A hitherto unknown class of C4‐symmetric Caryl−Cβ (C3, C8, C13, C18) axially chiral porphyrins has been synthesized and the application of their iridium (Ir) complexes in catalytic asymmetric C(sp3)−H functionalization is documented. Cyclotetramerization of enantioenriched axially chiral 2‐hydroxymethyl‐3‐naphthyl pyrroles under mild acidic conditions affords, after oxidation with 2,3‐dichloro‐5,6‐dicyano‐1,4‐benzoquinone (DDQ), the C4‐symmetric α,α,α,α‐atropenantiomer as an only isolable diastereomer. Both regioisomeric Ir(Por*)(CO)(Cl) complexes catalyze the carbene C−H insertion reaction affording the same enantiomer, albeit with slight difference in enantioselectivity. With the optimum Ir‐complex 3e, the 2‐substituted arylacetic acid derivatives were generated from diazo compounds and cyclohexadiene in excellent yields and enantioselectivities.

中文翻译：

---

C₄对称轴手性β-芳基卟啉的设计与合成及其在Ir(III)催化对映选择性CH烷基化中的应用

迄今为止未知的一类 C4 对称 Caryl−Cβ (C3, C8, C13, C18) 轴向手性卟啉已被合成，并且其铱 (Ir) 配合物在催化不对称 C(sp3)−H 功能化中的应用已被记录。对映体富集的轴向手性 2-羟甲基-3-萘基吡咯在温和酸性条件下进行环四聚，用 2,3-二氯-5,6-二氰基-1,4-苯醌 (DDQ) 氧化后，得到 C4 对称的 α,α ,α,α-atropopenantiomer 作为唯一可分离的非对映异构体。两种区域异构 Ir(Por*)(CO)(Cl) 配合物都催化卡宾 CH 插入反应，提供相同的对映体，尽管对映选择性略有不同。利用最佳的Ir配合物3e，由重氮化合物和环己二烯生成2-取代的芳基乙酸衍生物，具有优异的产率和对映选择性。