Synlett, Table of Contents Synlett 2024; 35(12): 1338-1344DOI: 10.1055/a-2184-6373 synpacts Pd-catalyzed Stereodivergent [4+2] Annulation to Access [6.7]-Fused N-Heterocycles Zhan-Cai Ma , Yuan Huang ∗ Recommend Article Abstract Buy Article All articles of this category Abstract Stereodivergent synthesis of N-heterocycle frameworks bearing 1,3-nonadjacent stereogenic centers through a single transformation remains a high-priority challenge in organic synthesis. Herein, we highlight our recent discovery of stereodivergent access to such useful structural motifs using Pd-catalyzed [4+2] annulation reactions of vinyl benzoxazinaones and seven-membered cyclic N-sulfonyl aldimines. A wide range of N-heterocycles with 1,3-nonadjacent stereogenic centers were obtained in high efficiency and stereodivergency. Importantly, the polarity of solvents was found to play a key role in switching the diastereoselectivity. 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