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A new transition-metal-free catalytic system which uses sodium iodide as the catalyst with formic acid as the hydrogen donor in a biphasic medium was reported for the reduction of the hydroxyl group and various unsaturated groups such as C＝C, C≡C, C＝N and C＝O. Using the same catalytic system, reductive N-formylation of nitroarenes with formic acid was explored to produce the corresponding amide in high selectivity. Moreover, the catalyst stability was evaluated and reaction mechanisms were studied and proposed for the three model reactions. [ABSTRACT FROM AUTHOR]