Constructing heterocyclic compounds by chemical fixation of CO2/CS2 as C1 building block is a promising theme. An efficient and environmentally friendly synthetic approach has been developed using CO2/CS2 to prepare complicated allenyl heterocycles with high yields and diastereoselectivities in metal-free manner under mild conditions. NIS promoted CO2 fixation and cyclization reaction by exclusive 1,4-syn-addition of 1,3-enynes rather than 1,2-addition or 3,4-addition. While CS2 participated in unique 1,4-syn-hydrothiolation of 1,3-enynes to afforded allenyl heterocycles with different reaction pattern.

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