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 )À 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 )À H alkylation of meso-cyclobutane-fused cyclohexenediones is also presented.

The first atroposelective desymmetrization of prochiral N-aryl maleimides through its conversion to axially chiral phthalimides is developed by applying a de novo arene construction strategy. Catalyzed by bis(3,5-dimethylphenyl)prolinol TMSether, this reaction proceeds through oxidative [4 + 2]-cycloaddition with α,β-unsaturated aldehydes to generate only a chiral C−N axis remote from the reaction sites with excellent enantioselectivity (up to 97.5:2.5 er).

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(sp2)−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(sp2)−H alkylation of meso‐cyclobutane‐fused cyclohexenediones is also presented.

Ladderane phospholipids, with their unusual ladder-like arrangement of fused 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 synthesis of [3]-ladderanol, a component of ladderane phospholipids, using an organocatalytic enantioselective desymmetrizing formal C(sp2)‒H alkylation. Our synthetic strategy rests on a late-stage introduction of chirality, thus allowing facile access to both the enantiomers of [3] ladderanol as well as its analog. This is the first time a desymmetrization strategy is applied to the synthesis of [3]-ladderanol. The scope of this desymmetrizing C(sp2)‒H alkylation of meso cyclobutane fused cyclohexenediones is also presented.