The catalytic cascade reactions of dienynes, e.g. I, leading to 1,2-dihydronaphthalenes, naphthalenes, and 1,4-dihydronaphthalenes, e.g. II, including the catalytic enantioselective carboformylation of alkenes with aldehydes or the cycloisomerization of enallenes have been developed by using the cationic rhodium(I)/xyl-binap or binap complex as a catalyst. [on SciFinder(R)]