Air‐Stable Pd(I) Dimer Enabled Remote Functionalization: Access to Fluorinated 1,1‐Diaryl Alkanes with Unprecedented Speed

While remote functionalization via chain walking has the potential to enable access to molecules via novel disconnections, such processes require relatively long reaction times and can be in need of elevated temperatures. This work features a remote arylation in less than 10 min reaction time at room temperature over a distance of up to 11 carbons. The unprecedented speed is enabled by the air‐stable Pd(I) dimer [Pd(μ‐I)(PCy(2) (t)Bu)](2), which in contrast to its P(t)Bu(3) counterpart does not trigger direct coupling at the initiation site, but regioconvergent and chemoselective remote functionalization to yield valuable fluorinated 1,1‐diaryl alkanes. Our combined experimental and computational studies rationalize the origins of switchability, which are primarily due to differences in dispersion interactions.