Breaking symmetry to generate asymmetry, commonly termed desymmetrization, is a remarkably powerful strategy for building molecular complexity. During the past few years, we have developed a number of organocatalytic enantioselective desymmetrization reactions including formal C(sp2)‒H alkylation1 and de novo construction of (hetero)arenes.2 We subsequently applied these reactions to the enantioselective synthesis complex targets. Naturally occurring ladderane phospholipids represent such target, which provided us with the motivation to develop some of these enantioselective desymmetrization reactions. This talk will focus on the application of our desymmetrizing C(sp2)‒H alkylation reaction to [3]-ladderanol,3[5]-ladderanoic4 acid as well as their unnatural analogues in an effort to unravel their biosynthetic hypothesis. In addition, our recent work on the enantioselective synthesis of an unnatural benzoanalogue of [3]-ladderanol through the application of our newly developed alkoxy-directed dienamine catalysis5 will also be discussed.