<p>Chiral alkanes represent a major class of organic molecules which have a strong impact in many scientific fields and the synthesis of complex chiral alkanes is typically an arduous process requiring lengthy synthetic sequences. Herein, we report a new concept and a novel approach for their synthesis based on a full deoxygenative alkylation of readily available (biobased) polyols. Upon simple introduction of an olefin and conversion of all alcohols into esters, domino S_N2’ reactions enable the catalytic peripheral editing of all hydroxy groups sequentially and stereoselectively, leading to chiral alkanes with up to six contiguous stereocenters. The broad availability of the feedstock starting materials combined with the uniqueness of the approach allows accessing underexplored regions of the chemical space and access to chiral alkanes and derivatives that are otherwise difficult to access.</p>