Skeletal editing represents an attractive strategy for adding complexity to a given molecular scaffold in chemical synthesis. Isodesmic reactions provide a complementary skeletal editing approach for the redistribution of chemical bonds in chemical synthesis. However, catalytic enantioselective isodesmic reaction is extremely scarce and enantioselective isodesmic reaction to synthesize atropisomeric compounds is unknown. Herein, we report a facile method to synthesize axially chiral aminoaryl quinoxalines through Cu(I)‐catalyzed dearomatization and sequential chiral phosphoric acid (CPA) catalyzed enantioselective isodesmic C‐N bond formation and cleavage from indoles and 1,2‐diaminoarenes under mild reaction conditions. In this process, the five‐membered ring of the indole scaffold was broken and a novel quinoxaline skeleton was constructed. This method allows the practical and atom‐economical synthesis of valuable axially chiral aminoaryl quinoxalines in high yields (up to 95%) and generally excellent enantioselectivities (up to 99% ee). Notably, this novel type of quinoxaline atropisomers has promising applications in developing axially chiral ligand in asymmetric catalysis. This strategy represents the first example of CPA‐catalyzed enantioselective isodesmic reaction to form axially chiral compounds.

中文翻译：

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铜催化的对映选择性骨骼编辑，通过正式的氮插入吲哚中合成偏异构氨基芳基喹啉


骨骼编辑代表了一种有吸引力的策略，可以增加化学合成中给定分子支架的复杂性。同干反应为化学合成中化学键的重新分布提供了一种互补的骨架编辑方法。然而，催化对映选择性同梢反应极为稀少，合成萎缩异构化合物的对映选择性同晃反应尚不清楚。在此，我们报道了一种通过 Cu（I） 催化的脱芳烃化和连续手性磷酸 （CPA） 催化的对映选择性异碁替性 C-N 键形成和在温和反应条件下从吲哚和 1,2-二氨基芳烃裂解合成轴向手性氨基芳基喹啉的简单方法。在这个过程中，吲哚支架的五元环被打破，并构建了一种新的喹喔啉骨架。该方法允许以高产率（高达 95%）和通常优异的对映选择性（高达 99% ee）实用且原子经济地合成有价值的轴向手性氨基芳基喹啉。值得注意的是，这种新型的喹喔啉阿托异构体在不对称催化中开发轴向手性配体方面具有广阔的应用前景。该策略代表了 CPA 催化的对映选择性同氪反应形成轴向手性化合物的第一个例子。