两种辅酶NAD+模型物催化的一级和二级苄醇的光催化氧化反应

pplication to organic reaction by coenzyme NAD+ models with catalytic amount have attracted increasing attentions. Many important organic reacions such as oxidation and reduction could be realized by virtue of catalytic ability of coenzyme NAD+ model. Many research groups have made important progress in this field. Under the reaction condition reported by Fukuzumi, only benzyl alcohol was oxidated to corresponding benzaldehyde, other derivatives such as some solid primary benzyl alcohols and secondary benzyl alcohols were not noted. Photocatalytic oxidation of primary and secondary benzyl alcohol to corresponding benzaldehyde or acetophenone using Acr+ClO4? or PhAcr+ClO4? as photocatalysts under visible light irradiation at room temperature. A series of 9 primary and 9 secondary benzyl alcohols were then investigated in presence of O2 using 5 mol % Acr+ClO4? and PhAcr+ClO4?. But common alcohols such as phenylethanol and cyclohexanol instead of the primary and secondary benzyl alcohol didn't proceed . On the basis of these observations and by reference to the literature, we propose a radical mechanism for the reaction. We find an interesting phenomenon that cinnamic aldehyde with lower yield (14%) and benzaldehyde with higher yield (84%) are obtained when cinnamic alcohol reacts with PhAcr+ClO4? as catalyst in this reaction system. The similar reation only produces benzaldehyde under Ar with other same reaction condition. Mechanism of the present reaction can be explained by two cycles.