A highly diastereo- and enantioselective intramolecular Alder-ene reaction with an alkene as the enophile has been developed by using a chiral N,N'-dioxide/nickel(ii) complex as the catalyst. This protocol provides a facile route towards the synthesis of diverse 3,4-disubstituted chroman, tetrahydroquinoline, piperidine and thiochroman derivatives in high yields with good to excellent diastereo- and enantioselectivities.