Regio‐ and Stereo‐Selective CH Linear Dienylation of Diverse Arenes and Heteroarenes

Herein, we report two distinct Rh(III)‐catalyzed CH activation strategies for the stereoselective synthesis of linear 1,3‐dienes employing allenyl carbinol acetates or 1,3‐dienes as [4C]‐dienylating agents. Both protocols accommodate a broad range of aryl and heteroaryl substrates, including indole, indoline, thiophene, pyrrole, benzothiophene, and dibenzofuran. The versatility and robustness of these protocols are further demonstrated through gram‐scale synthesis and postsynthetic functionalizations of the resulting dienes, underscoring their synthetic utility. Moreover, photophysical studies of the products indicate their potential applicability for optoelectronic applications. Rh(III)‐catalyzed C‐H dienylation of a diverse array of arenes and heteroarenes has been demonstrated with linear selectivity engaging allenyl carbinol acetates or 1,3‐dienes as dienylating agents.