Higher-order cycloadditions are a powerful strategy for the construction of polycycles in one step. However, an efficient and concise version for the induction of asymmetry is lacking. N-heterocyclic carbenes are widely used organocatalysts for asymmetric synthesis and could be an ideal choice for enantioselective higher-order cycloadditions. Here, we report an enantioselective [10 + 2] annulation between catalytically formed aza-benzofulvene intermediates and trifluoromethyl ketone derivatives. This protocol exhibits a wide scope, high yields, and good ee values, reflecting a robust and efficient higher-order cycloaddition. Density functional theory calculations provide an accurate prediction of the reaction enantioselectivity, and in-depth insight to the origins of stereocontrol.

高阶环加成是一种一步构建多环的强大策略。然而，缺乏用于诱导不对称性的高效简洁版本。N-杂环卡宾是广泛用于不对称合成的有机催化剂，可能是对映选择性高阶环加成的理想选择。在这里，我们报告了催化形成的氮杂-苯并富烯中间体和三氟甲基酮衍生物之间的对映选择性 [10 + 2] 环化。该协议具有广泛的范围、高产率和良好的 ee 值，反映了稳健且高效的高阶环加成。密度泛函理论计算提供了反应对映选择性的准确预测，并深入洞察了立体控制的起源。