Cross-Electrophile Coupling of Alcohols with Aryl and Vinyl Halides

Although alcohols represent one of the largest pools of commercially available alkyl substrates, approaches to di-rectly utilize them in cross-coupling and cross-electrophile coupling are limited. We report the use of alcohols in cross-electrophile coupling with aryl and vinyl halides to form C(sp3)–C(sp2) bonds in a one-pot strategy. This strategy allows the use of primary and secondary alcohols through their very fast (<1 min) in situ conversion to the corre-sponding alkyl bromides with compatible phosphonium activating reagents. The utility of the reaction is exempli-fied by its simple reaction setup, scalability, and broad scope (41 examples, 57% ± 15% ave yield). The reaction can be performed on the benchtop without the need for electro-chemical or photochemical equipment. Finally, translation to standard parallel synthesis techniques is demonstrated by successfully coupling all combinations of 8 alcohols with 12 aryl cores in a 96-well plate using only one (99% cover-age) or two (100% coverage) sets of conditions.