Jian Song, Xuening Li, Daquan Yu, Song‐Zhou Cai, Ting Wang, Xianjie Fang
Ketenes represent an important class of reactive intermediates that serve as key precursors in pharmaceutical and organic synthesis, enabling access to a diverse array of multifunctional and valuable compounds. Herein, we report a novel strategy for cobalt-catalyzed double carbonylation of cyclopropenes with carbon monoxide that proceeds via in situ-generated E - and Z -configured ketenes species, whose complementary roles are essential for the reaction’s success. This transformation exhibits a broad substrate scope and delivers a series of naphthyl allylates with high E -selectivity. Furthermore, a detailed and coherent catalytic mechanism is proposed based on systematic experimental studies and DFT calculations. This work offers a new perspective for the advancement of ketene chemistry.