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Abstract Diaryliodonium salts continue to emerge as versatile arylation reagents. This is especially true for unsymmetrical aryl(TMP)iodonium salts (TMP = 2,4,6-trimethoxyphenyl) because they undergo highly selective aryl transfer across diverse mechanistic settings. This account outlines our motivation for exploring the chemistry of aryl(TMP)iodonium salts and our efforts to develop streamlined synthetic methods to access them and the novel arylation reactions that use them. 

Arynes are versatile intermediates for organic synthesis and now they can be accessed from arenes in one or two-pot sequencesviaaryl thianthrenium (in situ) and aryl iodonium (isolated) intermediates, respectively. 

Arynes hold immense potential as reactive intermediates in organic synthesis as they engage in a diverse range of mechanistically distinct chemical reactions. However, the poor functional group compatibility of generating arynes or their precursors has stymied their widespread use. Here, we show that generating arynes by deprotonation of an arene and elimination of an “onium” leaving group is mild, efficient and broad in scope. This is achieved by using aryl(TMP)iodonium salts (TMP = 2,4,6-trimethoxyphenyl) as the aryne precursor and potassium phosphate as the base, and a range of arynophiles are compatible. Additionally, we have performed the first quantitative analysis of functional group compatibility for several methods to generate arynes, including the method developed here and the current state of the art. Finally, we show that a range of “sensitive” functional groups such as Lewis and Brønsted acids and electrophiles are compatible under our conditions. 

Arylboron compounds are widely available and synthetically useful reagents in which the boron group is typically substituted. Herein, we show that the boron group and orthohydrogen atom are substituted in a formal cycloaddition reaction. This transformation is enabled by a one-pot sequence involving diaryliodonium and aryne intermediates. The scope of arylboron reagents and arynophiles is demonstrated, and the method is applied to the formal synthesis of an investigational drug candidate.