The reductive coupling of aldehydes and alkenes is an emerging technology that holds the potential to reinvent carbonyl addition chemistry. However, existing enantioselective methods are limited to form “branched” products. Herein, we present a directed enantio- and diastereoselective alkylation of aldehydes with simple olefins to selectively yield linear coupling products. This is achieved by redox-neutral remote functionalization, whereby a tethering “catch–release” strategy decisively solves the key problems of reactivity and selectivity.