Intermolecular pnictogen bonding (PnB) catalysis has received increased interest in non‐covalent organocatalysis. It has been demonstrated that organic electron‐deficient pnictogen atoms can act as prospective Lewis acids. Here, we present a catalytic approach for the asymmetric synthesis of chiral PIII compounds by combining intramolecular PnB interactions and carbene catalysis. Our design features a pre‐chiral phosphorus molecules bearing two electron‐withdrawing benzoyl groups, resulting in the formation of a σ‐hole at the P atom. X‐ray and non‐covalent interaction (NCI) analysis indicate that these phosphorus substrates exhibit intrinsic PnB interactions between the oxygen atom of the formyl group and the phosphorus atom. This induces a conformational locking effect, leading to the crystallization of the phosphorus substrates in a preferred conformation (P212121 chiral group). Under the catalysis of N–heterocyclic carbene, the aldehyde moiety activated by the pnictogen bond selectively reacts with an alcohol to yield the corresponding chiral monoester/phosphorus products with excellent enantioselectivity. This Lewis acidic phosphorus center, aroused by the non‐polarized intramolecular pnictogen bond interaction, assists in conformational and selective regulations, providing unique opportunities for catalysis and beyond.

中文翻译：

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卡宾催化和磷键辅助合成 PIII 立体化合物

分子间磷元素键合（PnB）催化在非共价有机催化中受到越来越多的关注。已经证明，有机缺电子磷元素原子可以充当潜在的路易斯酸。在这里，我们提出了一种结合分子内 PnB 相互作用和卡宾催化来不对称合成手性 PIII 化合物的催化方法。我们的设计特点是预手性磷分子带有两个吸电子苯甲酰基，导致在 P 原子上形成 σ 空穴。 X射线和非共价相互作用（NCI）分析表明这些磷底物在甲酰基的氧原子和磷原子之间表现出固有的PnB相互作用。这会引起构象锁定效应，导致磷底物以优选构象（P212121 手性基团）结晶。在N-杂环卡宾的催化下，被磷元素键激活的醛部分选择性地与醇反应生成相应的具有优异对映选择性的手性单酯/磷产物。这种路易斯酸性磷中心由非极化分子内磷原键相互作用引起，有助于构象和选择性调节，为催化及其他方面提供了独特的机会。