Transition metal-catalyzed C–C bond functionalization has recently been identified as an increasingly versatile tool for organic syntheses, as otherwise unreactive functionalities can be used as efficient handles for synthetic manipulations. This work describes site-selective manganese(I)-catalyzed C–C hydroarylations of heteroarenes with substituted allenes. The C–C activations are efficiently catalyzed by MnBn(CO)₅ and afford 1,2,3-tri-substituted arenes with notable diastereoselectivity. Moreover, the ring-expansion reaction proceeds via a C–C allylation/Michael addition cascade, providing challenging 8-membered carbocycles, thus highlighting the unique characteristics of the MnBn(CO)₅ complex. Mechanistic studies reveal that the organometallic C–C activation occurs faster than typical C–H activations, thus providing a complementary approach to well-established methodologies for late-stage diversification.

过渡金属催化的C–C键功能化最近已被确定为有机合成的一种越来越多的工具，因为否则未反应的功能可以用作合成操作的有效方法。这项工作描述了现场芳构锰（I）催化的杂芳烃的CC加氢芳基化与取代的烯基。MnBn（CO）₅可有效催化C-C活化，并提供具有非对映选择性的1,2,3-三取代芳烃。此外，扩环反应通过CC烯丙基化/迈克尔加成级联反应进行，提供了具有挑战性的8元碳环，从而突出了MnBn（CO）₅的独特特征。复杂。机理研究表明，有机金属的C–C活化要比典型的C–H活化快，因此为成熟的后期多样化方法提供了一种补充方法。