Tandem Hydroxybenzothiophene Synthesis Mediated by LiN(SiMe ₃ ) ₂

Benzothiophenes are pivotal heterocycles in pharmaceuticals due to their broad biological activities. Existing methods often require harsh conditions, toxic reagents, or expensive transition metals. Herein, we report a one-pot transition-metal-free synthesis of benzothiophenes using readily available methyl 2-fluorobenzoate, benzyl mercaptans, and LiN(SiMe₃)₂ under mild conditions. This protocol enables efficient access to a diverse array of 2-aryl-3-hydroxybenzothiophenes with excellent functional group tolerance. Furthermore, this approach enhances sustainability and simplifies synthetic workflows, offering a practical complement to existing benzothiophene synthesis.