Stable BF ₂ Boracycles as Versatile Reagents for Selective Ortho C–H Functionalization

The development of new boron reagents continues to play a crucial role in advancing modern organic synthesis, particularly in C–H functionalization and cross‐coupling reactions. Herein, we report a metal‐free, robust, and scalable multigram protocol for the synthesis of stable BF 2 boracycles that require no column chromatography, providing a practical and efficient route to access this valuable boron species. The BF 2 boracycles exhibit enhanced stability and reactivity, making them highly versatile intermediates for late‐stage diversification. They undergo ipso ‐substitution to afford a wide array of derivatives, including halogenated (e.g., radioiodinated), hydroxylated, and azidated products. Furthermore, they display excellent reactivity in Suzuki–Miyaura cross‐coupling reactions, enabling both C(sp 2 )─C(sp 2 ) and C(sp 2 )─C(sp 3 ) bond formation. These results underscore the utility of BF 2 boracycles as powerful tools for selective functionalization in pharmaceutical synthesis and beyond. Our work represents a significant advancement in organoboron chemistry, offering both a streamlined synthetic approach and broad applicability for complex molecule construction.