Renhua Liu

A highly efficient catalytic system without transition metals has been developed for aerobic alcohol oxidations. Under the optimal reaction conditions, various alcohol substrates were converted into their corresponding carbonyl compounds by air with TEMPO/Br2/NaNO2 as catalyst, especially the oxidation of benzylic alcohols to benzaldehydes in high yields.

With the increasing requirement for analysis and separation of samples related to genomics, proteomics, metabolomics, pharmacology and agrochemistry, diverse stationary phases for liquid chromatography have been prepared by Cu(i)-catalyzed 1, 3-dipolar azide-alkyne cycloaddition reaction (CuAAC). It has been proved that CuAAC is a powerful tool for preparing covalently bonded stationary phases. In this tutorial review, we highlighted the preparation of separation materials by immobilization of functional groups on silica beads, polymer beads and agarose via CuAAC and their applications in liquid chromatography and related purposes, such as separation of polar compounds, enrichment of valuable bio-samples, orthogonal two-dimensional HPLC and chiral separation. Meanwhile, agarose-based separation materials for affinity chromatography are reviewed.

Hydrochloric acid, a very inexpensive and readily available inorganic acid, has been found to cooperate exquisitely with NaNO(2)/TEMPO in catalyzing the molecular-oxygen-driven oxidation of a broad range of alcohol substrates to the corresponding aldehydes and ketones. This transition-metal-free catalytic oxidative conversion is novel and represents an interesting alternative route to the corresponding carbonyl compounds to the metal-catalyzed aerobic oxidation of alcohols. The reaction is highly selective with respect to the desired product when carried out at room temperature in air at atmospheric pressure. Notably, the use of very inexpensive NaNO(2) and HCl in combination with TEMPO for this highly selective aerobic oxidation of alcohols in air at ambient temperature makes the reaction operationally and economically very attractive. The results of mechanistic studies, performed with the aid of electrospray ionization mass spectrometry (ESI-MS), are presented and discussed. TEMPO, TEMPOH, and TEMPO(+) were observed in the redox cycle by means of ESI-MS. On the basis of these observations, a mechanism is proposed that may provide an insight into the newly developed aerobic alcohol oxidation.

FeCl3-TEMPO-NaNO2 catalyses the selective and mild aerobic oxidation of a broad range of alcohols to the corresponding aldehydes and ketones.

A highly efficient catalytic system without transition metals in water has been developed for aerobic oxidations of benzylic alcohols. The newly developed catalyst system could oxidize benzylic alcohols and heteroaromatic analogues with 1 mol % TEMPO as a catalyst and with a catalytic amount of 1,3-dibromo-5,5-dimethylhydantoin and NaNO2 as cocatalysts. Under the optimal conditions, various alcohols could be converted into their corresponding aldehydes or ketones in high yields.