The direct oxidative cross-coupling of phenols is a very challenging transformation, as homo-coupling is usually very much preferred. Electrochemical methods circumvent the use of oxidizers or metal catalysts and are therefore highly attractive. Application of electrolytes with a high capacity for hydrogen bonding, such as methanol with formic acid or 1,1,1,3,3,3-hexafluoroisopropanol, allows a direct electrolysis in an undivided cell providing mixed 2,2’-biphenols with high selectivity. This mild method tolerates a variety of moieties, for example, tert-butyl groups, which are not compatible with other strong electrophilic media but vital for later catalytic applications of the formed products. The presentation will present the mechanistic details. These findings give rise to much broader scope in anodic cross-coupling reaction. Since no leaving functionalities are required this methodology not only shortcuts the synthesis but is rather very sustainable. References (a) Elsler, B.; Schollmeyer, D.; Dyballa, K. M.; Franke, R.; Waldvogel, S. R. Angew. Chem. Int. Ed. 2014, 53, 5210. (b) Kirste, A.; Schnakenburg, G.; Waldvogel, S. R. Org. Lett. 2011, 13, 3126. (c) Kirste, A.; Schnakenburg, G.; Stecker, F.; Fischer, A.; Waldvogel, S. R. Angew. Chem. Int. Ed. 2010, 49, 971. (d) Kirste, A.; Elsler, B.; Schnakenburg, G.; Waldvogel, S. R. J. Am. Chem. Soc. 2012, 134, 3571.

Metal- and reagent-free highly selective anodic cross-coupling reaction

249th National Meeting (2015)

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