LDA-mediated ortholithiation and subsequent anionic Fries rearrangement of N,N-dialkyl-O-phenyl carbamates in mono- and bis-chelating solvents were investigated. Variable temperature ⁶Li, ¹³C, and ¹⁵N NMR spectroscopies and DFT computations were used to characterize monosolvated mixed dimers (1) in solution. Rate studies reveal multiple pathways for the lithiation and rearrangement.