Time-dependent Rh(iii)-catalyzed chemodivergent reactions of 2-pyridylthiophenes with nitroalkenes

Abstract

Switchable divergent reactions are highly valuable as they offer controllable access to distinct products from identical substrates, yet they remain challenging due to the difficulty of designing catalysts or conditions that reliably toggle between pathways with high selectivity. Herein, we describe a time-dependent Rh(III)-catalyzed chemodivergent transformation of 2-pyridylthiophenes with nitroalkenes, providing rapid and efficient access to C3-alkylated and C3-acylated 2-pyridylthiophenes in moderate to excellent yields. A notable highlight of this strategy is the unconventional utilization of nitroalkenes as indirect acylating agents to achieve the C3-acylation of 2-pyridylthiophenes. Late-stage diversification of the resulting products further underscores the versatility and synthetic utility of this strategy.