Auto-Sustainable Enantioselective Heck-Matsuda Reaction: Application to the One-pot Desymmetrization of Cyclopentenol

One-pot reactions are an efficient approach in organic synthesis,this allows the construction of new molecules by reducing the numbers of steps and waste formation. In this work, we present the first example of an enantioselective version of the Heck-Matsuda reaction in one-pot procedure without the use of external addition of acid for the diazotization reaction as well as base for the arylation step. By the use of a PyOx-Pd complex for the desymmetrization of cyclopentenol, under the optimized conditions the arylated Heck-Matsuda adduct was obtained in high yield (up to 74% for two steps) and excellent enantiomeric excess (up to 99% ee). Our approach highlights the development of the Heck reaction in a sustainable way considering that there is no need of acidic and basic conditions or the previous preparation of diazonium salts. The evaluation of the reactional scope by changing the substitution pattern of the aryl fragment is underway.