New insights into the bifunctionality of vanadium phosphorous oxides: A chemical switch between oxidative scission and pinacol rearrangement of vicinal diols

New insights into the bifunctionality of vanadium phosphorus oxides (VPOs) were obtained. This study reports the precise tuning of experimental conditions, which act as the switch to direct the course of reaction selectively to obtain either CC oxidative scission or an acid-catalysed rearrangement of vicinal diols. The catalyst was synthesized and characterized to identify the active vanadyl pyrophosphate phase. The present method was extended further to develop a new environmentally benign and green catalytic protocol for oxidative cleavage of a variety of vicinal diols with 100% selectivity towards the corresponding aldehydes or ketones using H2O2 as the oxidizing agent.

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► New insights into the bifunctionality of VPOs as redox and solid acid catalyst were obtained.
► VPOs can act as the chemical switch between selective oxidative cleavage or pinacol–pinacolone rearrangement of vicinal diols.
► A new green method for oxidative cleavage of vicinal diols to aldehydes/ketones was established.