The first systematic evaluation of the electrostatic potential energy maps of iodonium ylides was conducted. We determined that they possess two σ‐holes of differing electron deficiencies, with the more electropositive σ‐hole located opposite the dative I−C bond to the β‐dicarbonyl motif, and the lesser electropositive σ‐hole located opposite the iodoarene C−I bond. We also conducted the first systematic evaluation of carboxylic acids, phenols and thiophenols in the O/S‐alkylation reaction of iodonium ylides. While carboxylic acids and thiophenols were found to be generally viable, only phenols possessing electron‐withdrawing substituents were effective. This high‐yielding and highly chemoselective reaction is believed to involve halogen‐bond activation of heteroatoms, and nicely complements existing diazo‐based methods for alkylation of acidic functional groups.
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