Stereoselective Gridization of Ladder‐Type Grids with Four Chiral Centers

Comprehensive Summary To address the stereoselective synthesis challenge in π‐stacked grids with four chiral centers, we utilized coplanar and highly rigid 11,12‐dihydroindeno[2,1‐ a ]fluorene‐11,12‐diol and 2,2'‐bithiophene as synthons, employing Friedel‐Crafts gridization (FCG). Leveraging the supramolecular interactions of S···S and π···π within the thiophene moiety, along with the steric effect of the 11,12‐dihydroindeno[2,1‐ a ]fluorene scaffold, we successfully achieved the exclusive generation of a single isomer of Ladder‐type π‐stacked grids (LGs‐IF) containing six theoretical isomers. By subsequently substituting 2,2'‐bithiophene with thiophene/bithiophene derivatives as synthons, we maintained an exceptionally high level of stereoselectivity. This study introduces a novel approach for the stereo‐controlled preparation of grids involving multi‐chiral centers.