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Understanding the Regiodivergence between Hydroarylation and Trifluoromethylarylation of 1,3-Dienes Using Anilines in
Carlos Corral Suarez1, Israel Fernández2, Ignacio Colomer1
1Instituto de Química Orgánica General (IQOG-CSIC), Juan de la Cierva 3, 28006 Madrid, Spain.
Abstract:
Conjugated dienes (1,3-dienes) are versatile and valuable chemical feedstocks that can be used as two-carbon or four-carbon synthons with vast applications across the chemical industry. However, the main challenge for their productive incorporation in synthetic routes is their chemo-, regio-, and stereoselective functionalization. Herein, we introduce a unified strategy for the 1,2-hydroarylation and 1,4-trifluoromethylarylation of 1,3-dienes using anilines in hexafluoroisopropanol. DFT calculations point toward a kinetically controlled process in both transformations, particularly in the trifluoromethylarylation, to explain the regiodivergent outcome. In addition, we perform an extensive program of functionalization and diversification of the products obtained, including hydrogenation, oxidation, cyclizations, or cross-coupling reactions, that allows access to a library of high-value species in a straightforward manner.
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