Flexible Total Synthesis of 11‐Deoxylandomycins and Their Non‐Natural Analogues by Way of Asymmetric Metal Catalysis

A de novo first collective total synthesis of 11‐deoxylandomycins is reported. A signature step is featured by the Pd‐catalyzed asymmetric addition of alcohol to ene‐alkoxyallenes that assembles oligomeric 2,3,6‐trideoxyoligosaccharides. The unique feature of the protocol is illustrated by a flexible access to various natural 11‐deoxylandomycins as well as non‐natural analogues.