Enantioselective Total Synthesis of [3]‐Ladderanol through Late‐Stage Organocatalytic Desymmetrization**
Sayan Ray, Subhajit Mondal, Santanu Mukherjee
Abstract
Abstract Ladderane phospholipids, with their unusual ladder‐like arrangement of concatenated cyclobutane rings, represent an architecturally unique class of natural products. However, despite their fascinating structure and other necessary impetus, only a few synthetic studies of these molecules have been reported so far. We have now devised a concise total synthesis of [3]‐ladderanol, a component of natural ladderane phospholipids, using an organocatalytic enantioselective desymmetrizing formal C(sp 2 )−H alkylation. Our synthetic strategy rests on the late‐stage introduction of chirality, thus allowing facile access to both enantiomers of [3]‐ladderanol as well as an analogue. This is the first time a desymmetrization strategy is applied to the synthesis of [3]‐ladderanol. The scope of this desymmetrizing C(sp 2 )−H alkylation of meso ‐cyclobutane‐fused cyclohexenediones is also presented.