Acyclic Stereocontrol in the Ireland–Claisen Rearrangement of α‐Branched Esters

To overcome the limitation of the poor diastereoselectivity of the title reaction with α-branched esters, chiral amides were used to generate the enolate intermediates diastereoselectively. The desired rearrangement then took place with efficient transfer of chirality to give densely functionalized products with at least one quaternary stereocenter (see scheme; PMB, TBS, and TBDPS are protecting groups).