A dearomatization-dislocation-coupling cascade rapidly transforms aromatic isocyanides into highly functionalized cyclohexadienes. The facile cascade installs an exceptional degree of molecular complexity: three carbon-carbon bonds, two quaternary stereocenters, and three orthogonal functionalities, a cyclohexadiene, a nitrile, and an isocyanide. The tolerance of arylisocyanides makes the method among the mildest dearomatizations ever reported, typically occurring within minutes at −78 °C. Experimental and computational analyses implicate an electron transfer-initiated mechanism involving an unprecedented isocyanide rearrangement followed by radical-radical anion coupling. The dearomatization is fast, proceeds via a complex cascade mechanism supported by experimental and computational insight, and provides complex, synthetically valuable cyclohexadienes.

脱芳构化-位错偶联级联将芳香族异氰化物快速转化为高度官能化的环己二烯。简单的级联安装了异常程度的分子复杂性：三个碳碳键、两个季立构中心和三个正交官能团、环己二烯、腈和异氰化物。芳基异氰化物的耐受性使该方法成为有史以来最温和的脱芳构化方法之一，通常在 -78 °C 下几分钟内发生。实验和计算分析表明电子转移引发的机制涉及前所未有的异氰化物重排，然后是自由基-自由基阴离子偶联。脱芳构化速度很快，通过实验和计算洞察力支持的复杂级联机制进行，并提供复杂的、