Chiral propargylic ether-based triene-ynes are synthesized with high enantiomeric purity by employing an asymmetric enyne addition to aldehydes catalyzed by 1,1'-bi-2-naphthol in combination with ZnEt2 , Ti(OiPr)4 and dicyclohexylamine at room temperature. These substrates are found to undergo a one-pot domino Pauson-Khand and Diels-Alder cycloaddition catalyzed by [RhCl(CO)2 ]2 under CO to generate a series of multicyclic products with high chemoselectivity and stereoselectivity. These products contain the multicyclic core structure of mangicol A which could facilitate the synthesis and study of this class of natural products.