FT-IR, etc. The evaluation results showed that Al-MCM-41 had higher catalytic activity for isomerization conversion of endo-tetrahydrodicyclo-pentadiene (endo-TCD) into exo-tetrahydrodicyclo-pentadiene (exo-TCD) and adamantane (AdH). Loading inorganic acid on the surface of Al-MCM-41 led increase of its catalytic activity and the yield of adamantane.
A new tertiary amine derivative of adamantane —N,N,N’,N’-tetramethyl-1, 3-disaminomethyl adamantane dihydrochloride (1), which is a key intermediate for preparing Gemini surfactants and bola surfactants, has been synthesized in this paper. The target compound (1) can be synthesized in high yield by using 1-adamantanecarboxylic acid as raw material. The structure of these compounds has been identified.
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