Comprehensive SummaryAxially chiral biaryls represent the most important class of atropisomers, and they widely exist in natural products and biologically active molecules. They also constitute a unique scaffold for chiral ligands and catalysts in organic synthesis. The development of synthetic methods to obtain such chiral compounds has received widespread attention, among which catalytically atroposelective ring‐opening of configurationally labile compounds represents one of the most attractive strategies. Various substrates with strained cyclic structures, such as the renowned Bringmann's lactones, can undergo asymmetric transformation into stable atropisomers. Known advancement primarily relies on metal catalyst combined with well‐designed chiral ligands, the approaches utilizing organocatalysis as a critical resolution strategy are notably scarce. In this study, we disclosed a N‐heterocyclic carbene (NHC)‐catalyzed asymmetric ring‐opening reaction of biaryl lactams via direct atroposelective nucleophilic activation. The optimized bulky carbene catalyst ensures that the reaction can proceed under mild conditions, affording the desired product with good to excellent yields and atroposelectivity.

中文翻译：

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卡宾催化联芳基内酰胺的不对称开环反应获得轴向手性联芳基化合物†

综合总结轴向手性联芳基是最重要的一类阻转异构体，广泛存在于天然产物和生物活性分子中。它们还构成了有机合成中手性配体和催化剂的独特支架。获得此类手性化合物的合成方法的发展受到了广泛的关注，其中构型不稳定化合物的催化逆向选择性开环是最有吸引力的策略之一。具有应变环状结构的各种底物，例如著名的布林曼内酯，可以不对称转化为稳定的阻转异构体。已知的进展主要依赖于金属催化剂与精心设计的手性配体相结合，利用有机催化作为关键拆分策略的方法非常稀缺。在这项研究中，我们披露了氮杂环卡宾（NHC）通过直接的阿托选择性亲核活化催化联芳内酰胺的不对称开环反应。优化的大体积卡宾催化剂确保反应可以在温和的条件下进行，以良好至优异的产率和对映选择性提供所需的产物。