Deprotonation of arenes with weak base: assessing and expanding the functional group compatibility of aryne chemistry

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 aryne precursors has stymied their widespread use. Here, we show that generating arynes can be both efficient and mild by deprotonating aryl(TMP)iodonium salts with potassium phosphate (TMP = 2,4,6-trimethoxyphenyl) and these conditions are uniquely compatible with acyclic diaryliodonium salts. We have also performed the first comparison of functional group compatibility by the method of additives across a range of reaction conditions, including the current state-of-the-art, to generate arynes. The scope of the reaction conditions includes sensitive functional groups such as benzylic halides, ketones, alcohols, and boronate esters that are not compatible with prior methods and charts a new course forward for aryne chemistry.